CN117599254A - Method for preparing super-lubrication antibacterial medical catheter coating in one step - Google Patents
Method for preparing super-lubrication antibacterial medical catheter coating in one step Download PDFInfo
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- CN117599254A CN117599254A CN202311626280.2A CN202311626280A CN117599254A CN 117599254 A CN117599254 A CN 117599254A CN 202311626280 A CN202311626280 A CN 202311626280A CN 117599254 A CN117599254 A CN 117599254A
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- medical catheter
- antibacterial
- lubricating
- coating
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- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000005461 lubrication Methods 0.000 title description 4
- 108010039918 Polylysine Proteins 0.000 claims abstract description 18
- 229920000656 polylysine Polymers 0.000 claims abstract description 18
- 230000001050 lubricating effect Effects 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- 239000004945 silicone rubber Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- -1 (methyl) glycidyl Chemical group 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 210000004666 bacterial spore Anatomy 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- KSSQRTHVSIYTGX-UHFFFAOYSA-N n,n-dimethylprop-2-enamide;ethane-1,2-diol Chemical compound OCCO.CN(C)C(=O)C=C KSSQRTHVSIYTGX-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/041—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
- A61L29/16—Biologically active materials, e.g. therapeutic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a method for preparing a super-lubricating antibacterial medical catheter coating in one step. The super-lubricating antibacterial coating with the interpenetrating polymer network structure is obtained by adopting direct dip coating and heating curing. The modified hyperbranched polylysine containing double bonds is bonded inside a substrate network, so that the modified hyperbranched polylysine is more firmly bonded in a coating and has high-efficiency broad-spectrum antibacterial effect. The invention only needs to immerse the catheter substrate in the coating containing both lubricating and antibacterial substances, so that the catheter has remarkable lubricating and antibacterial properties. The operation is simple and easy, and the one-step dip coating is beneficial to large-scale production.
Description
Technical Field
The invention relates to a method for preparing a super-lubricating antibacterial medical catheter coating in one step, and belongs to the field of medical materials.
Background
The medical catheter is used as a component of modern medicine, and the medical quality of preventing, treating and relieving diseases is greatly improved. According to incomplete statistics, the amount of medical catheters imported per year in China exceeds 1.5 hundred million yuan, and the use amount of the medical catheters per year accounts for 8.7% of the total medical instrument amount. As a necessary tool for implantation treatment, the development of medical science in China is greatly influenced by a large number of imports of medical catheters.
The most commonly used medical catheter materials are silicone rubber, polyvinyl chloride and polyurethane. Most of the materials have hydrophobic surfaces and large friction force in the access process, can cause various complications in the clinical use process, and the catheter has no bioactivity and is difficult to inhibit continuous infection caused by local wound surfaces of the access part. Therefore, the lubricating and antibacterial coating is constructed on the surface of the medical catheter, so that tissue damage can be effectively reduced, and bacteria can be killed to reduce tissue infection.
Currently, common methods for lubricating or hydrophilically modifying the surface of medical catheters mainly comprise a silane coupling agent grafting method, a swelling embedding initiator method and a direct coating method. The silane coupling agent grafting method requires the steps of treating a substrate by plasma, heating and curing, then grafting a lubricating layer and the like, and has the limitations of complex process, uneven coating, easy damage to the surface morphology of the substrate and the like. The swelling embedding initiator method is that firstly, an oil-soluble initiator is swelled on a polymer substrate, a lubricating monomer is grafted on a surface interface through the water-soluble initiator in solution, most of the substrate treated by the method is polymerized in solution, and the problems of raw material waste and high cost exist; the direct coating method is to directly solidify the coating on the catheter to form a film, and the coating obtained by the method is easy to fall off and monomer is easy to remain. Therefore, a preparation method of a general medical catheter which is simple, easy to produce in batches and can be lubricated permanently needs to be developed.
In recent years, bactericides such as drugs, metal ions and quaternary ammonium salts have been used for producing antibacterial coatings, but many disadvantages still remain. Antibiotics and other medicines often have no broad-spectrum bactericidal activity, and coated catheters are generally low in efficiency in inhibiting biofilm formation and are easy to generate drug resistance; the metal antibacterial agent is usually silver, copper or zinc, etc., however, the continuous precipitation and accumulation of antibacterial metal ions can destroy the microenvironment balance of surrounding tissues, and generate the problems of cytotoxicity, poor biocompatibility, etc.; the quaternary ammonium salt disinfectant belongs to a low-efficiency disinfectant, can not kill microorganisms such as fungi, tubercle bacillus, hydrophilic viruses, bacterial spores and the like, has more incompatibility and is relatively expensive. Therefore, the antibacterial coating material which is safe, efficient, broad-spectrum antibacterial, stable in performance, free of biotoxicity, low in cost and free of drug resistance and the efficient preparation method are lacked.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a method for preparing a super-lubrication antibacterial medical catheter coating in one step. The super-lubricating antibacterial coating with the interpenetrating polymer network structure is obtained by adopting direct dip coating and heating curing. The modified hyperbranched polylysine containing double bonds is bonded in a substrate network to obtain the coating which has broad-spectrum antibacterial property, stable performance, firm bonding and no toxicity. The method is simple and time-saving, and has excellent effect.
The technical scheme adopted by the invention is as follows:
a method of preparing a super-lubricious antimicrobial medical catheter coating in one step, the method comprising:
dip-coating the cleaned medical catheter into the super-lubricating antibacterial coating, taking out, heating for curing, washing with water, and drying to obtain the super-lubricating antibacterial coating with the interpenetrating polymer network structure. The super-lubricating antibacterial coating comprises the following components in parts by weight: 15-20 parts of hydrophilic monomer, 5-10 parts of lubricating polymer, 3-5 parts of modified hyperbranched polylysine, 0.1-0.5 part of cross-linking agent, 0.5-1 part of initiator, 45-70 parts of organic reagent and 20-40 parts of deionized water.
Further, the medical catheter material is at least one of polyurethane, polyvinyl chloride, silicone rubber and latex.
Further, the hydrophilic monomer is selected from one or more of acrylamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate and N-methylol acrylamide.
Further, the lubricating polymer is one or more selected from polyacrylamide, polyvinylpyrrolidone, polyethylene oxide and polyvinyl alcohol.
Further, the modified hyperbranched polylysine refers to double bonds contained by soaking in a modifying agent. The modifier is one or more of (methyl) acrylic anhydride and (methyl) glycidyl acrylate aqueous solution, the concentration of the solution is 1-1.5wt%, the temperature is 37 ℃, and the soaking time is 4-6h.
Further, the cross-linking agent is one or more of N, N-methylene bisacrylamide or ethylene glycol dimethacrylate.
Further, the initiator is a thermal initiator and is at least one selected from azodiisobutyronitrile, dibenzoyl peroxide and persulfate.
Further, the organic reagent is one or more of ethanol, isopropanol, ethylene glycol and propanol.
Further, the heating curing temperature is 60-90 ℃ and the curing time is 3-9h.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for preparing a super-lubricating antibacterial medical catheter coating, which avoids the problem of raw material waste by a one-step dip-coating and solidification preparation process, and has the advantages of simple process, simplicity in operation, low cost, good repeatability and rapid realization of the preparation of the super-lubricating antibacterial coating.
2. The invention provides a method for preparing a super-lubricating antibacterial medical catheter coating by a one-step method, wherein the contained antibacterial agent is hyperbranched polylysine, and the antibacterial agent can play a role in high-efficiency broad-spectrum bacteriostasis and sterilization by destroying bacterial cell membranes, DNA, improving the level of active oxygen in bacterial cells and the like.
3. The invention provides a method for preparing a super-lubricating antibacterial medical catheter coating by a one-step method, which is characterized in that modified hyperbranched polylysine with double bonds is bonded in a network, so that the problems of cytotoxicity and the like caused by insufficient effect of low content of an antibacterial agent or precipitation and accumulation of the antibacterial agent are avoided, and the efficient and stable sterilization effect is achieved.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention clearer, the present invention provides the following drawings for embodiment 1:
FIG. 1 is a diagram showing the appearance of a lubricated, antimicrobial, modified medical catheter made in accordance with the present invention in comparison to the appearance of an uncoated, raw medical catheter;
FIG. 2 is a schematic view of a coated catheter made in accordance with the present invention;
FIG. 3 is a plate colony chart of an uncoated raw medical catheter;
FIG. 4 is a graph of plate colonies coated with a lubricious antimicrobial coating prepared in accordance with the present invention;
FIG. 5 is a graph showing the coefficient of friction of a lubricated antimicrobial modified medical catheter made in accordance with the present invention and a 30-cycle test under water with an uncoated raw medical catheter;
FIG. 6 shows hyperbranched polylysine modified at different modifier concentrations in the present invention 1 H-NMR spectrum.
Detailed Description
The following examples further illustrate the technical aspects of the present invention, but are not intended to limit the present invention.
Example 1
Hyperbranched polylysine and glycidyl methacrylate were dissolved in 4g of water to prepare a 1wt% solution, which was reacted at 37℃for 4 hours. Continuously adding 1.5g of hydroxyethyl methacrylate, 1g of polyacrylamide, 0.01g of ethylene glycol dimethyl acrylamide, 0.05g of azobisisobutyronitrile and 4.5g of ethanol, and uniformly stirring to obtain the lubricating antibacterial coating. The polyurethane catheter was immersed in the above coating, lifted after dip-coating and placed in a 60 ℃ oven for 4 hours. Taking out the catheter, soaking in ultrapure water for 1 hour, flushing for three times, and drying to obtain the medical catheter with the coating. The appearance of the medical catheter with the coating is as shown in fig. 1, and the appearance of the catheter before modification are consistent. FIG. 2 is a schematic diagram of a coated catheter prepared according to the present invention, wherein the modified hyperbranched polylysine having double bonds is bonded within the network, avoiding antimicrobial agentsAnd the cytotoxicity caused by insufficient effect or precipitation and accumulation of the antibacterial agent due to low content. According to the antibacterial method, referring to GB/T31402-2015, the super-lubricating antibacterial coating is prepared on the sheet by the same process method because the contact area of the catheter is small and the catheter is not easy to test. FIG. 3 is a plate colony pattern of an uncoated lubricious antimicrobial coating; FIG. 4 is a graph of colony counts of plates coated with a lubricious antimicrobial coating, and as can be seen from a comparison of the colony counts in FIGS. 3 and 4, the superlubricious antimicrobial coating disclosed by the invention has excellent antimicrobial properties and can inhibit colonization of the catheter surface by bacteria. FIG. 5 is a graph showing the friction coefficients of a lubricated, antibacterial and modified medical catheter and an original medical catheter tested under water for 30 cycles, and from the results, it can be seen that the friction coefficient of the catheter with the coating prepared by the invention is 0.029, the friction coefficient of the catheter without the modification is 1.625, and the coating prepared by the invention can remarkably reduce the friction coefficient and has super-lubrication property; meanwhile, the friction coefficient of the disclosed super-lubricating antibacterial coating is almost unchanged in 30 cyclic friction tests, which shows that the coating almost does not fall off and the lubricity is not attenuated. FIG. 6 shows hyperbranched polylysine modified at different modifier concentrations in the present invention 1 H-NMR spectrum. The peak positions of the vinyl methacrylate groups in FIG. 6 occur at delta=6.2-6 and 5.8-5.6ppm, N-CH in glycidyl methacrylate 2 The peak position of the group appears in delta=3.2-3.6 ppm, -CH 3 The radical peak appears at δ=1.8 ppm. With increasing amounts of glycidyl methacrylate added, the peaks have a significant tendency to increase, demonstrating successful grafting of double bonds onto hyperbranched polylysine. The above data illustrate the successful formation of super-lubricious and antimicrobial coatings by the process of the present invention.
Example 2
Hyperbranched polylysine and acrylic anhydride were dissolved in 3g of water to prepare a 1.2wt% solution, which was reacted at 37℃for 5 hours. 1.5g of acrylamide, 0.8g of polyvinylpyrrolidone, 0.02g of ethylene glycol dimethacrylate, 0.08g of benzoyl peroxide and 5.5g of isopropanol are continuously added and stirred uniformly to obtain the lubricating antibacterial coating. The polyvinyl chloride pipe was immersed in the above coating, lifted after dip-coating and placed in an 80 ℃ oven for 5 hours. Taking out the catheter, soaking in ultrapure water for 1 hour, flushing for three times, and drying to obtain the medical catheter with lubricating and antibacterial effects.
Example 3
Hyperbranched polylysine and glycidyl acrylate were dissolved in 2g of water to prepare a 1.5wt% solution, which was reacted at 37℃for 6 hours. Continuously adding 1.5g g N-vinyl pyrrolidone, 0.5g polyethylene oxide, 0.04g N, N-methylene bisacrylamide, 0.1g ammonium persulfate and 7g ethylene glycol, and uniformly stirring to obtain the lubricating antibacterial coating. The silicone rubber catheter was immersed in the above coating, lifted after dip-coating and placed in a 90 ℃ oven for 8 hours. Taking out the catheter, soaking in ultrapure water for 1 hour, flushing for three times, and drying to obtain the medical catheter with lubricating and antibacterial effects.
Claims (9)
1. The method for preparing the super-lubricating antibacterial medical catheter coating by one step is characterized by immersing the cleaned medical catheter into the super-lubricating antibacterial coating, taking out, heating for curing, washing with water and drying to obtain the super-lubricating antibacterial coating with an interpenetrating polymer network structure; the super-lubricating antibacterial coating comprises the following components in parts by weight: 15-20 parts of hydrophilic monomer, 5-10 parts of lubricating polymer, 3-5 parts of modified hyperbranched polylysine, 0.1-0.5 part of cross-linking agent, 0.5-1 part of initiator, 45-70 parts of organic reagent and 20-40 parts of deionized water.
2. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the medical catheter material is at least one of polyurethane, polyvinyl chloride, silicone rubber and latex.
3. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the hydrophilic monomer is one or more selected from the group consisting of acrylamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate and N-methylolacrylamide.
4. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the lubricating polymer is one or more selected from the group consisting of polyacrylamide, polyvinylpyrrolidone, polyethylene oxide and polyvinyl alcohol.
5. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the modified hyperbranched polylysine is prepared by soaking the hyperbranched polylysine in a modifier so that the hyperbranched polylysine contains double bonds; the modifier is one or more of (methyl) acrylic anhydride and (methyl) glycidyl acrylate aqueous solution, the concentration of the modifier solution is 1-1.5wt%, the temperature is 37 ℃, and the soaking time is 4-6h.
6. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the cross-linking agent is one or more of N, N-methylenebisacrylamide or ethylene glycol dimethacrylate.
7. The method for preparing the super-lubricating antibacterial medical catheter coating according to claim 1, wherein the initiator is a thermal initiator and is at least one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide and persulfates.
8. The method for preparing the super-lubricating antibacterial medical catheter coating according to claim 1, wherein the organic reagent is one or more of ethanol, isopropanol, ethylene glycol and propanol.
9. The method for preparing the super-lubricated antibacterial medical catheter coating according to claim 1, wherein the heating curing temperature is 60-90 ℃ and the curing time is 3-9h.
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