CN116410510A - Method for modifying surface of material and surface modified material obtained based on method - Google Patents

Method for modifying surface of material and surface modified material obtained based on method Download PDF

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CN116410510A
CN116410510A CN202111668658.6A CN202111668658A CN116410510A CN 116410510 A CN116410510 A CN 116410510A CN 202111668658 A CN202111668658 A CN 202111668658A CN 116410510 A CN116410510 A CN 116410510A
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substrate
coupling agent
mmol
solution
initiator
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唐增超
雷杰华
黄佳磊
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Jiangsu Biosurf Biotech Co Ltd
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Jiangsu Biosurf Biotech Co Ltd
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Priority to CN202111668658.6A priority Critical patent/CN116410510A/en
Priority to PCT/CN2022/139960 priority patent/WO2023125100A1/en
Publication of CN116410510A publication Critical patent/CN116410510A/en
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

Abstract

The invention relates to a method for modifying the surface of a material and a surface modified material obtained by the method. The method of the invention comprises the following steps: (1) Dissolving, suspending or dispersing a polymerization monomer, a coupling agent and an initiator in a solvent to prepare a reaction solution; (2) contacting a substrate with the reaction solution; (3) Polymerizing the reaction liquid on the surface of the substrate by microwave radiation to obtain the surface modified substrate. By the method, the polymerized monomer can successfully modify the surface of the material, thereby changing the hydrophilicity/hydrophobicity and lubricity of the surface of the material, and increasing the biological functionality, protein adsorption resistance, antibacterial property, anticoagulation property and the like.

Description

Method for modifying surface of material and surface modified material obtained based on method
Technical Field
The invention relates to a material surface modification method and a surface modified material obtained based on the method, belonging to the field of material surface modification or modification.
Background
Modification (modification) of the surface of a material can generally bring about the introduction or promotion of different functions for the material, such as promotion of hydrophilic function, lubricating function, antibacterial function, antifouling function, anticoagulant function, protein adsorption function, etc. The functionalization of material surfaces has been done by various methods, mainly by surface grafting polymers or by applying functional coatings.
The traditional modification mode of the material surface grafted polymer generally needs to modify an initiator on the material surface firstly, then initiates polymerization in a solution, and the process at least needs several hours or even tens of hours, so that the disadvantages of multiple steps, complex process, high risk, low productivity and the like are involved in the actual process production; in addition, it is not universal for some substrates that are difficult to modify and have complex shapes. Another way of modifying the surface graft polymer requires the introduction of reactive groups, such as polyphenols or PU based primer layers, by primer modification, which also involves some of the problems described above. Another method of directly applying a coating generally has the problems of weak coating and easy falling off due to lack of binding force with the surface.
Microwave polymerization is a new polymerization mode, and has the advantages of fast heating rate, fast reaction rate, high monomer conversion rate and the like, and can complete the polymerization within a few minutes, while the traditional solution polymerization can take a few hours or even tens of hours. The microwave polymerization method generates heat through the self-movement of monomer molecules, and the polymerization reaction is more uniformly and efficiently completed without the need of reaction at high temperature.
At present, microwave is mainly utilized by microwave polymerization in solution, and is intensively applied to the field of chemical synthesis, but is less applied to the field of material surface modification. In the aspect of small amount of material surface modification, the prior art is based on the mode of firstly modifying an initiator on the material surface and then utilizing microwave radiation to carry out subsequent polymerization.
CA2252877A1 discloses a graft polymerization process for modifying the surface of an object, wherein the object is coated with an initiator and at least one compound selected from hydrophilic polymers, hydrophobic polymers, biofunctional compounds or combinations thereof, and the surface of the material is modified with infrared radiation, microwave radiation or high pressure polymerization to impart desired properties thereto. However, this method requires the use of special microwave grafting initiators, is complicated in steps and requires the use of special radiation facilities and expensive gamma ray sources. Meanwhile, the grafting of the initiator is also limited by different substrate surfaces, so that the initiator has no universality in industrial production.
In document 1, schubert et al successfully coupled low molar mass molecules (propargyl alcohol) and high molar mass molecules (poly (2-ethyl-2-oxazoline)) having acetylene functional groups to the surface of silicon azide substrates using CuAAC under microwave irradiation. (reaction conditions: 50w,75-120 ℃ C., 5-45 min)
In document 2, cai et al first photo-graft an alkynyl chain protected by a Trimethylgermanium (TMG) group onto the surface of an activated silicon substrate to form a "clickable" monolayer. The coupling of the azido oligomeric ethylene Oxide (OEG) to the silicon substrate surface is based on copper-catalyzed "click" chemistry under microwave irradiation. The principle is also that an initiator is grafted first and then microwave irradiation polymerization is carried out.
In document 3, lee et al propose a Microwave assisted coating process (Microwave-Assisted Coating process, MAC), demonstrating that Microwave radiation can significantly accelerate the coating speed of dopamine (PDA), and propose a mechanism: microwaves generate free radicals and the free radicals participate in the synergistic effect of oxidation. However, this document does not relate to polymerization.
In summary, there is no related art in the prior art that applies a microwave polymerization one-step process to the surface modification of materials.
Document 1: haensch, c.; erdmenger, t.; fijten, m.w.; hoeppen, s.; schubert, U.S. Fast surface modification by microwave assisted click reactions on silicon substrates, langmuir 2009,25 (14), 8019-24.
Document 2: li, Y; wang, j.; cai, C., rapid grafting of azido-labeled oligo (ethylene glycol) s onto an alkynyl-terminated monolayer on nonoxidized silicon via microwave-accepted "click" reaction, langmuir 2011,27 (6), 2437-45.
Document 3: lee, m.; lee, s.h.; oh, I.K.; lee, H., microwave-Accelerated Rapid, chemical oxidation-Free, material-Independent Surface Chemistry of Poly (dopamine), small 2017,13 (4).
Disclosure of Invention
Problems to be solved by the invention
Thus, what is more needed is a more convenient method of grafting a material onto the surface of an object that does not require complex pretreatment of the material and that can be modified functionally using only one step. There is also a need for a method that is fast and allows coating objects that cannot be coated with conventional methods.
Solution for solving the problem
Based on the above, the present invention relates to the following technical solutions.
[1] A method of modifying a surface of a material, comprising the steps of:
(1) Dissolving, suspending or dispersing a polymerization monomer, a coupling agent and an initiator in a solvent to prepare a reaction solution;
(2) Contacting a substrate with the reaction solution;
(3) Polymerizing the reaction liquid on the surface of the substrate by microwave radiation to obtain the surface modified substrate.
[2] The method according to [1], wherein the polymerization monomer in the step (1) is one or more selected from the group consisting of (meth) acrylamide-based monomers, cationic-based monomers, heparin-based monomers, heparinoids-based monomers, sodium styrenesulfonate, N-vinylpyrrolidone, (meth) acrylic acid-based monomers, (meth) acrylic acid ester-based monomers, fibrinolytic-based monomers, and zwitterionic-based monomers.
[3] The method according to [1] or [2], wherein the coupling agent in step (1) is selected from one or more of a silane coupling agent and a titanate coupling agent.
[4] The method according to [1] or [2], wherein the initiator in the step (1) is selected from one or more of azo-type initiators, peroxide-type initiators.
[5] The method according to [4], wherein the initiator is selected from one or more of azodicarbonyl valeric acid, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, ammonium persulfate, azobisisobutyronitrile hydrochloride.
[6] The method according to [1] or [2], wherein the amounts of the polymerized monomer, the coupling agent and the initiator in step (1) are respectively: the molar ratio of the polymerized monomer to the coupling agent is (1-100): 1, the molar ratio of the polymerized monomer to the initiator is (10-1000): 1.
[7] the method according to [1] or [2], wherein the concentration of the polymerized monomer in the reaction liquid in the step (1) is 0.001 to 10g/ml.
[8] The method according to [1] or [2], wherein the substrate in step (2) is subjected to one or more of plasma treatment, corona treatment, radiation treatment, ozone treatment, and chemical agent treatment in advance.
[9] The method according to [1] or [2], wherein the microwave irradiation is performed for 0.5 to 30 minutes in the step (3), the polymerization temperature of the microwave irradiation is 50 to 200 ℃, and the power of the microwave irradiation is 50 to 2500w.
[10] A surface modified material prepared by the method of any one of the preceding claims.
ADVANTAGEOUS EFFECTS OF INVENTION
Unlike the complex technological process of grafting initiator onto the surface of material and subsequent polymerization, the present invention utilizes microwave polymerization process and one-step process to modify the surface of material.
The polymerization reaction is rapid (the polymerization reaction can be finished within 5 min), and the method is different from the traditional coating method, so that the yield and the yield can be greatly increased, and the effect of modifying the surface of the material can be realized by well grafting the polymerization monomer on the surface of the material; the solvent used is nontoxic and harmless; the types of available base materials are wide, and the processing and forming of the finally obtained material are not limited; the invention has the advantages of easy operation, simple preparation method and equipment, low production cost and easy industrialization; the method of the invention can be widely used in various fields, and is particularly suitable for modifying the surfaces of medical instruments (such as tubes, guide wires and the like), high polymer materials, metal base materials, inorganic materials and the like, thereby changing the hydrophilicity/hydrophobicity and lubricity of the surfaces of the materials, and increasing the biological functionality, protein adsorption resistance, antibacterial property, anticoagulation property and the like.
Drawings
FIG. 1 is an infrared plot of a substrate obtained by microwave polymerization on a silicone rubber (polydimethylsiloxane, PDMS) substrate at different polymerization times.
Fig. 2 is an infrared image of a substrate obtained by microwave polymerization on a silicone rubber (polydimethylsiloxane, PDMS) substrate and a comparative PDMS substrate (comparative example 3) without microwave polymerization, as a control, in example two, example six, example ten, example fourteen, example eighteen, and example twenty two.
Fig. 3 is an infrared plot of a substrate obtained by microwave polymerization on a nylon elastomer (Pebax) substrate, and a control Pebax substrate without microwave polymerization (comparative example 4), for example three, example seven, example eleven, example fifteen, example nineteen, and example twenty-three.
Fig. 4 is an infrared plot of a substrate obtained by microwave polymerization on a Thermoplastic Polyurethane (TPU) substrate and a comparative TPU substrate without microwave polymerization (comparative example 5) for example four, example eight, example twelve, example sixteen, example twenty-four.
Fig. 5 is an infrared image of a substrate obtained by microwave polymerization on a polyvinyl chloride (PVC) substrate in example five, example nine, example thirteen, example seventeen, example twenty-one, and a PVC substrate (comparative example 6) without microwave polymerization as a control.
FIG. 6 is a graph showing the bactericidal effect of microcatheter surface coating measured using a flat plate coating method for example twenty-six and unmodified stainless steel materials (comparative example 7).
Fig. 7 is a graph showing the thrombolytic capacity of the surfaces of the twenty-two to twenty-five and unmodified TPU substrates (comparative example 5) of examples.
Detailed Description
Numerous specific details are set forth in the following description in order to provide a better understanding of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
The various reaction materials used in the process of the present invention are commercially available, unless otherwise specified.
The invention relates to a method for modifying the surface of a material, which comprises the following steps:
(1) Dissolving, suspending or dispersing a polymerization monomer, a coupling agent and an initiator in a solvent to prepare a reaction solution;
(2) Contacting a substrate with the reaction solution;
(3) Polymerizing the reaction liquid on the surface of the substrate by microwave radiation to obtain the surface modified substrate.
The invention is illustrated in the following substeps.
Step (1)
The polymerization monomer participating in the microwave polymerization method of the present invention is not particularly limited as long as it has a double bond that can undergo polymerization reaction.
The polymeric monomer in step (1) may be selected from, for example, one or more of (meth) acrylamide-based monomers, cationic-based monomers, heparin-based monomers, heparinoids-based monomers, sodium styrenesulfonate, N-vinylpyrrolidone, (meth) acrylic acid-based monomers, (meth) acrylic acid ester-based monomers, fibrinolytic-based monomers, zwitterionic-based monomers.
Examples of the (meth) acrylamide monomer include methacrylamide, acrylamide, methoxymethyl methacrylamide, methoxymethyl acrylamide, n-butoxymethyl methacrylamide, n-butoxymethyl acrylamide, isobutoxymethyl methacrylamide, isobutoxymethyl acrylamide, t-butylaminopropyl methacrylamide, t-butylaminopropyl acrylamide, dimethylaminopropyl methacrylamide and dimethylaminopropyl acrylamide.
Examples of the cationic monomer include quaternary ammonium salt monomers such as diallylamine, dimethyldiallylammonium chloride, diethyldiallylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylbenzyl ammonium chloride, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propane-1-sulfonate, and the like; guanidine monomers such as guanidine, metformin, diphenylguanidine, tetramethylguanidine, etc.; quaternary phosphonium salt monomers such as triphenylphosphine, tetraphenylphosphine bromide, methyltriphenylphosphine bromide, ethyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, etc.; chitosan, and the like.
Examples of the heparin-like monomer and the heparinoid monomer include general heparin (for example, mucopolysaccharide sulfate composed of D-glucosamine, L-iduronic acid, and D-glucuronic acid alternately), low molecular heparin (for example, enoxaparin, dalteparin, nadroparin, and the like), heparin derivatives (for example, fondaparinux sodium), and heparin analogues (for example, danapaparin sodium), and the like.
Examples of the (meth) acrylic monomer and the (meth) acrylic monomer include (meth) acrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, and n-butyl acrylate.
As the fibrinolytic monomer, vinyl lysine monomer and the like can be exemplified.
Examples of the zwitterionic monomer include phosphorylcholine, carboxybetaine, and sulfobetaine.
The coupling agent in step (1) is not particularly limited and may be selected from one or more of a silane coupling agent and a titanate coupling agent.
Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, anilinomethyl triethoxysilane, anilinomethyl trimethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-isocyanatotrimethoxysilane, 3-isocyanatotriethoxysilane, epoxytrimethoxysilane, epoxytriethoxysilane, and the like.
As the titanate coupling agent, for example, isopropyl tris (dioctyl pyrophosphoyloxy) titanate, monoalkoxy unsaturated fatty acid titanate, isopropyl dioleate acyloxy (dioctyl phosphoric acyloxy) titanate, isopropyl tris (dioctyl phosphoric acyloxy) titanate, and the like can be cited.
The initiator in the step (1) is not particularly limited and may be selected from one or more of azo-type initiators and peroxide-type initiators. Preferably, the initiator may be selected from one or more of azodicyanopentanoic acid, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, ammonium persulfate, azobisisobutyronitrile hydrochloride.
The amounts of the polymerized monomer, the coupling agent and the initiator in the step (1) are respectively as follows: the molar ratio of the polymerized monomer to the coupling agent is (1-100): 1, the molar ratio of the polymerized monomer to the initiator is (10-1000): 1. if the ratio of the polymerized monomer to the coupling agent is too small, the graft amount of the polymerized monomer is small, and a surface coating having a desired function cannot be obtained, and if the ratio of the polymerized monomer to the coupling agent is too large, the adhesion of the coupling agent to the substrate surface is lacking, resulting in weak adhesion of the coating to the substrate surface. In addition, if the ratio of the polymerization monomer to the initiator is too small, the molecular weight of the polymer surface is limited; if the ratio of the polymerization monomer to the initiator is too large, the graft density on the polymer surface may be lowered.
The concentration of the polymerized monomer in the reaction liquid in the step (1) is 0.001 to 10g/ml, preferably 0.005 to 0.5g/ml. If the concentration of the polymerized monomer is too small, the graft density on the polymer surface decreases, and if the concentration of the polymerized monomer is too large, an excessively thick gel layer is formed on the polymer surface.
The solvent used in step (1) is not particularly limited, and for example, an organic solvent such as methanol, ethanol, acetone, methyl ethyl ketone, and the like can be used.
Step (2)
Step (2) of the present invention involves contacting the substrate with the reaction liquid obtained in step (1).
The substrate of the present invention is not particularly limited, and for example, a silicone rubber substrate such as a Polydimethylsiloxane (PDMS) substrate, a nylon elastomer (Pebax) substrate, a Thermoplastic Polyurethane (TPU) substrate, a polyvinyl chloride (PVC) substrate, a polyolefin substrate, a polyester substrate, and other polymer substrates, an inorganic material such as a ceramic material or a glass material, and a metal material such as a stainless steel material, a nickel-titanium alloy, or copper may be used.
The substrate is preferably subjected to one or more of plasma treatment, radiation treatment (e.g., ultraviolet radiation, radiation), ozone treatment, chemical agent treatment in advance. The treatments may be those conventionally used, for example, those which may be used
Figure BDA0003452311320000081
The plasma technology cleans the surface of the substrate to remove release agent, additives and the like on the surface of the substrate; the surface of the base material is subjected to acid treatment by hydrochloric acid, nitric acid and the like and/or alkali treatment by sodium hydroxide, potassium hydroxide and the like so as to achieve the aim of cleaning the surface of the base material.
Step (3)
In the invention, the reaction liquid on the surface of the substrate can be subjected to microwave radiation by using a known microwave device. The coupling agent may be bonded to the substrate surface by microwave irradiation, between the polymerized monomers and the coupling agent, or between the coupling agent and the substrate surface.
In the step (3), the microwave radiation is carried out for 0.5 to 30min, preferably 1 to 20min, the temperature of the microwave radiation is 50 to 200 ℃, preferably 50 to 100 ℃, and the power of the microwave radiation is 50 to 2500w, preferably 500 to 1500w. If the microwave irradiation time is short, the polymerization reaction efficiency is low, and the grafting degree is not high; excessive time, temperature or power of microwave radiation may cause some damage to the substrate. In the present specification, the temperature at which the polymerization by microwave radiation is carried out means the temperature at which the polymerization by microwave radiation actually occurs.
The invention also relates to a surface modified material prepared by the method. The surface modified material prepared by the method can be widely applied to various fields, in particular to the field of medical appliances.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The materials used, or the instruments, unless otherwise specified, are conventional products available commercially.
In the examples, the following abbreviations represent the following substances.
MEDSA:3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propane-1-sulfonate
AA: acrylamide
SS: sodium styrene sulfonate
PVP: polyvinylpyrrolidone
TAC: methacryloyloxyethyl trimethyl ammonium chloride
Lys: vinyl lysine
ACVA: azodicyanovaleric acid
Example 1
[ preparation of Silicone rubber-MEDSA composite substrate ]
mu.L (0.02% V/V,0.04 mmol) vinyltrimethoxysilane, 111mg (0.4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 1.12mg (0.004 mmol) of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask containing 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 5min in the solution, and tumbling N 2 15min. Setting microwave power 900w, heating temperature 75 deg.c, reaction time 30s,60s, 90s, 120s and 150s, to obtain the composite substrate with the coating on the surface.
The reaction formula is as follows:
Figure BDA0003452311320000101
example one study was made of the results of microwave polymerization carried out at different reaction times in the present invention. From fig. 1, it is seen that strong absorption peaks are shown on the infrared plot at a reaction time of 60s or more, which indicates that graft polymerization reaction occurs between silicone rubber, MEDSA and vinyltrimethoxysilane after microwave irradiation, and that the MEDSA successfully modifies the surface of the silicone rubber.
Example two
[ preparation of Silicone rubber-MEDSA composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 11.2mg (0.04 mmol) of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask containing 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
In comparison with example one, example two changed the amounts of vinyltrimethoxysilane, MEDSA and ACVA and the reaction time, and the results showed that graft polymerization occurred between the silicone rubber, MEDSA and vinyltrimethoxysilane, and that the MEDSA successfully modified the surface of the silicone rubber (fig. 2).
Example III
[ preparation of Pebax-MEDSA composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask with 30mL of 75% ethanolA solution was obtained. Completely immersing a nylon elastomer (Pebax) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example IV
[ preparation of TPU-MEDSA composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to give a solution. Completely immersing a Thermoplastic Polyurethane (TPU) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example five
[ preparation of PVC-MEDSA composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to give a solution. Completely immersing a polyvinyl chloride (PVC) substrate pretreated with oxygen plasma for 10min in the solution, and bubbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example six
[ preparation of Silicone rubber-AA composite substrate ]
mu.L (0.2% V/V,0.2 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of acrylamide (AA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Subsequently, setting microwave powerThe rate is 900w, the heating temperature is 75 ℃, the reaction time is 5min, and the composite substrate with the coating on the surface is obtained.
Example seven
[ preparation of Pebax-AA composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of acrylamide (AA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a nylon elastomer (Pebax) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example eight
[ preparation of TPU-AA composite substrate ]
mu.L (0.2% V/V,0.6 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of acrylamide (AA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Thermoplastic Polyurethane (TPU) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example nine
[ preparation of PVC-AA composite substrate ]
mu.L (0.2% V/V,0.8 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of acrylamide (AA) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a polyvinyl chloride (PVC) substrate pretreated with oxygen plasma for 10min in the solution, and bubbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples ten
[ preparation of Silicone rubber-SS composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxy1110mg (4 mmol) of sodium Styrene Sulfonate (SS) and 11.2mg of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 2min, and obtaining the composite substrate with the coating on the surface.
Example eleven
[ preparation of Pebax-SS composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of sodium Styrene Sulfonate (SS) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a nylon elastomer (Pebax) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Then setting the microwave power to 500w, heating the temperature to 75 ℃, and reacting for 10min to obtain the composite substrate with the coating on the surface.
Example twelve
[ preparation of TPU-SS composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of sodium Styrene Sulfonate (SS) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Thermoplastic Polyurethane (TPU) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 60 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example thirteen
[ preparation of PVC-SS composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of sodium Styrene Sulfonate (SS) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a polyvinyl chloride (PVC) substrate pretreated with oxygen plasma for 10min in the solution, and bubbling N 2 15min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples fourteen
[ preparation of Silicone rubber-PVP composite base Material ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of polyvinylpyrrolidone (PVP) and 11.2mg of azodicyanopentanoic acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example fifteen
[ preparation of Pebax-PVP composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of polyvinylpyrrolidone (PVP) and 11.2mg of azodicyanopentanoic acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a nylon elastomer (Pebax) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples sixteen
[ preparation of TPU-PVP composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of polyvinylpyrrolidone (PVP) and 11.2mg of azodicyanopentanoic acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Thermoplastic Polyurethane (TPU) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example seventeen
[ preparation of PVC-PVP composite base Material ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of polyvinylpyrrolidone (PVP) and 11.2mg of azodicyanopentanoic acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a polyvinyl chloride (PVC) substrate pretreated with oxygen plasma for 10min in the solution, and bubbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example eighteen
[ preparation of Silicone rubber-TAC composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of methacryloyloxyethyl Trimethyl Ammonium Chloride (TAC) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples nineteenth
[ preparation of Pebax-TAC composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of methacryloyloxyethyl Trimethyl Ammonium Chloride (TAC) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a nylon elastomer (Pebax) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example twenty
[ preparation of TPU-TAC composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of methacryloyloxyethyl trimethylammonium chloride (TAC) and 11.2mg of azodicyanopentanoic Acid (AC)VA) was dissolved in a three-necked flask containing 30ml of 75% ethanol to obtain a solution. Completely immersing a Thermoplastic Polyurethane (TPU) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Example twenty-one
[ preparation of PVC-TAC composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of methacryloyloxyethyl Trimethyl Ammonium Chloride (TAC) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a polyvinyl chloride (PVC) substrate pretreated with oxygen plasma for 10min in the solution, and bubbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples twenty two
[ preparation of Silicone rubber-Lys composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) vinyllysine (Lys) and 11.2mg azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples twenty-three
[ preparation of Pebax-Lys composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) vinyllysine (Lys) and 11.2mg azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL75% ethanol to obtain a solution. Completely immersing a nylon elastomer (Pebax) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Subsequently, setting microwave powerThe rate is 900w, the heating temperature is 75 ℃, the reaction time is 5min, and the composite substrate with the coating on the surface is obtained.
Examples twenty-four
[ preparation of TPU-Lys composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) vinyllysine (Lys) and 11.2mg azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL75% ethanol to obtain a solution. Completely immersing a Thermoplastic Polyurethane (TPU) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Examples twenty-five
[ preparation of PVC-Lys composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) vinyllysine (Lys) and 11.2mg azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL75% ethanol to obtain a solution. Completely immersing a polyvinyl chloride (PVC) substrate pretreated with oxygen plasma for 10min in the solution, and bubbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
As can be seen from fig. 2 to 5, in examples two to twenty-fifth, after the microwave irradiation, a graft polymerization reaction occurs between the polymerized monomer, the coupling agent and the surface of the substrate, and the polymerized monomer successfully modifies the surface of the substrate.
Examples twenty-six
[ preparation of stainless Material-TAC composite substrate ]
mu.L (0.2% V/V,0.4 mmol) of vinyltrimethoxysilane, 1110mg (4 mmol) of methacryloyloxyethyl Trimethyl Ammonium Chloride (TAC) and 11.2mg of azodicyanovaleric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a stainless steel substrate pretreated with oxygen plasma for 10min in advance in the solution, and tumbling N 2 30min. Along with itSetting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
Comparative example
Comparative example 1
[ preparation of Silicone rubber-MEDSA composite substrate ]
mu.L (0.2% V/V,0.8 mmol) vinyltrimethoxysilane, 111mg (0.4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 11.2mg (0.04 mmol) of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask containing 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
In comparative example 1, the ratio of polymerized monomer to coupling agent was 0.5:1, the graft amount of the polymerized monomer is insufficient.
Comparative example 2
[ preparation of Silicone rubber-MEDSA composite substrate ]
mu.L (0.2% V/V,0.4 mmol) vinyltrimethoxysilane, 1110mg (4 mmol) 3- [ [2- (methacryloyloxy) ethyl ]]Dimethyl ammonium group]Propane-1-sulfonate (MEDSA) and 1120mg (4 mmol) of azodicarbonyl valeric acid (ACVA) were dissolved in a three-necked flask equipped with 30mL of 75% ethanol to obtain a solution. Completely immersing a Polydimethylsiloxane (PDMS) substrate pretreated with oxygen plasma for 10min in the solution, and tumbling N 2 30min. Setting microwave power 900w, heating at 75 ℃ for 5min, and obtaining the composite substrate with the coating on the surface.
In comparative example 2, the ratio of initiator to polymerized monomer was 1:1, the graft amount of the monomer is insufficient.
Comparative example 3
Unmodified silicone rubber (PDMS) was taken.
Comparative example 4
Unmodified Pebax was taken.
Comparative example 5
The unmodified TPU is taken.
Comparative example 6
Unmodified PVC was taken.
Comparative example 7
Unmodified stainless steel material was used.
Characterization of Performance
1. Characterization of Water contact Angle
And horizontally placing the sample to be tested on a water contact angle tester, contacting a water drop with the volume of 5 mu L with the surface of the sample through a syringe, and measuring the included angle between the tangent line extending from the solid-liquid-gas three-phase contact point to the liquid-gas interface and the liquid-solid interface after the surface of the water drop is stabilized for 2s, thus obtaining the water contact angle of the sample.
2. Characterization of anti-protein adsorption test fibrinogen adsorption
By iodine chloride (ICl) method 125 I labelling fibrinogen, fibrinogen was passed through AG1-X4 anion exchange resin column to remove free iodine. The labeled protein was added to platelet-free plasma at a concentration of about 10% of the plasmin concentration in normal plasma. The substrate was placed in the above protein solution and incubated for 3h, rinsed three times with phosphate buffer solution for 10min each time, blotted dry with filter paper and transferred to a clean tube and tested for its emission using an automatic gamma particle counter. The amount of protein adsorbed was calculated as mass per unit area.
The test results are shown in Table 1. Compared with an unmodified silicon rubber substrate, the water contact angle is obviously reduced due to the introduction of the functional monomer after the microwave modification, and the adsorption quantity of fibrinogen is also greatly reduced, so that the substrate after the microwave modification has good hydrophilic and anti-fouling properties.
TABLE 1
Group of Water contact angle (°) Fg adsorption quantity (. Mu.g/cm) 2 )
Example two 36 0.08
Examples fourteen 38 0.10
Comparative example 3 85 0.86
Comparative example 1 68 0.72
Comparative example 2 72 0.82
3. Testing of antibacterial Properties
After the E.coli was grown on the substrate surface for 2-3 hours, the substrate was taken out, immersed in a centrifuge tube containing 1mL of phosphate buffer solution (pH=7.4), and centrifuged at 5000rpm for 5 minutes to collect bacteria on the substrate surface. mu.L of the collected bacterial liquid is coated on an agar culture plate by a flat plate coating method, and is placed in a 37 ℃ incubator for culturing for 18 hours, taken out and photographed.
The test results are shown in fig. 6. FIG. 6 shows the bactericidal effect of microcatheter surface coating as measured by plate coating in example twenty-six and comparative example 7. As can be seen from FIG. 6, the bacteria collected from the substrate subjected to the microwave modification treatment have substantially died, no colony was formed, and a large number of colonies were formed on the unmodified substrate, and the antibacterial effect was poor.
4. Testing thrombolytic Properties
The substrate sample was immersed in a tris buffer (ph=7.4) for 1h, taken out, immersed in normal human plasma for 3h, taken out, and rinsed three times with tris buffer. The sample was immersed in t-PA for 10min. The pellet was rinsed 3 times with tris buffer, the substrate was removed, blotted dry with filter paper, 100 μl of plasma was added, and 100 μl of 0.025M calcium chloride solution was added. All the above-mentioned infusions were carried out in a 37℃incubator, and the added plasma and t-PA were preheated in the 37℃incubator. The absorbance at 405nm was measured with a microplate reader, the time interval was set to 30s, and the total duration of the test was not less than 1h.
The test results are shown in fig. 7. Figure 7 shows the thrombolytic ability of the surfaces of the twenty-two to twenty-five and unmodified TPU substrates (comparative example 5) of the examples. Over time, the absorbance gradually increased to a maximum value, indicating complete thrombus formation during this period. After the thrombus is completely formed, the absorbance of each substrate subjected to microwave surface modification gradually decreases, and the generated thrombus is proved to be dissolved until the thrombus is completely dissolved, and the absorbance is restored to the initial value. The surface of the base material has certain thrombolytic and anticoagulant capacities after microwave modification.

Claims (10)

1. A method for modifying a surface of a material, comprising the steps of:
(1) Dissolving, suspending or dispersing a polymerization monomer, a coupling agent and an initiator in a solvent to prepare a reaction solution;
(2) Contacting a substrate with the reaction solution;
(3) Polymerizing the reaction liquid on the surface of the substrate by microwave radiation to obtain the surface modified substrate.
2. The method according to claim 1, wherein the polymeric monomer in step (1) is selected from one or more of (meth) acrylamide-based monomers, cationic-based monomers, heparin-based monomers, heparinoids-based monomers, sodium styrenesulfonate, N-vinylpyrrolidone, (meth) acrylic monomers, (meth) acrylic acid ester-based monomers, fibrinolytic monomers, zwitterionic-based monomers.
3. The method according to claim 1 or 2, wherein the coupling agent in step (1) is selected from one or more of a silane coupling agent, a titanate coupling agent.
4. The method according to claim 1 or 2, wherein the initiator in step (1) is selected from one or more of azo-type initiators, peroxide-type initiators.
5. The method of claim 4, wherein the initiator is selected from one or more of azodicarbonyl valeric acid, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, ammonium persulfate, azobisisobutyronitrile, and hydrochloride.
6. The method according to claim 1 or 2, wherein the amounts of the polymerized monomer, the coupling agent and the initiator in step (1) are respectively: the molar ratio of the polymerized monomer to the coupling agent is (1-100): 1, the molar ratio of the polymerized monomer to the initiator is (10-1000): 1.
7. the method according to claim 1 or 2, wherein the concentration of the polymerized monomer in the reaction liquid in step (1) is 0.001-10g/ml.
8. The method of claim 1 or 2, wherein the substrate in step (2) is pre-subjected to one or more of plasma treatment, corona treatment, radiation treatment, ozone treatment, chemical agent treatment.
9. The method according to claim 1 or 2, wherein the microwave irradiation in step (3) is performed for 0.5 to 30 minutes, the polymerization temperature of the microwave irradiation is 50 to 200 ℃, and the power of the microwave irradiation is 50 to 2500w.
10. A surface modified material prepared by the method of any one of the preceding claims.
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Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4373009A (en) * 1981-05-18 1983-02-08 International Silicone Corporation Method of forming a hydrophilic coating on a substrate
US5344455A (en) * 1992-10-30 1994-09-06 Medtronic, Inc. Graft polymer articles having bioactive surfaces
EP0860213A3 (en) * 1997-01-03 2002-10-16 Therapol SA Bioactive coating on surfaces
GB2325934A (en) * 1997-06-03 1998-12-09 Polybiomed Ltd Treating metal surfaces to enhance bio-compatibility and/or physical characteristics
US6143354A (en) * 1999-02-08 2000-11-07 Medtronic Inc. One-step method for attachment of biomolecules to substrate surfaces
BR0317587A (en) * 2002-12-20 2005-11-22 Ciba Sc Holding Ag Process for forming functional layers
JP4284415B2 (en) * 2004-04-12 2009-06-24 国立大学法人群馬大学 Method for coating metal material surface with polymer and metal material coated with polymer
US20070048349A1 (en) * 2005-08-29 2007-03-01 Bausch & Lomb Incorporated Surface-modified medical devices and methods of making
CN102888016B (en) * 2012-09-12 2014-03-05 常州大学 Preparation method of lithium-ion secondary battery diaphragm with crosslinking composite layer
CN102912335B (en) * 2012-09-24 2015-11-25 河南科技大学 Medical metal material of a kind of surface modification and preparation method thereof
CN104004214A (en) * 2014-05-26 2014-08-27 北京化工大学 Method for enhancing hydrophobicity of surface of butyl rubber
JP6154370B2 (en) * 2014-12-26 2017-06-28 住友ゴム工業株式会社 Surface-modified metal and method for modifying metal surface
CN106377801A (en) * 2016-11-18 2017-02-08 青岛科技大学 Super-smooth intravascular catheter coating and preparation method thereof
CN107141502B (en) * 2017-05-31 2019-08-23 泰州度博迈医疗器械有限公司 A kind of antibacterial silicon rubber, preparation method and applications
CN111686310B (en) * 2019-03-11 2022-03-29 国家纳米科学中心 Antibacterial catheter and preparation method and application thereof
JP2021011530A (en) * 2019-07-05 2021-02-04 岩崎電気株式会社 Method for surface modification of inorganic material
CN111234288A (en) * 2020-01-19 2020-06-05 东华大学 Preparation method of hydrophilic polymer antifogging coating

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