CN112574460A - Polymer medical instrument with hydrophilic lubricating coating and preparation method thereof - Google Patents

Polymer medical instrument with hydrophilic lubricating coating and preparation method thereof Download PDF

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Publication number
CN112574460A
CN112574460A CN202011492001.4A CN202011492001A CN112574460A CN 112574460 A CN112574460 A CN 112574460A CN 202011492001 A CN202011492001 A CN 202011492001A CN 112574460 A CN112574460 A CN 112574460A
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coating
hydrophilic
lubricating coating
medical instrument
medical
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程思博
念国栋
夏崟
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Suzhou Ningzhi New Materials Development Co ltd
Harvard University
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Suzhou Ningzhi New Materials Development Co ltd
Harvard University
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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
    • C08J7/04Coating
    • C08J7/056Forming hydrophilic coatings
    • 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • C08J7/04Coating
    • C08J7/0427Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J7/123Treatment by 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/452Lubricants
    • 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
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • 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
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/12Agar-agar; Derivatives thereof
    • 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
    • C08J2439/00Characterised 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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • C08J2471/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02Polyalkylene oxides

Abstract

The invention provides a polymer medical appliance with a hydrophilic lubricating coating and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing a hydrophilic high polymer material, an initiator and a solvent to obtain a precursor solution of the hydrophilic lubricating coating; (2) after oxygen plasma treatment is carried out on the polymer medical instrument, soaking treatment is carried out in the pretreatment liquid; wherein the pretreatment liquid contains a photoinitiator; (3) and (3) coating the precursor solution obtained in the step (1) on the surface of the polymer medical device treated in the step (2), and then carrying out photocuring to obtain the polymer medical device with the hydrophilic lubricating coating. The macromolecular medical device with the hydrophilic lubricating coating provided by the invention has stable and long-acting super-lubricating and hydrophilic characteristics, and the preparation method does not have a monomer polymerization process, so that the hydrophilic lubricating coating can be ensured to have excellent biocompatibility.

Description

Polymer medical instrument with hydrophilic lubricating coating and preparation method thereof
Technical Field
The invention belongs to the technical field of medical instruments, and relates to a polymer medical instrument with a hydrophilic lubricating coating and a preparation method thereof.
Background
The medical instrument surface coated with the medical lubricating coating has lower surface friction coefficient, such as a guide wire, a PTCA catheter, a catheter, an endoscope and the like, when the medical instrument is inserted and pulled out, the friction between the instrument and human tissues can be reduced, the pain of a patient in an operation can be relieved, the operation difficulty of a doctor can be effectively reduced, and the defect that severe lesion can not enter a lesion part due to large friction resistance can be avoided.
At present, the surface friction coefficient of implantable or interventional medical devices in blood and tissue environments can be reduced by coating hydrophilic coatings, but the existing problems of the hydrophilic coatings comprise complex manufacturing process, poor lubricity, insufficient durability and the like, the lubricating performance in the long-term use process cannot be maintained, and the development of the coating process is not facilitated.
CN 107754017A takes hydrophilic polymer, polyhydroxy polymer, anhydride cross-linking agent and dispersion medium as coating material, the prepared coating is applied on the surface of medical equipment and then heated, cured and formed, and the hydrogel network coating formed by three-dimensional cross-linking is obtained. Although the lubricity and hydrophilicity of the hydrophilic coatings are improved on medical instruments and consumables, the coating materials cannot form effective chemical bond connection with the base materials, so that the hydrophilic coatings generally have the problems of falling off or failure and the like in the long-term use process, and the fallen off coating materials can further block blood vessels, thereby causing more serious side effects. WO-0405909a1 discloses the use of plasticizers in crosslinked hydrophilic coatings of hydrophilic polymers on substrates; the plasticizer forms part of a polymer solution that is applied to a substrate, which may be a medical device such as a catheter, guidewire, or endoscope, and, after application, the polymer solution is dried and cured. Medical devices coated with a hydrophilic coating are wetted with water prior to use on a patient, the plasticizer having the effect of providing a hydrophilic coating that exhibits high abrasion resistance and a low coefficient of friction when wetted; this patent application uses water to lubricate the hydrophilic coating, by using water as the major component in the wetting agent, the wetting time is extremely short, and the hydrophilic coating is generally not lubricated anymore within a period of 15 minutes after wetting or after removal of the medical device from the package. CN 110819183A selects water-soluble monomer as coating precursor liquid material, utilizes silane coupling agent as functional group for bonding, and realizes firm hydrophilic coating on the surface of medical apparatus by initiating polymerization-dip coating-heating curing method, but the coating material may contain unreacted monomer raw material, which affects biocompatibility of the whole apparatus, and the whole coating process has long time, thus being not beneficial to large-scale production.
Generally, the current hydrophilic coating material and preparation method cannot ensure long-time and stable lubricating performance, and meanwhile, certain defects exist in the aspect of manufacturing process, the mass and rapid production process cannot be met, and the required cost is high, so that a new hydrophilic lubricating coating needs to be provided to meet the application requirement.
Disclosure of Invention
The invention aims to provide a polymer medical appliance with a hydrophilic lubricating coating and a preparation method thereof. The macromolecular medical device with the hydrophilic lubricating coating provided by the invention has stable and long-acting super-lubricating and hydrophilic characteristics, and the preparation method does not have a monomer polymerization process, so that the hydrophilic lubricating coating can be ensured to have excellent biocompatibility.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a polymer medical device with a hydrophilic lubricating coating, the method comprising the following steps:
(1) mixing a hydrophilic high polymer material, an initiator and a solvent to obtain a precursor solution of the hydrophilic lubricating coating;
(2) after oxygen plasma treatment is carried out on the polymer medical instrument, soaking treatment is carried out in the pretreatment liquid;
wherein the pretreatment liquid contains a photoinitiator;
(3) coating the precursor solution obtained in the step (1) on the surface of the polymer medical instrument treated in the step (2),
(4) and (4) carrying out ultraviolet curing on the coated instrument obtained in the step (3) to obtain the polymer medical instrument with the hydrophilic lubricating coating.
The hydrophilic lubricating coating is arranged on the surface of the medical instrument, so that the medical instrument has a lubricating effect, the friction coefficient of the surface of the medical instrument is reduced, and meanwhile, the preparation method provided by the invention can ensure that a firm covalent bond is formed between the finally obtained hydrophilic lubricating coating and the medical instrument, namely, the finally obtained medical instrument has long-term and stable hydrophilic lubricating performance.
The hydrophilic high molecular material is selected from the precursor solution of the hydrophilic lubricating coating selected by the invention, and the hydrophilic high molecular material does not contain small molecular monomers, so that the finally obtained hydrophilic lubricating coating does not contain small molecular substances, and the good biocompatibility of the coating is further ensured.
In addition, the preparation method provided by the invention is easy to coat by methods such as dipping or spin coating, the thickness of the coating is uniform and controllable, oxygen is not required to be isolated in the curing process of the coating, and the coating can be cured by ultraviolet irradiation in a very short time, so that the preparation process of the coating is effectively simplified, and the preparation cost of the coating is reduced; the preparation method provided by the invention is simple and feasible, has a simple coating process, and is suitable for large-scale batch production.
Preferably, the photoinitiator is selected from any one or a combination of at least two of benzophenone, michler's ketone, diphenoxybenzophenone, alkyl substituted benzophenone, thioxanthone, anthraquinone, coumarone, camphorquinone, sodium benzoate, acetophenone, p-chlorobenzophenone or benzaldehyde.
According to the invention, the photoinitiator is added into the pretreatment liquid, so that a functional group for chemical bonding with the coating is introduced on the surface of the polymer guide wire, and the stable bonding of the coating and the polymer substrate is realized.
Preferably, the solvent for the pretreatment liquid is selected from any one of methanol, ethanol, isopropanol, acetone or toluene or a combination of at least two of the above.
Preferably, the photoinitiator is contained in the pretreatment liquid in an amount of 5 to 10% by mass, for example, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or the like. Too low a concentration of photoinitiator may not form sufficient chemical bonds on the surface of the polymer substrate, and too much may affect the biocompatibility of the coating.
Preferably, the hydrophilic polymer material in step (1) is selected from any one or a combination of at least two of alginate, hyaluronic acid, agarose, chitosan, collagen, gelatin, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate, methylcellulose or polyisopropylacrylamide.
The hydrophilic polymer material selected by the invention is a water-soluble polymer material, has strong hydrophilicity, transparent optical property and good biocompatibility, and can be used for improving the rejection reaction of uncoated medical instruments in vivo and reducing the side effect of the medical instruments. Meanwhile, the coating material has a certain antibacterial effect, and the service performance of related instruments and consumables can be improved; in addition, the coating can dissolve certain medicines and can be used for fixed-point slow release of the medicines in the process of implanting the device.
Preferably, the initiator of step (1) is selected from hydrogen abstraction type initiators, further preferably any one or a combination of at least two of benzophenone, Michler's ketone, benzophenone oxide, alkyl substituted benzophenone, thioxanthone, anthraquinone, coumarone, camphorquinone, sodium benzoate, acetophenone, p-chlorobenzophenone or benzaldehyde.
Preferably, the solvent in step (1) is selected from any one of water, methanol, ethanol, acetone, formamide, N-dimethylformamide or dimethyl sulfoxide or a combination of at least two of the above.
Preferably, in the precursor solution of step (1), the mass percentage of the hydrophilic polymer material is 5-20%, for example, 6%, 8%, 10%, 12%, 13%, 15%, 16%, 17%, 18%, 19%, etc.
Preferably, in the precursor solution of step (1), the initiator is contained in an amount of 0.1-2% by mass, for example, 0.2%, 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, etc.
Preferably, the polymer medical device in step (2) comprises an implantable medical device or an interventional medical device.
Preferably, the polymer material for the medical device is selected from any one of silicone rubber, polyethylene, polystyrene, polypropylene, polyamide, polyether block polyamide, polylactic acid, polyimide, polymethyl methacrylate or polyurethane or a combination of at least two of the above.
Preferably, the medical device comprises an artificial organ, a stent, an intravascular catheter, a guidewire or a sheath embolization device.
Preferably, the oxygen plasma treatment time in step (2) is 1-5min, such as 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, etc.
Preferably, the soaking time in step (2) is 1-5min, such as 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, etc.
Preferably, the coating method in step (3) is selected from dipping and/or spin coating.
Preferably, the impregnation is carried out at a pulling speed of 10-300mm/min, such as 20mm/min, 50mm/min, 80mm/min, 100mm/min, 120mm/min, 150mm/min, 200mm/min, 230mm/min, 270mm/min, 290mm/min, etc.
Preferably, the photo-curing is uv-curing.
Preferably, the medical device and the ultraviolet lamp are spaced apart by 10-50mm, such as 12mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm, 48mm, etc., when photocuring is performed.
Preferably, the illumination intensity of the ultraviolet lamp is 0.1-2W/cm2E.g. 0.2W/cm2、0.4W/cm2、0.5W/cm2、0.8W/cm2、1.0W/cm2、1.2W/cm2、1.4W/cm2、1.6W/cm2、1.8W/cm2And the like.
Preferably, the photocuring time is 1-90min, such as 5min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 85min, and the like.
Preferably, the preparation method further comprises: cleaning and drying the medical instrument before step (2).
Preferably, the solvent for cleaning comprises any one of water, ethanol, isopropanol, acetone, heptane or n-hexane or a combination of at least two thereof.
Preferably, the drying is air drying, and the air drying time is 1-5min, such as 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, and the like.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing a hydrophilic high polymer material, an initiator and a solvent to obtain a precursor solution of the hydrophilic lubricating coating, wherein in the precursor solution, the mass percentage of the hydrophilic high polymer material is 5-20%, and the mass percentage of the initiator is 0.1-2%;
(2) cleaning medical instruments, airing for 1-5min, carrying out oxygen plasma treatment on the cleaned medical instruments for 1-5min, and soaking in a pretreatment liquid containing a photoinitiator for 1-5 min;
(3) coating the precursor solution obtained in the step (1) on the surface of the medical instrument treated in the step (2) by a dipping or spin coating method
(4) And (4) carrying out ultraviolet curing on the coated medical instrument obtained in the step (3) for 1-90min to obtain the polymer medical instrument with the hydrophilic lubricating coating.
In a second aspect, the invention provides a medical polymer device with a hydrophilic lubricating coating prepared according to the preparation method of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the hydrophilic lubricating coating is arranged on the surface of the medical instrument, so that the medical instrument has a lubricating effect, the friction coefficient of the surface of the medical instrument is reduced, and meanwhile, the preparation method provided by the invention can ensure that a firm covalent bond is formed between the finally obtained hydrophilic lubricating coating and the medical instrument, namely the finally obtained medical instrument has long-term and stable hydrophilic lubricating performance;
(2) hydrophilic high molecular materials are selected from the precursor solution of the hydrophilic lubricating coating, and small molecular monomers are not included, so that the finally obtained hydrophilic lubricating coating does not include small molecular substances, and the good biocompatibility of the coating is further ensured;
(3) the preparation method provided by the invention enables the coating to be easily coated by methods such as dipping or spin coating, the thickness of the coating is uniform and controllable, oxygen is not required to be isolated in the curing process of the coating, and the coating can be cured by ultraviolet irradiation in a very short time, so that the preparation process of the coating is effectively simplified, and the preparation cost of the coating is reduced;
(4) the preparation method provided by the invention is simple and feasible, has a simple coating process, and is suitable for large-scale batch production.
Drawings
FIG. 1 is a flow chart of the preparation of the polymeric medical device with a hydrophilic lubricating coating according to the present invention.
Fig. 2 is a friction-displacement graph in a friction test of a Pebax guidewire with a hydrophilic lubricious coating provided in example 1 of the invention.
Fig. 3 is a friction-displacement graph in a friction test of the Pebax guidewire provided in comparative example 1 of the present invention.
Fig. 4 is a friction-displacement graph in a friction test of a TPU guidewire with a hydrophilic lubricious coating provided in example 2 of the invention.
Fig. 5 is a friction-displacement graph in a friction test of the TPU guidewire provided by comparative example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A Pebax (polyether block polyamide) guide wire with a hydrophilic lubricating coating is prepared by the following steps:
(1) uniformly dissolving 13% by mass of polyvinylpyrrolidone (type Sigma-Aldrich # PVP360, molecular weight of about 360000) and 0.5% by mass of benzophenone in a mixed solution of water and ethanol (volume ratio of 1:1) to obtain a precursor solution of the hydrophilic lubricating coating;
(2) sequentially cleaning the surface of the Pebax guide wire with isopropanol, ethanol and water, and airing for 3 min;
(3) carrying out oxygen plasma treatment on the Pebax guide wire for 1min, and further soaking in acetone solution with the mass fraction of 10% of benzophenone for 5min to activate the surface of the Pebax guide wire;
(4) coating the precursor solution obtained in the step (1) on the surface of the Pebax guide wire treated in the step (3) by using a dipping method, wherein the pulling speed in the dipping method is 100 mm/min;
(5) carrying out ultraviolet curing on the coated Pebax guide wire coating obtained in the step (4), wherein the distance between the Pebax guide wire and an ultraviolet lamp is 50mm, and the illumination intensity of the ultraviolet lamp is 0.3W/cm2And curing for 10min to obtain the Pebax guide wire with the hydrophilic lubricating coating.
Example 2
The embodiment provides a TPU guide wire with a hydrophilic lubricating coating, and the preparation method comprises the following steps:
(1) uniformly dissolving 10% by mass of polyethylene glycol (type is Supelco 81206, the molecular weight is about 218000) and 0.2% by mass of benzophenone in a mixed solution of water and ethanol (the volume ratio is 1.2:1) to obtain a precursor solution of the hydrophilic lubricating coating;
(2) cleaning the surface of the TPU guide wire by using isopropanol and water in sequence, and airing for 5 min;
(3) carrying out oxygen plasma treatment on the TPU guide wire for 2min, and further soaking the TPU guide wire in an ethanol solution of benzophenone with the mass fraction of 5% for 2min to activate the surface of the TPU guide wire;
(4) coating the precursor solution obtained in the step (1) on the surface of the TPU guide wire treated in the step (3), wherein the coating is realized by a dipping method, and the pulling speed is 60 mm/min;
(5) carrying out ultraviolet curing on the coated stainless steel guide wire coating obtained in the step (4), wherein the distance between a Pebax guide wire and an ultraviolet lamp is 50mm, and the illumination intensity of the ultraviolet lamp is 0.6W/cm2And curing for 5min to obtain the TPU guide wire with the hydrophilic lubricating coating.
Example 3
The embodiment provides a Pebax guide wire with a hydrophilic lubricating coating, and the preparation method is as follows:
(1) uniformly dissolving agarose (the model is Sigma-Aldrich # A1296) with the mass fraction of 5% and coumarone with the mass fraction of 2% in a mixed solution of water and ethanol (the volume ratio is 1.2:1) to obtain a precursor solution of the hydrophilic lubricating coating;
(2) sequentially cleaning the surface of the Pebax guide wire with isopropanol and water, and airing for 1 min;
(3) carrying out oxygen plasma treatment on the Pebax guide wire for 5min, and further soaking in an ethanol solution of coumarone with the mass fraction of 8% for 1min to activate the surface of the Pebax guide wire;
(4) coating the precursor solution obtained in the step (1) on the surface of the Pebax guide wire treated in the step (3), wherein the coating is realized by a dipping method, and the pulling speed is 40 mm/min;
(5) and (4) carrying out ultraviolet curing on the coated Pebax guide wire coating obtained in the step (4), wherein the distance between the Pebax guide wire and an ultraviolet lamp is 10mm, and the illumination intensity of the ultraviolet lamp is 0.1W/cm2And curing for 30min to obtain the Pebax guide wire with the hydrophilic lubricating coating.
Comparative example 1
Example 1 provides a Pebax (polyether block polyamide) guidewire.
Comparative example 2
Example 2 provides a TPU guidewire.
Comparative example 3
CN 110819183 a provides example 3, namely, a hydrophilic lubricating coating for thermoplastic polyurethane elastomer (TPU) surface is provided, which is prepared by the following method:
(1) cleaning the surface of the TPU guide wire by using acetone, ethanol and water in sequence, and drying for later use;
(2) putting the cleaned TPU guide wire obtained in the step (1) into an oxygen plasma cleaning machine for surface activation treatment for 20min, taking out and putting into deionized water for later use;
(3) preparing 25% sodium acrylate (type: Sigma-Aldrich 408220) water solution, and adjusting pH to 3.5 with 0.1mol/l hydrochloric acid solution; adding 9 μ L of 3- (trimethoxysilyl) propyl methacrylate (model: Sigma-Aldrich 440159) as silane coupling agent to each ml of solution, wherein the final mass concentration is 0.94%, and stirring until the mixture is hydrolyzed completely; adding 2 μ L of ethanol solution of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (model: Sigma-Aldrich 410896) with a molar concentration of 0.1mol/L into each ml of solution, stirring well, and then sucking into a syringe; placing the injector under ultraviolet light to carry out free radical polymerization reaction for 30min to obtain hydrogel precursor liquid for preparing the hydrophilic lubricating coating;
(4) taking out the TPU guide wire obtained in the step (2), and coating the coating precursor liquid obtained in the step (3) on the surface of the guide wire in a dip-coating mode;
(5) after the coating is shaped, putting the TPU into a closed container, heating the TPU in a 65 ℃ oven for 24 hours to fully crosslink and solidify the hydrogel precursor liquid, and finally forming a hydrophilic lubricating coating on the surface of the TPU.
Comparative example 4
The difference from example 1 is that in this comparative example, the pretreatment liquid was an aqueous solution of trimethoxy (propyl) silane with a mass fraction of 10%.
Comparative example 5
The difference from example 1 is that step (1) is: uniformly dissolving 13% by mass of polyvinylpyrrolidone and 5% by mass of benzophenone in a mixed solution of water and ethanol (volume ratio of 1:1) to obtain a precursor solution of the hydrophilic lubricating coating.
Comparative example 6
The difference from example 1 is that the mass fraction of polyvinylpyrrolidone in the precursor liquid of the hydrophilic lubricating coating in this example is 1%.
Performance testing
The polymer medical devices provided in examples 1 to 4 and comparative examples 1 to 4 were subjected to a performance test by the following method:
(1) and (3) friction test: fixing two ends of a sample with the length of 15cm and the diameter of 0.3mm on a chuck of a material testing machine, wherein the maximum measuring range of a sensor of the used material testing machine is 10N, placing a water tank filled with pure water on an operation table of the material testing machine, controlling the temperature of the water to be 37 ℃, placing a chuck capable of applying certain pre-pressure in the water tank, covering the contact part of the chuck and a guide wire by a silica gel gasket, controlling the pressure to be 0.5N, clamping the guide wire to be tested in the middle, paying attention to the fact that the free end of the guide wire cannot touch the bottom or the inner wall of the water tank, and ensuring that the guide wire is vertical to a pressure head;
after the experiment begins, the material testing machine is loaded back and forth at the speed of 100mm/min to drive the guide wire to move up and down, the cyclic loading frequency is 20 times, during the cyclic loading, the part of the guide wire, which is in contact with the chuck, generates reciprocating friction, and the magnitude of the friction force is recorded by the testing software;
fig. 2 is a graph of friction versus displacement in a friction test of the Pebax guidewire provided with a hydrophilic lubricious coating in example 1, fig. 3 is a graph of friction versus displacement in a friction test of the Pebax guidewire provided in comparative example 1 (bare uncoated guidewire), and it can be seen from a comparison of fig. 2 and fig. 3 that the bare Pebax guidewire without a coating (comparative example 1) has a relatively high frictional resistance with an average value of about 0.6N; the friction resistance of the Pebax guide wire with the hydrophilic lubricating coating prepared in the example 1 is obviously reduced, the average value is about 0.03N, and the lubricating property required by the Pebax guide wire is met.
Fig. 4 is a graph of friction versus displacement in a friction test of the TPU guidewire provided with a hydrophilic lubricious coating in example 2, fig. 5 is a graph of friction versus displacement in a friction test of the TPU guidewire provided in comparative example 2 (bare guidewire without coating), and from a comparison of fig. 4 and fig. 5, the bare TPU guidewire without coating (comparative example 2) has a greater frictional resistance, with an average value of about 0.6N; the friction resistance of the TPU guide wire with the hydrophilic lubricating coating prepared in the example 2 is obviously reduced, the average value is about 0.02N, and the lubricating property required by the TPU guide wire can be met.
(2) Biocompatibility: part 5 of the biological evaluation of medical devices according to GB/T16886.5-2017: cytotoxicity test-in vitro method, MTT method was used to evaluate potential cytotoxicity of samples.
The results of the performance tests on the examples and comparative examples are shown in table 1:
TABLE 1
Figure BDA0002841005170000121
According to the embodiment and the performance test, the polymer medical instrument with the hydrophilic lubricating coating has good lubricating property and coating firmness, and the friction force is basically unchanged in a repeated reciprocating friction test, so that the lubricating property of the polymer medical instrument with the hydrophilic lubricating special layer has long-acting stability; meanwhile, the preparation method of the invention is suitable for various polymer medical instruments; wherein, the friction force of the coating under the condition that the positive pressure is 0.5N is below 0.1N, the cell viability value of 100 percent of leaching liquor of the coating is above 72 percent, and the biocompatibility is good.
As can be seen from the comparison between example 1 and comparative example 3, the hydrophilic lubricating coating obtained by the present invention has better biocompatibility than the precursor solution for preparing the hydrophilic lubricating coating by using the monomer. As can be seen from the comparison between example 1 and comparative example 4, the hydrophilic lubricating coating obtained by the preparation method of the present invention has stable interfacial chemical bonding with the medical device, thereby ensuring that the medical device can obtain stable and long-lasting hydrophilic lubricity.
The applicant states that the present invention is illustrated by the above examples of the polymeric medical device with hydrophilic lubricating coating and the method for preparing the same, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. A preparation method of a polymer medical appliance with a hydrophilic lubricating coating is characterized by comprising the following steps:
(1) mixing a hydrophilic high polymer material, an initiator and a solvent to obtain a precursor solution of the hydrophilic lubricating coating;
(2) after oxygen plasma treatment is carried out on the polymer medical instrument, soaking treatment is carried out in the pretreatment liquid;
wherein the pretreatment liquid contains a photoinitiator;
(3) coating the precursor solution obtained in the step (1) on the surface of the polymer medical instrument treated in the step (2);
(4) and (3) carrying out ultraviolet curing on the coated instrument to finally obtain the polymer medical instrument with the hydrophilic lubricating coating.
2. The production method according to claim 1, wherein the photoinitiator is selected from any one or a combination of at least two of benzophenone, Michler's ketone, benzophenone oxide, alkyl-substituted benzophenone, thioxanthone, anthraquinone, coumarone, camphorquinone, sodium benzoate, acetophenone, p-chlorobenzophenone, or benzaldehyde;
preferably, the solvent for the pretreatment liquid is selected from any one of methanol, ethanol, isopropanol, acetone or toluene or a combination of at least two of the above;
preferably, in the pretreatment liquid, the photoinitiator is 5-10% by mass.
3. The method according to claim 1 or 2, wherein the hydrophilic polymer material in step (1) is selected from any one or a combination of at least two of alginate, hyaluronic acid, agarose, chitosan, collagen, gelatin, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, sodium polyacrylate, sodium polymethacrylate, methylcellulose, or polyisopropylacrylamide;
preferably, the initiator of step (1) is selected from hydrogen abstraction type initiators, further preferably any one or a combination of at least two of benzophenone, Michler's ketone, benzophenone oxide, alkyl substituted benzophenone, thioxanthone, anthraquinone, coumarone, camphorquinone, sodium benzoate, acetophenone, p-chlorobenzophenone or benzaldehyde;
preferably, the solvent in step (1) is selected from any one of water, methanol, ethanol, acetone, formamide, N-dimethylformamide or dimethyl sulfoxide or a combination of at least two of the above.
4. The method according to any one of claims 1 to 3, wherein in the precursor solution of step (1), the hydrophilic polymer material is contained in an amount of 5 to 20% by mass;
preferably, in the precursor solution in the step (1), the mass percentage of the initiator is 0.1-2%.
5. The method according to any one of claims 1 to 4, wherein the polymeric medical device of step (2) comprises an implantable medical device or an interventional medical device;
preferably, the polymer material for the medical device is selected from any one or a combination of at least two of silicone rubber, polyethylene, polystyrene, polypropylene, polyamide, polyether block polyamide, polylactic acid, polyimide, polymethyl methacrylate or polyurethane;
preferably, the medical device comprises an artificial organ, a stent, an intravascular catheter, a guidewire or a sheath embolization device.
Preferably, the preparation method further comprises: cleaning and drying the medical instrument prior to step (2);
preferably, the solvent for cleaning comprises any one of water, ethanol, isopropanol, acetone, heptane or n-hexane or a combination of at least two of the above;
preferably, the drying is air drying, and the air drying time is 1-5 min.
6. The production method according to any one of claims 1 to 5, wherein the oxygen plasma treatment of step (2) is performed for 1 to 5 min;
preferably, the soaking time in the step (2) is 1-5 min.
7. The method for preparing according to any one of claims 1 to 6, wherein the coating in step (3) is performed by a method selected from dipping and/or spin coating;
preferably, the dipping is carried out at a pulling speed of 10 to 300 mm/min.
8. The production method according to any one of claims 1 to 7, wherein the photo-curing of step (3) is ultraviolet curing;
preferably, when the light curing is carried out, the distance between the medical instrument and the ultraviolet lamp is 10-50 mm;
preferably, the illumination intensity of the ultraviolet lamp is 0.1-2W/cm2
Preferably, the photocuring time is 1-90 min.
9. The method according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) mixing a hydrophilic high polymer material, an initiator and a solvent to obtain a precursor solution of the hydrophilic lubricating coating, wherein in the precursor solution, the mass percentage of the hydrophilic high polymer material is 5-20%, and the mass percentage of the initiator is 0.1-2%;
(2) cleaning medical instruments, and then airing for 1-5 min; carrying out oxygen plasma treatment on the cleaned medical apparatus for 1-5min, and then soaking the medical apparatus in pretreatment liquid containing a photoinitiator for 1-5 min;
(3) coating the precursor solution obtained in the step (1) on the surface of the medical instrument treated in the step (2) by a dipping or spin coating method;
(4) and (4) carrying out ultraviolet curing on the coated medical instrument obtained in the step (3) for 1-90min to obtain the polymer medical instrument with the hydrophilic lubricating coating.
10. Polymeric medical device with a hydrophilic lubricious coating prepared by the method of any one of claims 1-9.
CN202011492001.4A 2020-12-16 2020-12-16 Polymer medical instrument with hydrophilic lubricating coating and preparation method thereof Pending CN112574460A (en)

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CN113908345A (en) * 2021-10-11 2022-01-11 浙江海圣医疗器械股份有限公司 Preparation method of super-smooth hydrophilic coating
CN114344574A (en) * 2021-12-31 2022-04-15 东华大学 Hydrophilic coating with antibacterial and antifouling functions and preparation method thereof
CN114712568A (en) * 2022-06-07 2022-07-08 中国人民解放军总医院第一医学中心 Surface modified silicone rubber stomach tube and preparation method thereof
CN114748700A (en) * 2022-04-22 2022-07-15 华南理工大学 Super-hydrophilic coating for TPU coated guide wire and preparation method thereof
CN115160625A (en) * 2022-07-26 2022-10-11 华南理工大学 Method for modifying polymer catheter on surface of polyethylene glycol hydrogel

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CN103933616A (en) * 2014-03-20 2014-07-23 北京迪玛克医药科技有限公司 Method for preparing coating on surface of intervention catheter, intervention catheter and interventional device
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CN113908345A (en) * 2021-10-11 2022-01-11 浙江海圣医疗器械股份有限公司 Preparation method of super-smooth hydrophilic coating
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