CN115814172B - Anti-fouling wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof - Google Patents
Anti-fouling wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof Download PDFInfo
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- CN115814172B CN115814172B CN202211524294.9A CN202211524294A CN115814172B CN 115814172 B CN115814172 B CN 115814172B CN 202211524294 A CN202211524294 A CN 202211524294A CN 115814172 B CN115814172 B CN 115814172B
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- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 27
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Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention belongs to the technical field of surface modification of medical polymer materials, and particularly relates to an anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of a medical instrument and a preparation method thereof. The invention grafts a double-network hydrogel hydrophilic coating formed by mutually penetrating a polysaccharide copolymer network and a polyampholyte copolymer network on the surface of a medical instrument, and the coating is combined with the surface of the medical instrument through covalent bonds. The prepared hydrophilic coating has a double-network structure, so that the strength and toughness of the hydrophilic coating are obviously enhanced, the friction and abrasion resistance is improved, and the zwitterionic component in the coating has extremely high hydrophilicity and protein adsorption resistance, so that the non-specific adhesion performance of the coating to protein is good. Meanwhile, the prepared hydrophilic coating is combined with the surface of the medical instrument through covalent bonds, so that the combination strength is high, and the problems of stripping, falling and the like can not occur in the using process. In addition, the prepared hydrogel coating has no effects of sensitization, cytotoxicity, rejection and the like.
Description
Technical Field
The invention belongs to the technical field of surface modification of medical polymer materials, and particularly relates to an anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of a medical instrument and a preparation method thereof.
Background
With the development of interventional medicine, implantable medical devices have been widely used in clinical treatment. The performance of implantable medical devices (e.g., catheters, electrodes, electronics, etc.) has a significant impact on the surgical procedure, operator, and patient during and after implantation. In the process of inserting the medical catheter into the airway, blood vessel, abdominal cavity, alimentary canal and other parts, the friction force between the outer wall of the catheter and the tissue is large, which causes difficult operation and even causes complications such as mucosal injury, ulcer, inflammation, edema and the like of the tissue. When being implanted for a long time, substances such as proteins, biological macromolecules and the like are adsorbed and deposited on the surface of the instrument, so that the problems of inflammation, hyperplasia, stenosis, adhesion and the like are often induced, and damage and pain are caused to a patient. The main reasons for depositing biological macromolecules such as proteins on the surface are that the protein molecules and the surface of the instrument have hydrophobic effect, electrostatic effect, hydrogen bond and other effects, and the proteins adsorbed on the surface of the instrument promote the deposition of other small molecules and cells, so that serious biofouling is formed. Therefore, constructing a hydrophilic coating on the surface of the instrument, isolating the instrument from tissues and organs, lubricating the surface of the instrument, reducing friction, and reducing adsorption and deposition of biomolecules such as proteins and the like is a key technology to be solved urgently.
The lubricant widely used clinically at present is that lubricant such as silicone oil, vaseline and the like is coated on the surface of a catheter before operation, so that the friction force between the catheter and tissues is reduced. However, since the lubricant itself is liquid or semisolid, the lubricant is unstable on the surface of the catheter, and easily flows and falls off in the friction process, so that the lubricating layer becomes thin, part of the lubricant remains in the cavity and even causes partial obstruction of the cavity, and complications are caused. Therefore, the invention patent CN110665070B is prepared by compounding poloxamer micelle with hyaluronic acid or sodium hyaluronate, coating the compound on the surface of a medical catheter to form a hydrophilic coating, reducing the water contact angle to 20 degrees and the minimum wet friction coefficient to be 0.0632. The coating is adsorbed on the surface through hydrophobic interaction with the high molecular catheter, but the technology still has the problem that the bonding force between the coating and the catheter surface is not firm enough. In order to firmly bond the hydrophilic lubricating layer with the surface, the invention patent CN110885665B adsorbs a compound containing catechol component and polyamino component as a base layer on the surface of a medical instrument, and then prepares a zwitterionic polymer containing dopamine component on the base layer to prepare the stable super-hydrophilic coating. However, most medical catheters or medical instruments are made of inert materials, chemical bonds are difficult to form with hydrophilic polymers, the binding force between the hydrophilic coating and a polymer substrate is weak, the mechanical property of the hydrophilic coating with a single network structure is poor, the coating is not resistant to friction or scraping, and risks of breakage and falling exist in the application process. The hydrophilic polymer link branches are fixed on the surface of the medical instrument by chemical reaction, so that the polymer hydrophilic coating can be firmly combined on the surface of the instrument. Such as for example. The invention patent application CN113908345A firstly photoinitiates a primer on the surface of the instrument, then coats a surface layer coating and realizes polymerization through photoinitiation, and the ultra-smooth hydrophilic coating is obtained after water swelling, and the interface of the coating is firmly combined and is not easy to fall off, but the coating is easy to break after repeated friction due to the poor breeding strength, so that the invention is not beneficial to the application under more complex conditions (such as a central venous catheter and the like), and the problem of nonspecific adsorption of protein can exist during long-term implantation in vivo. The invention patent CN111097072B utilizes a silane coupling agent to modify the surface of a high molecular instrument to obtain a reactive functional group, and then chemically bonds the hydrophilic lubricating coating on the basis to prepare the hydrophilic lubricating coating which is firmly bonded, thereby reducing the friction coefficient, reducing the friction force and preventing damage caused by friction. The lubricating layer has strong binding force with the instrument and is not easy to fall off. However, the coating has poor mechanical strength, further severely reduces mechanical properties after swelling, is easy to damage when rubbed with tissues, reduces lubricating property, and possibly has the problem of nonspecific adsorption of protein.
Meanwhile, the super-hydrophilic coating is constructed on the surface of the instrument, and the formed hydration layer is utilized to block deposition of biomolecules such as proteins, and is one of main ideas for resisting biofouling. The repeated units of the zwitterionic polymer have equivalent positive and negative charges, are generally electrically neutral, have extremely low adsorption rate of protein on the surface of the polyamphoterion, and modify the zwitterionic on the surface of the instrument to form a super-hydrophilic coating, thereby having extremely strong biofouling resisting effect. For example, the invention patent application CN114652900A grafts a polyvinyl acetate layer on the surface of a medical catheter, and then prepares a hydrogel layer copolymerized by hydrophilic monomers and zwitterionic monomers to obtain a hydrophilic coating resistant to protein adsorption, wherein the water contact angle is 20 degrees, the relative protein adsorption rate is 20 percent, but the grafted hydrophilic polymer layer has weak strength and is not resistant to friction. The invention patent CN107236143B synthesizes a block copolymer of dimethylaminoethyl methacrylate and sulfobetaine methacrylate, and ultraviolet light is crosslinked and solidified on the surface of polyurethane modified by KH570 to form a cationic-zwitterionic copolymer coating, and the prepared coating can resist 50-70% of bovine serum albumin adhesion on average and has an antibacterial effect. However, the polyzwitterionic single network is easy to excessively swell in solution or body fluid, so that the strength is greatly reduced, and the polyzwitterionic single network is easy to scratch or abrade when being rubbed, so that the lubricating property and the anti-fouling property are reduced.
In summary, the hydrophilic coating prepared by the prior method can endow the surface of the device with good lubricating performance and reduce friction, but the coating has weak anti-biofouling capability, and the bonding strength between the coating and the substrate is low, so that the risks of abrasion, abrasion and falling off exist during repeated friction; meanwhile, most of the coatings do not contain a crosslinked structure, or a crosslinked network is fragile, swells after absorbing water or body fluid, and becomes more fragile, so that the coatings are easy to wear or damage when contacting or rubbing with tissues in the use process, and further the lubricating performance is lost. Therefore, the preparation of the hydrophilic coating which has high strength and toughness and firmly combined interface and can inhibit the adsorption of nonspecific proteins on the surface of the medical instrument is a technical problem to be solved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a hydrophilic lubricating coating grafted on the surface of a medical instrument, and the prepared coating has firm bonding, high strength and toughness, good non-specific adhesion performance of lubrication and protein resistance, and can effectively solve the problems of weak biofouling resistance of the coating, lower bonding strength between the coating and a substrate and abrasion, abrasion and falling risks during repeated friction.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the invention provides a preparation method of an anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of a medical instrument, which comprises the following steps:
s1, cleaning the surface of a medical instrument, activating the surface of the instrument through plasma treatment after drying, and introducing active groups;
s2, soaking the instrument treated in the step S1 in an acidic solution of a silane coupling agent, so that the silane coupling agent reacts with functional groups on the surface of the instrument to be grafted on the surface of the instrument;
s3, firstly, preparing a coating precursor solution by using acrylic acid or methacrylic acid ester group modified polysaccharide, acrylic acid, methacrylic acid or derivatives thereof and a photoinitiator; then coating the coating precursor solution on the surface of the device treated in the step S2;
s4, the medical device containing the coating solution prepared in the step S3 is placed under blue light, ultraviolet light, X-ray or electron beam for radiation, so that the initiator and high polymer in the solution generate free radicals and react with functional groups on the surface of the device, meanwhile, free radical polymerization and crosslinking are carried out between polysaccharide and monomer, so that a crosslinking network (a polysaccharide-methacrylic acid or polysaccharide-acrylic acid copolymer network is formed on the surface of the device, and silane coupling agent functional groups on the surface of the medical device react with double bonds suspended on polysaccharide molecular chains to generate covalent bonds) is formed on the surface of the device, and a dehydrated gel coating is prepared on the surface of the device after drying and dehydration;
s5, firstly dissolving a zwitterionic monomer, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and a photoinitiator in water to prepare a solution; then soaking the device containing the dehydrated gel coating prepared in the step S4 in the solution to swell the gel coating and absorb the monomer, the cross-linking agent and the initiator solution;
s6, the device processed in the step S5 is placed under blue light, ultraviolet light, X-ray or electron beam to radiate, free radicals are initiated, free radical polymerization and cross-linking are carried out on monomers and cross-linking agents in the solution, a new network (a zwitterionic, polyethylene glycol methacrylate and hydroxyethyl methacrylate copolymer network) is formed in the network formed in the step S4, and therefore the anti-fouling wear-resistant hydrophilic lubricating coating is prepared on the surface of the medical device.
The invention firstly modifies reactive functional groups such as double bonds on the surface of a medical instrument, then grafts hydrophilic polymer crosslinked network, introduces a second network monomer containing amphoteric ions into the hydrophilic polymer crosslinked network, and prepares a second network after in-situ polymerization, thereby obtaining the polyamphoteric hydrophilic double-network hydrogel grafted on the surface of the medical instrument and obtaining the high-strength and high-toughness anti-fouling hydrophilic lubricating coating.
Preferably, in step S5, the zwitterionic monomer comprises one or more of 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate.
Preferably, the composition of the solution in step S5 is: 0.5 to 30 weight percent of zwitterionic monomer, 0.5 to 20 weight percent of polyethylene glycol methacrylate, 0.01 to 0.5 weight percent of polyethylene glycol dimethacrylate, 0.5 to 18 weight percent of hydroxyethyl methacrylate, 0.01 to 0.05 weight percent of photoinitiator and the balance of water.
Preferably, in step S3, the polysaccharide modified with acrylate or methacrylate groups includes alginic acid methacrylate, chitosan methacrylate, hyaluronic acid methacrylate, chondroitin sulfate methacrylate, dextran methacrylate.
Preferably, in the coating precursor solution of step S3, the concentration of the polysaccharide is 0.3wt% to 5wt%, the concentration of the acrylic acid, methacrylic acid or derivatives thereof is 0.5wt% to 3wt%, the concentration of the photoinitiator is 0.01 to 0.05wt%, and the balance is water.
Preferably, in step S2, the silane coupling agent is one or more of vinyltriacetoxy silane (a-151), vinyltrimethoxysilane (a-171), vinyltris (ethoxymethoxy) silane (a-172), and γ -methacryloxypropyl trimethoxysilane (a-174).
Preferably, in the step S2, the silane coupling agent acid solution comprises 0.5-7wt% of silane coupling agent, 2-12% of water and the balance of ethanol; the pH value of the solution is 3.0-5.8 (the pH value of the silane coupling agent solution is adjusted by adopting dilute hydrochloric acid or dilute acetic acid).
Preferably, the irradiation time of step S4 is 3S-60min; the irradiation time in the step S6 is 3S-30min.
Preferably, in step S1, the plasma treatment includes an oxygen plasma treatment and an ammonia plasma treatment to introduce reactive groups such as carboxyl groups, hydroxyl groups, or amino groups.
Preferably, in step S1, the medical device is made of any one of silica gel, polydimethylsiloxane, polyvinyl chloride, polyurethane, polypropylene, polyethylene terephthalate, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, and copolyester EcoFlex.
Preferably, the soaking time in the steps S2 and S5 is 5-180 min.
Preferably, in the step S4, the drying and dehydration is freeze-drying and dehydration, the temperature of the freeze-drying and dehydration is between-4 ℃ and-20 ℃, the time is between 30 and 120 minutes, and the water content in the coating after dehydration is between 0 and 5 weight percent.
Preferably, the photoinitiator described in step S3 and step S5 is I2959.
In another aspect, the invention provides an anti-fouling and wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device, which is prepared by the preparation method in the first aspect.
The coating prepared by the invention is a hydrogel coating and consists of a polysaccharide network and a polydiionic copolymer network which are mutually penetrated, wherein the polysaccharide network is a polysaccharide-acrylic acid or polysaccharide-methacrylic acid copolymer, the polydiionic copolymer network is an amphiphilic monomer, polyethylene glycol methacrylate or hydroxyethyl methacrylate copolymer network, and the hydrogel network coating and the surface of a medical instrument are combined through covalent bonds (the propenyl or the methylpropenyl of the polysaccharide network and the surface of the medical instrument form covalent bonds). The prepared zwitterionic component in the hydrogel coating has extremely high hydrophilicity and protein adsorption resistance, reduces the water contact angle of the surface of the instrument to 7.8, remarkably reduces the protein adsorption rate, remarkably reduces the wet friction coefficient of the surface of the instrument, can reach 0.063 at the minimum, remarkably reduces the friction force between the instrument and human tissues, and reduces the friction and damage to the tissues and organs caused by the movement of the instrument in the human body.
Compared with the prior art, the invention has the beneficial effects that:
the invention grafts a double-network hydrogel hydrophilic coating formed by mutually penetrating a polysaccharide copolymer network (polysaccharide-acrylic acid or polysaccharide-methacrylic acid copolymer) and a polyzwitterionic copolymer network (amphiphilic monomer, polyethylene glycol methacrylate and hydroxyethyl methacrylate copolymer network) on the surface of a medical instrument, and the coating and the surface of the medical instrument are combined through covalent bonds (propenyl or methylpropenyl of the polysaccharide network and the surface of the medical instrument form covalent bonds). The prepared hydrophilic coating has a double-network structure, so that the strength and toughness of the hydrophilic coating are obviously enhanced, the friction and abrasion resistance is improved, and the zwitterionic component in the coating has extremely high hydrophilicity and protein adsorption resistance, so that the non-specific adhesion performance of the coating to protein is good. Meanwhile, the prepared hydrophilic coating is combined with the surface of the medical instrument through covalent bonds, so that the combination strength of the hydrophilic coating and the surface of the instrument is high, and the problems of stripping, falling and the like can not occur in the using process. In addition, no cytotoxic or biotoxic substance is used in the surface treatment process of the medical apparatus, the polysaccharide polymer used has good biosafety, the cytotoxicity of the monomer used is low, and the prepared hydrogel coating has no effects of sensitization, cytotoxicity, rejection and the like. Therefore, the hydrophilic coating prepared by the method has important application value in the aspect of implantable medical devices.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
Alginic acid methacrylate, chitosan methacrylate, hyaluronic acid methacrylate, chondroitin sulfate methacrylate, dextran methacrylate in the following examples were purchased from Shenzhen Huano biosciences, inc.
Example 1 preparation method of high-toughness wear-resistant hydrophilic coating on surface of medical instrument
The preparation method comprises the following steps:
(1) Sequentially ultrasonically cleaning the surface of a medical instrument (a central venous catheter made of polyurethane) for 3 minutes by isopropanol, acetone, absolute ethyl alcohol and deionized water respectively, and drying by nitrogen; the cleaned medical apparatus is placed in an oxygen plasma (model: PT-10Plus, shenzhen Sanand Boda electro-mechanical technologies Co., ltd.) atmosphere for 30 minutes (power 200w, oxygen is pure oxygen) to generate active groups such as hydroxyl and carboxyl on the surface. In the present embodiment, the medical device to be applied is not limited to the polyurethane central venous catheter.
(2) And (3) placing the medical device treated in the step (1) in an acidic solution of a newly prepared silane coupling agent, soaking for 2 hours, hydrolyzing the silane coupling agent positioned on the surface of the device, and simultaneously performing condensation reaction with hydroxyl groups, carboxyl groups and the like on the surface of the device, so that the silane coupling agent molecules and hydrolysis condensation products thereof are grafted on the surface. The preparation method of the silane coupling agent acid solution comprises the following steps: 0.5wt% of a silane coupling agent a151, 2wt% of deionized water and 97.5wt% of absolute ethanol were uniformly mixed, and A1 mol/L hydrochloric acid solution was added dropwise to the uniform silane coupling agent solution while stirring, and ph=3.0 of the solution was adjusted. After the reaction is finished, the surface of the reaction product is sequentially washed by absolute ethyl alcohol and deionized water for 3 minutes respectively, so as to remove the silane coupling agent and the ethyl alcohol adsorbed on the surface.
(3) Firstly, alginic acid methacrylate, acrylic acid and a photoinitiator 2959 are dissolved in deionized water to prepare colorless and transparent hydrophilic coating precursor solution. The composition of the solution is: 2wt% alginic acid methacrylate, 0.5wt% acrylic acid, 0.01wt% photoinitiator 2959 (I2959), the balance deionized water. Then coating the prepared hydrophilic coating precursor solution on the surface of the medical instrument grafted with the silane coupling agent in the step (2), and irradiating for 15 minutes by using 365nm ultraviolet light to decompose I2959 to generate free radicals, so as to initiate free radical reaction, and make double bonds on the silane coupling agent on the surface of the medical instrument and alginic acid methacrylate and acrylic acid on the near surface generate copolymerization to form covalent bonds; meanwhile, double bonds in alginic acid methacrylate in the hydrophilic coating are copolymerized with acrylic acid and crosslinked to generate a crosslinked network structure, and finally, a covalent-bonding hydrophilic gel coating is formed on the surface of the medical instrument.
(4) And (3) placing the medical device coated with the hydrophilic coating in the step (3) in a freeze dryer (LGJ-10C, tetracyclic Furicida) for drying in vacuum at-50 ℃ for 48 hours, and removing water in the surface hydrophilic coating.
(5) Immersing the medical device treated in the step (4) in an aqueous solution containing 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and a photoinitiator 2959 for 2 hours, swelling the coating on the surface of the device and absorbing the aqueous solution containing 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and the photoinitiator 2959. The composition of the aqueous solution used in this step is: 0.5wt% of 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate, 1wt% of polyethylene glycol methacrylate, 0.05wt% of polyethylene glycol dimethacrylate, 0.5wt% of hydroxyethyl methacrylate, 0.01wt% of photoinitiator and the balance of deionized water.
(6) And (3) placing the medical device treated in the step (5) under 365nm ultraviolet light for irradiation for 30min, and initiating free radical polymerization to form an interpenetrating hydrophilic network structure.
(7) And (3) sequentially ultrasonically cleaning the medical instrument treated in the step (6) with absolute ethyl alcohol and deionized water for 3 minutes to prepare the high-strength and high-toughness hydrophilic lubricating coating grafted on the surface of the medical instrument.
Example 2 preparation method of high-toughness wear-resistant hydrophilic coating on surface of medical instrument
The preparation method comprises the following steps:
(1) Cleaning the surface of the medical device and treating the surface with oxygen plasma in the same way as in example 1;
(2) And (3) placing the medical device treated in the step (1) in an acidic solution of a newly prepared silane coupling agent, soaking for 2 hours, hydrolyzing the silane coupling agent positioned on the surface of the device, and simultaneously performing condensation reaction with hydroxyl groups, carboxyl groups and the like on the surface of the device, so that the silane coupling agent molecules and hydrolysis condensation products thereof are grafted on the surface. The preparation method of the silane coupling agent acid solution comprises the following steps: 2wt% of a silane coupling agent A171, 5wt% of deionized water and 93wt% of absolute ethyl alcohol were uniformly mixed, and A1 mol/L hydrochloric acid solution was added dropwise to the uniform silane coupling agent solution while stirring, and the pH of the solution was adjusted to 3.0 to 5.8. After the reaction is finished, sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water to remove the silane coupling agent and the ethyl alcohol adsorbed on the surface.
(3) Chitosan methacrylate, acrylic acid and a photoinitiator 2959 are dissolved in deionized water to prepare colorless and transparent hydrophilic coating precursor solution. The composition of the solution is: 2wt% of chitosan methacrylate, 1wt% of acrylic acid, 0.01wt% of photoinitiator 2959 and the balance of deionized water. Then coating the prepared hydrophilic coating precursor solution on the surface of the medical instrument grafted with the silane coupling agent in the step (2), and irradiating with 365nm ultraviolet light to decompose I2959 to generate free radicals, so as to initiate free radical reaction, and copolymerizing double bonds on the silane coupling agent on the surface of the medical instrument with alginic acid methacrylate and acrylic acid on the near surface to form covalent bonds; meanwhile, double bonds in alginic acid methacrylate in the hydrophilic coating are copolymerized with acrylic acid and crosslinked to generate a crosslinked network structure, and finally, a covalent-bonding hydrophilic gel coating is formed on the surface of the medical instrument.
(4) The drying treatment was the same as in example 1;
(5) Immersing the medical device treated in the step (4) in an aqueous solution containing 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and a photoinitiator 2959 for 2 hours, swelling the coating on the surface of the device and absorbing the aqueous solution containing 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and the photoinitiator 2959. The composition of the aqueous solution used in this step is: 15wt% of 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate, 10wt% of polyethylene glycol methacrylate, 0.5wt% of polyethylene glycol dimethacrylate, 1wt% of hydroxyethyl methacrylate, 0.01wt% of a photoinitiator and the balance of deionized water.
(6) And (3) placing the medical device treated in the step (5) under the electron beam of 0.5MeV for irradiation for 3s, and initiating free radical polymerization to form an interpenetrating hydrophilic network structure.
(7) And (3) ultrasonically cleaning the medical instrument treated in the step (6) by using absolute ethyl alcohol and deionized water in sequence to prepare the high-strength and high-toughness hydrophilic lubricating coating grafted on the surface of the medical instrument.
Example 3 preparation method of high-toughness wear-resistant hydrophilic coating on surface of medical instrument
The preparation method comprises the following steps:
(1) Cleaning the surface of the medical device and treating the surface with oxygen plasma in the same way as in example 1;
(2) And (3) placing the medical device treated in the step (1) in an acidic solution of a newly prepared silane coupling agent, soaking for 2 hours, hydrolyzing the silane coupling agent positioned on the surface of the device, and simultaneously performing condensation reaction with hydroxyl groups, carboxyl groups and the like on the surface of the device, so that the silane coupling agent molecules and hydrolysis condensation products thereof are grafted on the surface. The preparation method of the silane coupling agent acid solution comprises the following steps: 7wt% of a silane coupling agent A172, 5wt% of deionized water and 88wt% of absolute ethyl alcohol are uniformly mixed, 1mol/L hydrochloric acid solution is added dropwise into the uniform silane coupling agent solution while stirring, and the pH of the solution is adjusted to be 3.0-5.8. After the reaction is finished, sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water to remove the silane coupling agent and the ethyl alcohol adsorbed on the surface.
(3) Hyaluronic acid methacrylate, acrylic acid and a photoinitiator 2959 are dissolved in deionized water to prepare colorless and transparent hydrophilic coating precursor solution. The composition of the solution is: 0.3wt% hyaluronic acid methacrylate, 0.5wt% methacrylic acid, 0.01wt% photoinitiator 2959, the balance deionized water. Then coating the prepared hydrophilic coating precursor solution on the surface of the medical instrument grafted with the silane coupling agent in the step (2), and irradiating with 365nm ultraviolet light to decompose I2959 to generate free radicals, so as to initiate free radical reaction, and copolymerizing double bonds on the silane coupling agent on the surface of the medical instrument with alginic acid methacrylate and acrylic acid on the near surface to form covalent bonds; meanwhile, double bonds in alginic acid methacrylate in the hydrophilic coating are copolymerized with acrylic acid and crosslinked to generate a crosslinked network structure, and finally, a covalent-bonding hydrophilic gel coating is formed on the surface of the medical instrument.
(4) The drying treatment was the same as in example 1;
(5) Immersing the medical device treated in the step (4) in an aqueous solution containing 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and a photoinitiator 2959 for 2 hours, swelling the coating on the surface of the device and absorbing the aqueous solution containing 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and the photoinitiator 2959. The composition of the aqueous solution used in this step is: 30wt% of 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate, 0.5wt% of polyethylene glycol methacrylate, 0.5wt% of polyethylene glycol dimethacrylate, 0.5wt% of hydroxyethyl methacrylate, 0.05wt% of photoinitiator and the balance of deionized water.
(6) And (3) placing the medical device treated in the step (5) under 365nm ultraviolet light for irradiation for 20min, and initiating free radical polymerization to form an interpenetrating hydrophilic network structure.
(7) And (3) ultrasonically cleaning the medical instrument treated in the step (6) by using absolute ethyl alcohol and deionized water in sequence to prepare the high-strength and high-toughness hydrophilic lubricating coating grafted on the surface of the medical instrument.
Example 4 preparation method of high-toughness wear-resistant hydrophilic coating on surface of medical instrument
The preparation method comprises the following steps:
(1) Cleaning the surface of the medical device and treating the surface with oxygen plasma in the same way as in example 1;
(2) And (3) placing the medical device treated in the step (1) in an acidic solution of a newly prepared silane coupling agent, soaking for 2 hours, hydrolyzing the silane coupling agent positioned on the surface of the device, and simultaneously performing condensation reaction with hydroxyl groups, carboxyl groups and the like on the surface of the device, so that the silane coupling agent molecules and hydrolysis condensation products thereof are grafted on the surface. The preparation method of the silane coupling agent acid solution comprises the following steps: 3wt% of a silane coupling agent A174, 3wt% of deionized water and 94wt% of absolute ethyl alcohol are uniformly mixed, 1mol/L hydrochloric acid solution is added dropwise into the uniform silane coupling agent solution while stirring, and the pH of the solution is adjusted to be 3.0-5.8. After the reaction is finished, sequentially carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water to remove the silane coupling agent and the ethyl alcohol adsorbed on the surface.
(3) Chondroitin sulfate methacrylate, acrylic acid and a photoinitiator 2959 are dissolved in deionized water to prepare a colorless transparent hydrophilic coating precursor solution. The composition of the solution is: 3wt% chondroitin sulfate methacrylate, 1wt% methacrylic acid, 0.05wt% photoinitiator 2959, and the balance deionized water. Then coating the prepared hydrophilic coating precursor solution on the surface of the medical instrument grafted with the silane coupling agent in the step (2), and irradiating with 365nm ultraviolet light to decompose I2959 to generate free radicals, so as to initiate free radical reaction, and copolymerizing double bonds on the silane coupling agent on the surface of the medical instrument with alginic acid methacrylate and acrylic acid on the near surface to form covalent bonds; meanwhile, double bonds in alginic acid methacrylate in the hydrophilic coating are copolymerized with acrylic acid and crosslinked to generate a crosslinked network structure, and finally, a covalent-bonding hydrophilic gel coating is formed on the surface of the medical instrument.
(4) The drying treatment was the same as in example 1;
(5) Immersing the medical device treated in step (4) in an aqueous solution containing 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and a photoinitiator 2959 for 2 hours, swelling the coating on the surface of the device and absorbing the aqueous solution containing 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and the photoinitiator 2959. The composition of the aqueous solution used in this step is: 5wt% of 3- [ N, N-dimethyl- [2- (2-methylprop-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt, 20wt% of polyethylene glycol methacrylate, 0.5wt% of polyethylene glycol dimethacrylate, 0.5wt% of hydroxyethyl methacrylate, 0.05wt% of photoinitiator and the balance of deionized water.
(6) And (3) placing the medical device treated in the step (5) under 365nm ultraviolet light for irradiation for 10min, and initiating free radical polymerization to form an interpenetrating hydrophilic network structure.
(7) And (3) ultrasonically cleaning the medical instrument treated in the step (6) by using absolute ethyl alcohol and deionized water in sequence to prepare the high-strength and high-toughness hydrophilic lubricating coating grafted on the surface of the medical instrument.
Example 5 preparation method of high-toughness wear-resistant hydrophilic coating on surface of medical instrument
The preparation method comprises the following steps:
(1) Cleaning the surface of the medical device and treating the surface with oxygen plasma in the same way as in example 4;
(2) The procedure for grafting silane coupling agent molecules was as in example 4;
(3) Dextran methacrylate, acrylic acid and a photoinitiator 2959 are dissolved in deionized water to prepare a colorless transparent hydrophilic coating precursor solution. The composition of the solution is: 5wt% dextran methacrylate, 2wt% methacrylic acid, 0.05wt% photoinitiator 2959, the remainder being deionized water. Then coating the prepared hydrophilic coating precursor solution on the surface of the medical instrument grafted with the silane coupling agent in the step (2), and irradiating with 365nm ultraviolet light to decompose I2959 to generate free radicals, so as to initiate free radical reaction, and copolymerizing double bonds on the silane coupling agent on the surface of the medical instrument with alginic acid methacrylate and acrylic acid on the near surface to form covalent bonds; meanwhile, double bonds in alginic acid methacrylate in the hydrophilic coating are copolymerized with acrylic acid and crosslinked to generate a crosslinked network structure, and finally, a covalent-bonding hydrophilic gel coating is formed on the surface of the medical instrument.
(4) The drying treatment was the same as in example 4;
(5) Immersing the medical device treated in the step (4) in an aqueous solution containing 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and a photoinitiator 2959 for 2 hours, swelling the coating on the surface of the device and absorbing the aqueous solution containing 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, hydroxyethyl methacrylate and the photoinitiator 2959. The composition of the aqueous solution used in this step is: 12 weight percent of 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, 10 weight percent of polyethylene glycol methacrylate, 0.1 weight percent of polyethylene glycol dimethacrylate, 2 weight percent of hydroxyethyl methacrylate, 0.02 weight percent of photoinitiator and the balance of deionized water.
(6) Initiating free radical polymerization as in example 4;
(7) And (3) ultrasonically cleaning the medical instrument treated in the step (6) by using absolute ethyl alcohol and deionized water in sequence to prepare the high-strength and high-toughness hydrophilic lubricating coating grafted on the surface of the medical instrument.
Comparative example 1 medical device with surface not modified by grafting
The surface of the medical instrument is sequentially ultrasonically cleaned by isopropanol, acetone, absolute ethyl alcohol and deionized water, and is dried by nitrogen, so that the medical instrument (blank control) with the surface not grafted and modified is obtained.
Comparative example 2A method for preparing a hydrophilic coating on a medical device surface
The preparation method comprises the following steps:
(1) Sequentially ultrasonically cleaning the surface of the medical instrument by isopropanol, acetone, absolute ethyl alcohol and deionized water, and blow-drying by nitrogen;
step (2) to step (7) are the same as in example 1, and a hydrophilic coating is prepared on the surface of the medical device.
Comparative example 3A method for preparing a hydrophilic coating on a medical device surface
The preparation process is identical to example 5, except that step (2) of grafting the silane coupling agent molecule is absent.
Comparative example 4A method of preparing a hydrophilic coating on a medical device surface
(1) Cleaning the surface of the medical device and treating the surface with oxygen plasma in the same way as in example 3;
(2) The procedure for grafting silane coupling agent molecules was as in example 3;
(3) The method of immersing the hydrophilic coating precursor solution and initiating the radical reaction is the same as in example 3, eventually forming a covalently bonded hydrophilic gel coating on the surface of the medical device.
Comparative example 5A method of preparing a hydrophilic coating on a medical device surface
The preparation method is the same as in example 4, except that step (3) of preparing a covalently bonded hydrophilic gel coating is absent, and step (4) of drying treatment is absent.
Comparative example 6A method of preparing a hydrophilic coating on a medical device surface
The preparation was identical to example 5, except that the solution of step (5) was free of zwitterionic monomer (2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate).
Experimental example 1 Performance test of surface coating of medical device
(1) Hydrophilic performance test:
the samples prepared in examples 1 to 5 and comparative examples 1 to 6 were placed on a sample stage of a water contact angle analyzer (Bei Ta DSA-X Roll, china) and 2. Mu.l of deionized water was dropped on the surface thereof, and the contact angle of the water drop with the surface was measured. Seven measurements were made at different locations on each sample and the measured water contact angles were averaged. The results are shown in Table 1.
As can be seen from Table 1, the water contact angles of examples 1-5 are all below 20, well below 93.1 for the clean medical device surface of comparative example 1; comparative examples 2 and 3 show that the excellent hydrophilicity of the dual network hydrogel coatings is independent of their degree of grafting to the medical device surface, and depends primarily on the composition of the coating; the water contact angle of comparative example 4 is 17.2 °, indicating that the polysaccharide network, in particular the hyaluronic acid network itself, also has good hydrophilic properties; the water contact angle of comparative example 5 was 16.9 °, indicating that the polyzwitterionic hydrogel network possesses excellent hydrophilic properties; the water contact angle of the double-network hydrogel coating of comparative example 6 is 26.4 degrees and is larger than that of examples 1-5, which indicates that the polyzwitterionic network in the double-network hydrogel is a key for obviously reducing the water contact angle of the surface of the coating and improving the hydrophilic performance of the coating.
TABLE 1 results of hydrophilic Performance test of device-modifying coatings
| Sample numbering | Water contact angle (°) |
| Example 1 | 15.2 |
| Example 2 | 11.5 |
| Example 3 | 7.8 |
| Example 4 | 16.7 |
| Example 5 | 14.3 |
| Comparative example 1 | 93.1 |
| Comparative example 2 | 18.2 |
| Comparative example 3 | 17.6 |
| Comparative example 4 | 17.2 |
| Comparative example 5 | 16.9 |
| Comparative example 6 | 26.4 |
(2) Friction coefficient test:
the coefficient of friction of the medical device and its surface coatings was measured using a rotary rheometer and the wet coefficient of friction of the surface finish coatings (samples prepared in examples 1-5 and comparative examples 1-6) was measured using a An Dongpa MCR302 rheometer platform. The test piece was fixed on a glass plate, placed in a solution tank of a rotary rheometer, the plate was pressed against the surface of the sample with deionized water as a lubricating liquid, the positive pressure load was 0.6N, the rotor was rotated unidirectionally at a rotational speed of 1mm/s, the friction force was measured, and the friction coefficient was calculated, and the test results were shown in Table 2.
As can be seen from the test results of table 2, the polysaccharide coating and the zwitterionic coating significantly reduced the coefficient of friction of the medical device surface; comparative example 1 shows that the coefficient of friction of the clean medical device surface is 0.681, comparative example 4 shows that the coefficient of friction is reduced to 0.094 after the medical device surface is modified with the hyaluronic acid coating, comparative example 5 shows that the coefficient of friction is reduced to 0.077 after the medical device surface is modified with the polyzwitterionic coating, comparative example 2 and comparative example 3 show that the coefficient of friction is reduced to 0.073 and 0.081 after the medical device surface is modified with the polysaccharide/polyzwitterionic dual-network hydrogel, comparative example 6 shows that the coefficient of friction is 0.387 for the polysaccharide/poly (ethylene glycol-hydroxyethyl methacrylate) copolymer dual-network hydrogel coating, indicating that the polyzwitterionic component in the dual-network hydrogel is a key factor for obtaining super-hydrophilic lubrication characteristics. Thus, examples 1-5 all exhibited very low coefficients of friction, with very good lubricating properties.
Table 2 results of coefficient of friction test of instrument trim coatings
| Sample numbering | Coefficient of friction |
| Example 1 | 0.102 |
| Example 2 | 0.093 |
| Example 3 | 0.063 |
| Example 4 | 0.078 |
| Example 5 | 0.082 |
| Comparative example 1 | 0.681 |
| Comparative example 2 | 0.073 |
| Comparative example 3 | 0.081 |
| Comparative example 4 | 0.094 |
| Comparative example 5 | 0.077 |
| Comparative example 6 | 0.387 |
(3) Protein adsorption test:
by quartz crystal microbalance (Tatsuro, goda, yuji, et al, interaction of Protein Adsorption through Its Intrinsic Electric Charges: A Comparative Study Using a Field-Effect Transistor, surface Plasmon Resonance, and Quartz Crystal Microbalance [ J ]]Langmuir,2012,28 (41): 14730-14738) for measuring the adsorption of proteins on the surfaces of medical instruments, polysaccharide/polyzwitterionic double-network hydrogel coating and polysaccharide/poly (ethylene glycol-hydroxyethyl methacrylate) copolymer double-network hydrogel coating, and after treating the surfaces with 100% human serum for 10 minutes, the average mass of proteins adsorbed per unit area of the surfaces was measured. Test results show that, on a medical device-like surface,the protein adsorption amount is about 573ng/cm 2 On the surface of the polysaccharide/poly (ethylene glycol-hydroxyethyl methacrylate) copolymer double-network hydrogel coating, the protein adsorption capacity is about 265ng/cm 2 On the surface of the polysaccharide/polyzwitterionic double-network hydrogel coating, the protein adsorption quantity is less than 75ng/cm 2 。
(4) Abrasion resistance test:
to evaluate the abrasion resistance of the hydrophilic coating, test pieces prepared in examples 1 to 5 and comparative examples 2 to 6 were subjected to a one-way frictional abrasion test in water using a spherical indenter under a load of 2.16N, and abrasion was observed. The test results show that the surface of the examples 1-5 is subjected to 500 friction tests, and the surface appearance is not changed obviously. The surface of the device in comparative example 2 is not activated by plasma, has no functional group, has no covalent bond combination between the surface and the coating, and the coating is broken and falls off after 10 times of friction; the surface of the comparative example 3 is not modified by the silane coupling agent, the acting force between the coating and the surface of the instrument is weak, and the coating is damaged and falls off after being rubbed for 14 times; comparative examples 4 and 5 each contained only a single network hydrogel coating, which was covalently bonded to the instrument surface, but the coating itself was poor in mechanical properties and failed after several rubs; the coating of the comparative example 6 has good strength and toughness, is combined with the surface of the instrument in a covalent bond, and still keeps the coating intact after 500 times of friction test, and is not damaged or shed.
From the test results, the double-network polyzwitterionic hydrogel coating prepared by the method is firmly combined with the surface of a medical instrument, has good hydrophilicity, low friction coefficient, good lubricating property and good protein-resistant non-specific adhesion performance, and has high strength and toughness and friction and abrasion resistance. The hydrophilic coating prepared by the method has important application value in the aspect of implantable medical devices.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. The preparation method of the anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of the medical device is characterized by comprising the following steps of:
s1, cleaning the surface of a medical instrument, activating the surface of the instrument through plasma treatment after drying, and introducing active groups;
s2, soaking the instrument treated in the step S1 in an acidic solution of a silane coupling agent, so that the silane coupling agent reacts with functional groups on the surface of the instrument to be grafted on the surface of the instrument;
s3, firstly, preparing a coating precursor solution by using acrylic acid or methacrylic acid ester group modified polysaccharide, acrylic acid, methacrylic acid or derivatives thereof and a photoinitiator; then coating the coating precursor solution on the surface of the device treated in the step S2;
s4, the medical device containing the coating solution prepared in the step S3 is placed under the radiation of blue light, ultraviolet light, X-ray or electron beam, so that the initiator and high polymer in the solution generate free radicals and react with functional groups on the surface of the device, and meanwhile, free radical polymerization and crosslinking are carried out between polysaccharide and monomer, so that a crosslinked network is formed on the surface of the device, and a dehydrated gel coating is prepared on the surface of the device after drying and dehydration;
s5, firstly dissolving a zwitterionic monomer, a cross-linking agent and a photoinitiator in water to prepare a solution, wherein the cross-linking agent consists of polyethylene glycol methacrylate, polyethylene glycol dimethacrylate and hydroxyethyl methacrylate; then soaking the device containing the dehydrated gel coating prepared in the step S4 in the solution to swell the gel coating and absorb the monomer, the cross-linking agent and the initiator solution;
s6, placing the device processed in the step S5 under blue light, ultraviolet light, X-ray or electron beam to radiate, triggering free radicals to enable monomers and cross-linking agents in the solution to undergo free radical polymerization and cross-linking, and forming a new network in the network formed in the step S4, so that the anti-fouling wear-resistant hydrophilic lubricating coating is prepared on the surface of the medical device.
2. The method of claim 1, wherein in step S5, the zwitterionic monomer is selected from one or more of 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 3- [ N, N-dimethyl- [2- (2-methylpropan-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonate, and 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate.
3. The method for preparing an anti-fouling and wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device according to claim 1, wherein the composition of the solution in step S5 is as follows: 0.5 to 30 weight percent of zwitterionic monomer, 0.5 to 20 weight percent of polyethylene glycol methacrylate, 0.01 to 0.5 weight percent of polyethylene glycol dimethacrylate, 0.5 to 18 weight percent of hydroxyethyl methacrylate, 0.01 to 0.05 weight percent of photoinitiator and the balance of water.
4. The method for preparing an anti-fouling and wear-resistant hydrophilic lubricating coating grafted on a surface of a medical device according to claim 1, wherein in the step S3, the polysaccharide modified by acrylate or methacrylate groups is selected from alginic acid methacrylate, chitosan methacrylate, hyaluronic acid methacrylate, chondroitin sulfate methacrylate or dextran methacrylate.
5. The method for preparing an anti-fouling and wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device according to claim 1, wherein the concentration of polysaccharide in the coating precursor solution in the step S3 is 0.3-5 wt%, the concentration of acrylic acid, methacrylic acid or derivatives thereof is 0.5-3 wt%, the concentration of photoinitiator is 0.01-0.05 wt%, and the balance is water.
6. The method for preparing an anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device according to claim 1, wherein in the step S2, the silane coupling agent is one or more of vinyl triacetoxy silane (a-151), vinyl trimethoxy silane (a-171), vinyl tris (ethoxymethoxy) silane (a-172) and gamma-methacryloxypropyl trimethoxy silane (a-174).
7. The method for preparing an anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device according to claim 1, wherein in step S2, the composition of the silane coupling agent acidic solution is as follows: 0.5 to 7 weight percent of silane coupling agent, 2 to 12 percent of water and the balance of ethanol; the pH value of the solution is 3.0-5.8.
8. The method for preparing the anti-fouling wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device according to claim 1, wherein the irradiation time in the step S4 is 3S-60min; the irradiation time in the step S6 is 3S-30min.
9. The method of claim 1, wherein in step S1, the plasma treatment comprises oxygen plasma treatment and ammonia plasma treatment to introduce carboxyl, hydroxyl or amino active groups.
10. An anti-fouling and wear-resistant hydrophilic lubricating coating grafted on the surface of a medical device, which is prepared by the preparation method according to any one of claims 1 to 9.
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