CN112341851A - Mixed charge polymer coating and method of polymer coating - Google Patents
Mixed charge polymer coating and method of polymer coating Download PDFInfo
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- CN112341851A CN112341851A CN202011170502.0A CN202011170502A CN112341851A CN 112341851 A CN112341851 A CN 112341851A CN 202011170502 A CN202011170502 A CN 202011170502A CN 112341851 A CN112341851 A CN 112341851A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 68
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 44
- 239000002861 polymer material Substances 0.000 claims abstract description 64
- 239000000178 monomer Substances 0.000 claims abstract description 55
- 125000000129 anionic group Chemical group 0.000 claims abstract description 48
- 125000002091 cationic group Chemical group 0.000 claims abstract description 48
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 34
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
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- 230000004048 modification Effects 0.000 claims description 9
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- 125000000524 functional group Chemical group 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 description 24
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- 241000589517 Pseudomonas aeruginosa Species 0.000 description 14
- 206010041925 Staphylococcal infections Diseases 0.000 description 13
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 13
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- 238000000338 in vitro Methods 0.000 description 10
- PNOXUQIZPBURMT-UHFFFAOYSA-M potassium;3-(2-methylprop-2-enoyloxy)propane-1-sulfonate Chemical compound [K+].CC(=C)C(=O)OCCCS([O-])(=O)=O PNOXUQIZPBURMT-UHFFFAOYSA-M 0.000 description 10
- -1 quaternary ammonium salt cations Chemical class 0.000 description 8
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 8
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 8
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- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 3
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- 229960003085 meticillin Drugs 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 2
- 241000588626 Acinetobacter baumannii Species 0.000 description 1
- 241000194033 Enterococcus Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191963 Staphylococcus epidermidis Species 0.000 description 1
- 108010059993 Vancomycin Proteins 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- YZBQHRLRFGPBSL-RXMQYKEDSA-N carbapenem Chemical compound C1C=CN2C(=O)C[C@H]21 YZBQHRLRFGPBSL-RXMQYKEDSA-N 0.000 description 1
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- 230000002572 peristaltic effect Effects 0.000 description 1
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- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960003165 vancomycin Drugs 0.000 description 1
- MYPYJXKWCTUITO-LYRMYLQWSA-N vancomycin Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-N 0.000 description 1
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials For Medical Uses (AREA)
Abstract
A mixed charge polymer coating comprising an anionic monomer, a cationic monomer, and a solution for dissolving the anionic monomer, the cationic monomer. The invention also provides a mixed charge polymer coating method, which comprises the following coating steps: respectively cleaning the surface of a polymer material to be grafted by using methanol and distilled water, and then carrying out vacuum drying treatment; after vacuum drying, the surface of the polymer material is treated by ozone gas; putting the polymer material treated by the ozone gas into a vacuum box for extraction to remove the ozone gas and oxygen on the surface of the polymer material and diffused into the polymer material; soaking the treated polymer material in a mixed solution of an anionic monomer and a cationic monomer, and introducing inert gas into the solution; after introducing inert gas, reducing ions are added to initiate polymerization. The mixed charge polymer coating provided by the invention is applied to the surface of a polymer material, so that the broad-spectrum antibacterial property of the material can be effectively improved.
Description
The technical field is as follows:
the invention relates to the technical field of polymer coatings, in particular to a mixed charge polymer coating with broad-spectrum antibacterial action and a polymer coating method.
Background art:
with the development of science and technology and the improvement of living standard, people pay more attention to their health conditions, thus promoting the vigorous development of the field of medical polymer materials and leading a plurality of biomedical polymer materials to be produced. Such as: the polyurethane elastomer has the characteristics of excellent mechanical property, wear resistance, biocompatibility and the like, and is widely applied to the aspects of artificial heart auxiliary devices, medical catheters, orthopedic bandages and the like. However, in medical environments, there are inevitably many bacteria which may adhere to the surface of the material, cause infection during contact with human tissues, increase morbidity and mortality, and cause economic loss due to medical complications, so it is important to impart excellent antibacterial properties to the biomedical polymer material.
In order to make general materials have an antibacterial function, we often add a kind of bactericidal group to the material body, such as: silver ion (Ag)+) Titanium dioxide (TiO)2) Quaternary ammonium salt micromolecules, iodine, antibiotics and the like, and the bacteria on the surface of the material are killed by releasing the micromolecule bactericide, so that the growth and the propagation of the bacteria are inhibited. In contrast, surface modification technology can make the material obtain surface characteristics different from the bulk properties while keeping the bulk properties unchanged, so that surface modification has become an active and challenging research field in the field of biomaterials nowadays. Grafting is one of the important methods for surface modification, and is generally to treat the existing high molecular material by chemical or physical means to generate free radical reactive active centers on the surface of the material, and then to initiate the polymerization of grafting monomers on the surface of the material by using the active centers to generate a polymer graft layer, so as to achieve the purpose of introducing specific functional groups to improve the surface performance of the material. The surface graft polymerization method can be classified into a chemical graft method, a plasma graft method, a high-energy radiation graft method, a photograft method, an ozonization graft method, and the like according to the generation manner of the free radicals on the surface of the material. They have advantages and disadvantages and are suitable for different applications. The chemical grafting method has complex process, the reaction is limited by a container, and large-scale parts are more difficult to process, so that the method is greatly limited in use. The plasma grafting method has low reaction environment temperature, the action on the surface of the material only relates to a few to hundreds of nanometers, and the performance of the matrix is not influenced; the method has no strict requirements on the processed materials and has universal adaptability; disposable shapeMore complex materials, good uniformity of material surface treatment and the like. However, plasma grafting requires vacuum equipment and is not suitable for large-scale operation. The high-energy radiation grafting method is carried out at normal temperature, has good repeatability, but has more factors influencing the reaction, such as radiation dose, monomer concentration, chain regulator concentration and the like. In addition, high-energy radiation can penetrate through the surface layer of the grafted high-molecular material to enter the body, and the performance of the body is influenced. High energy radiation grafting methods rely on radiation sources and have limited mass processing. The photografting method has many outstanding characteristics, mild conditions, low energy of long-wave ultraviolet light, can not be absorbed by high molecular materials, but can be absorbed by a photoinitiator to initiate reaction, not only can achieve the purpose of surface modification, but also cannot influence the material body, and has the advantages of simple process, convenient operation, easy control and low equipment investment, thereby being a surface modification technology which is expected to realize industrialization. However, the photografting method can only treat the surface of the material which can be irradiated by ultraviolet light, but can not reach places which can be irradiated by ultraviolet light, such as: the inner surface of the polymer conduit appears to be ineffective. The ozonization grafting method solves the problems well, and compared with other grafting methods, the ozonization method has the advantages of simple equipment, wide applicability, capability of treating complex surface shapes and the like.
The invention content is as follows:
in view of the foregoing, there is a need for a hybrid charge polymer coating.
There is also a need to provide a hybrid charge polymer coating process.
A mixed charge polymer coating comprising an anionic monomer, a cationic monomer, and a solution for dissolving the anionic monomer, the cationic monomer.
Preferably, the mixed charge polymer coating is a surface grafting modification for improving the antibacterial performance of the material, and the antibacterial principle of the grafting modification comprises the following steps: (1) the surface of the polymer material is modified to exclude bacteria from being adsorbed to the surface of the material, so that the formation of a biological film is prevented from the source; (2) the bacteria are contacted through the antibacterial functional groups fixed on the surface of the polymer material to cause the death of the bacteria; (3) meanwhile, the surface of the polymer material is modified to exclude bacteria from being adsorbed to the surface of the material, so that the formation of a biological film is prevented from the source; and, the bacteria are killed by contacting the bacteria with the antibacterial functional groups immobilized on the surface of the polymer material.
Preferably, the solution is a mixture of water and an isopropanol solution, and the anionic monomer is an anionic monomer containing a polymerizable double bond.
Preferably, the cationic monomer is a cationic monomer having a polymerizable double bond.
A hybrid charge polymer coating process comprising the following coating steps:
cleaning the surface of a polymer material to be grafted, and then carrying out vacuum drying treatment;
step two, after vacuum drying, using ozone gas to treat the surface of the polymer material;
step three, putting the polymer material treated by the ozone gas into a vacuum box for extraction to remove the ozone gas and the oxygen on the surface of the polymer material and diffused into the polymer material;
soaking the treated polymer material in a mixed solution of an anionic monomer and a cationic monomer, and introducing inert gas into the solution;
and step five, adding reducing ions to initiate polymerization reaction after introducing inert gas.
Preferably, in step one, the surface of the polymer material to be grafted is washed with methanol and distilled water, respectively.
Preferably, in the second step, after vacuum drying, the surface of the polymer material is treated with ozone gas, and then treated with an ozone generator.
Preferably, in the third step, the polymer material treated by the ozone gas is put into a vacuum box to be extracted so as to remove the ozone gas and the oxygen gas on the surface of the polymer material and diffused into the polymer material.
Preferably, the inert gas in the fourth step is preferably nitrogen or argon.
Preferably, in the fifth step, the added reducing ion is ferrous ion, preferably ammonium ferrous sulfate hexahydrate or ferrous sulfate, after the polymerization reaction at room temperature, the polymer material is taken out, the inner and outer surfaces of the polymer material are respectively and repeatedly cleaned by methanol and distilled water to remove unreacted monomers and non-grafted polymers, and the polymer material is dried in vacuum.
The mixed charge polymer coating provided by the invention is grafted to the surface of the polymer material, so that the antibacterial property of the polymer material can be effectively improved, and particularly, the antibacterial rates of the mixed charge polymer coating of anionic 3-sulfopropyl methacrylate potassium (SPM) and cationic (3-acrylamidopropyl) trimethyl ammonium chloride (AMPTMA) to methicillin-resistant staphylococcus aureus (MRSA BBA38) and pseudomonas aeruginosa (PAO1) after 30 days can respectively reach 99.98% and 99.89%.
In the invention, the material grafted by the mixed charge polymer coating simultaneously has the following two antibacterial principles: (1) the surface of the material is modified to exclude bacteria from being adsorbed to the surface of the material, so that the formation of a biological film is prevented from the source; (2) the bacteria are killed by the contact of the antibacterial functional groups fixed on the surface of the material. In particular, grafting zwitterionic polymers on the surface of a material to improve the antibacterial performance of the material is one of the most widely studied methods. The amphoteric ion polymer is a high molecular material which is electrically neutral as a whole and simultaneously contains anionic and cationic groups on the same monomer side chain. Because the amphoteric ion polymer contains positive charges and negative charges, the amphoteric ion polymer can form a firm and stable hydration layer in aqueous solution through the combined action of hydration and ion solvation, and can well inhibit the adhesion of proteins and bacteria (antibacterial principle (1)). In addition, there are four major types of cationic groups of zwitterionic polymers: quaternary ammonium salt cations, quaternary phosphonium salt cations, pyridinium ions, imidazolium ions; there are three main types of anionic groups: sulfonate anions, carboxylate anions and phosphate anions. Among them, cationic groups such as quaternary ammonium salts, quaternary phosphonium salts, etc. have strong antibacterial effects, and the bactericidal mechanism thereof is relatively mature (antibacterial principle (2)). Therefore, in the present invention, we try to reconstitute zwitterionic polymers by combining two different anionic and cationic monomers. A mixed charge polymer coating with two antibacterial principles is constructed by changing the proportional relation between anionic monomers and cationic monomers, and the coating is fixed on the surface of a polymer material by using a surface graft polymerization method to improve the antibacterial property of the material, particularly the broad-spectrum antibacterial property of the outer surface of some irregular objects and the inner surface of most materials, such as: the inner surface of the polymer conduit, etc.
Description of the drawings:
in order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic flow diagram of a process for grafting a mixed charge polymer coating onto the surface of a polyurethane catheter;
FIG. 2 is a schematic diagram of the chemical structures of three anionic monomers and three cationic monomers;
in fig. 1: methods for treating the surface of a polyurethane catheter with ozone S1-S3.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention provides the following specific examples.
Referring to fig. 2, the mixed charge polymer coating includes a mixture of an anionic monomer, a cationic monomer, water and an isopropyl alcohol solution. The anionic monomer is one or more of 3-sulfopropyl acrylate Sylvite (SPM), 3-sulfopropyl acrylate Sylvite (SPA) and 2-acrylamido-2-methyl propyl sulfonate (AMPA). The cationic monomer is one or more of (3-acrylamidopropyl) trimethyl ammonium chloride (AMPTMA), acryloyloxyethyl trimethyl ammonium chloride (AETMA) and methacryloyloxyethyl trimethyl ammonium chloride (MAETMA). The molar ratio of anionic monomer to cationic monomer is 1: 1. The volume ratio of water to isopropanol solution was 1: 1. The ratio of the total mass of the added anionic and cationic monomers to the volume of the water/isopropanol mixed solution was 10% (w/v).
A hybrid charge polymer coating process comprising the following coating steps:
step one, respectively cleaning the surface of a polymer material to be grafted by using methanol and distilled water, and then carrying out vacuum drying treatment;
step two, after vacuum drying, using ozone gas to treat the surface of the polymer material; after vacuum drying, the surface of the polymer material is treated with ozone gas for 25 to 45 minutes, typically 30 minutes, but may be treated for several seconds to infinite time depending on the size of the polymer material.
Step three, putting the polymer material treated by the ozone gas into a vacuum box for extraction to remove the ozone gas and the oxygen on the surface of the polymer material and diffused into the polymer material; and (3) putting the polymer material treated by the ozone into a vacuum box, wherein the vacuum degree of the vacuum box is less than 10 Pa, and treating for 0.8-1.2 hours to remove ozone gas and oxygen on the surface of the polymer material and diffused into the polymer material. The closer the vacuum of the vacuum box is to the vacuum (0 pa) the better, the typical treatment is for 1 hour, but it can be carried out for a few seconds to infinite time depending on the size of the polymer material.
Soaking the treated polymer material in a mixed solution of an anionic monomer, a cationic monomer, water and an isopropanol solution, and introducing inert gas into the solution; soaking the treated polymer material in a mixed solution of an anionic monomer, a cationic monomer, water and an isopropanol solution, wherein the molar ratio of the anionic monomer to the cationic monomer is 1:1, the volume ratio of the water to the isopropanol solution is 1:1, and the ratio of the total mass of the added anionic monomer to the volume of the water/isopropanol mixed solution is 10% (w/v).
Step five, after introducing inert gas, adding reducing ions to initiate polymerization reaction; the inert gas is nitrogen or argon, and the time for introducing the inert gas is 25 minutes to 45 minutes, generally 30 minutes. Adding ferrous ion as reducing ion, preferably ammonium ferrous sulfate hexahydrate or ferrous sulfate, adding ferrous ion in the ratio of the mass to the volume of the water/isopropanol mixed solution of 0.1% (w/v), polymerizing at room temperature for 24 hr, taking out the polymer material, washing the inner and outer surfaces of the polymer material with methanol and distilled water repeatedly to eliminate unreacted monomer and un-grafted polymer, and vacuum drying. The reaction is carried out at room temperature for 24 hours in the present embodiment, but the reaction temperature of the reaction can be from 0 ℃ to 100 ℃, and the reaction time can be from several seconds to infinity according to the size of the polymer material.
In the embodiment of the invention, a polyurethane catheter is selected as the polymer matrix material for carrying out an antibacterial test, and the following nine embodiments of mixed charge polymer coatings are provided:
referring to fig. 1, the method for grafting the mixed charge polymer coating on the surface of the polyurethane catheter specifically comprises the following steps: step one S1, respectively cleaning the inner and outer surfaces of the polyurethane conduit with methanol and distilled water; step two S2, after vacuum drying, simultaneously treating the inner surface and the outer surface of the conduit for 30 minutes by using ozone gas, wherein the speed of an ozone generator is 15L/min; step three S3, the conduit treated with ozone gas is put into a vacuum box to extract for 1 hour, the vacuum degree is less than 10 Pa, so as to remove the ozone gas and oxygen on the surface of the conduit and diffused into the conduit. Subsequently, in step four S4, the treated catheter is immersed in a water/isopropanol mixed solution in which the molar ratio of the cationic monomer to the anionic monomer is 1:1, the volume ratio of the water to the isopropanol solution is 1:1, the ratio of the total mass of the added anionic and cationic monomers to the volume of the water/isopropanol mixed solution is 10% (w/v), and the solution is injected into the catheter by a peristaltic pump, thereby maintaining the circulation of the liquid inside and outside the catheter. And step S5, introducing inert gas into the solution for 30 minutes, adding a proper amount of ferrous ions to initiate polymerization reaction, wherein the ratio of the mass of the added ferrous ions to the volume of the water/isopropanol mixed solution is 0.1% (w/v). After reacting at room temperature for 24 hours, the vessel was taken out, and the inner and outer surfaces of the vessel were repeatedly washed with methanol and distilled water, respectively, to remove unreacted monomers and ungrafted polymer, and vacuum-dried.
The internal and external surfaces of the catheter are subjected to grafting mixed charge polymer coating treatment by adopting the following nine examples to improve the antibacterial property of the material, wherein the six bacteria are respectively: methicillin-resistant staphylococcus aureus (MRSA BBA38), vancomycin-resistant enterococcus (VRE V583), methicillin-resistant staphylococcus epidermidis (MRSE 35984), pseudomonas aeruginosa (PAO1), escherichia coli (E.coli UT189), carbapenem-resistant acinetobacter baumannii (AB-1)
The specific embodiment is as follows:
the first embodiment is as follows: anionic SPM and cationic AMPTMA mixed charge polymer grafted polyurethane catheter
The antibacterial rates of the anionic SPM and cationic AMPTMA mixed charge polymer grafted polyurethane catheters on MRSA BBA38, VRE V583, MRSE35984, PAO1, e.coli UT189 and AB-1 were 99.97%, 99.88%, 99.11%, 99.77%, 99.58% and 99.95%, respectively, as measured by a 24 hour in vitro biofilm method.
Example two: anionic SPM and cationic AETMA mixed charge polymer grafted polyurethane catheters;
the antibacterial rates of the anionic SPM and cationic AETMA mixed charge polymer grafted polyurethane catheters on MRSA BBA38, VRE V583, MRSE35984, PAO1, e.coli UT189 and AB-1 were 99.96%, 99.32%, 96.45%, 96.53%, 98.41% and 99.94%, respectively, as measured by a 24-hour in vitro biofilm method.
Example three: an anionic SPM and cationic MAETMA hybrid charge polymer grafted polyurethane catheter;
the antibacterial rates of the polyurethane catheter grafted with the mixed charge polymer of the anionic SPM and the cationic MAETMA were respectively 99.95%, 98.80%, 72.47%, 92.41%, 96.99% and 99.93% for MRSA BBA38, VRE V583, MRSE35984, PAO1, E.coli UT189 and AB-1, as measured by a 24-hour in vitro biofilm method.
Example four: a mixed charge polymer grafted polyurethane catheter of anionic SPA and cationic AMPTMA;
the antibacterial rates of the anionic SPA and cationic AMPTMA mixed charge polymer grafted polyurethane catheters on MRSA BBA38, VRE V583, MRSE35984, PAO1, E.coli UT189 and AB-1 were 92.92%, 99.07%, 99.93%, 96.77%, 99.07% and 99.91%, respectively, as measured by a 24-hour in vitro biofilm method.
Example five: a mixed charge polymer grafted polyurethane catheter of anionic SPA and cationic AETMA;
the antibacterial rates of the anionic SPA and cationic AETMA mixed charge polymer grafted polyurethane catheters on MRSA BBA38, VRE V583, MRSE35984, PAO1, e.coli UT189 and AB-1 were 67.65%, 97.37%, 89.53%, 90.67%, 98.85% and 99.87%, respectively, as measured by a 24 hour in vitro biofilm method.
Example six: a mixed charge polymer grafted polyurethane catheter of anionic SPA and cationic MAETMA;
the antibacterial rates of the polyurethane catheter grafted by the mixed charge polymer of the anionic SPA and the cationic MAETMA on MRSA BBA38, VRE V583, MRSE35984, PAO1, E.coli UT189 and AB-1 were respectively 97.18%, 99.45%, 95.10%, 89.53%, 98.85% and 99.96% as measured by a 24-hour in vitro biofilm method.
Example seven: a mixed charge polymer grafted polyurethane conduit of anionic AMPA and cationic AMPTMA;
the antimicrobial rates of the mixed charge polymer-grafted polyurethane catheters, anionic AMPA and cationic AMPTMA, were 99.97%, 36.90%, 98.85%, 94.25%, 98.52% and 99.72% for MRSA BBA38, VRE V583, MRSE35984, PAO1, E.coli UT189 and AB-1, respectively, as measured by a 24 hour in vitro biofilm method.
Example eight: a mixed charge polymer grafted polyurethane catheter of anionic AMPA and cationic AETMA;
the antimicrobial rates of the anionic AMPA and cationic AETMA mixed charge polymer grafted polyurethane catheters were 99.78%, 39.73%, 61.10%, 92.78%, 97.76% and 99.83%, respectively, on MRSA BBA38, VRE V583, MRSE35984, PAO1, E.coli UT189 and AB-1, as measured by a 24 hour in vitro biofilm method.
Example nine: a mixed charge polymer grafted polyurethane catheter of anionic AMPA and cationic MAETMA;
the antibacterial rates of the anionic AMPA and cationic MAETMA mixed charge polymer grafted polyurethane catheters on MRSA BBA38, VRE V583, MRSE35984, PAO1, E.coli UT189 and AB-1 were respectively 99.95%, 96.21%, 49.88%, 98.18%, 99.37% and 98.77% as measured by a 24-hour in vitro biofilm method.
The antibacterial rates of the polyurethane catheter grafted with the mixed charge polymer of anionic SPM and cationic AMPTMA by the in vitro biofilm method for 30 days were 99.98% and 99.89%, respectively, for MRSA BBA38 and PAO 1. In comparison, the antimicrobial properties of the currently commercialized silver ion-supplemented catheters against MRSA BBA38 and PAO1 were ineffective on the fifth and third days, respectively.
Claims (10)
1. A mixed charge polymer coating characterized by: the mixed charge polymer coating includes an anionic monomer, a cationic monomer, and a solution for dissolving the anionic monomer and the cationic monomer.
2. The mixed-charge polymer coating of claim 1, wherein: the mixed charge polymer coating is surface grafting modification for improving the antibacterial performance of the material, and the antibacterial principle of the grafting modification comprises the following steps: (1) the surface of the polymer material is modified to exclude bacteria from being adsorbed to the surface of the material, so that the formation of a biological film is prevented from the source; (2) the bacteria are contacted through the antibacterial functional groups fixed on the surface of the polymer material to cause the death of the bacteria; (3) meanwhile, the surface of the polymer material is modified to exclude bacteria from being adsorbed to the surface of the material, so that the formation of a biological film is prevented from the source; and, the bacteria are killed by contacting the bacteria with the antibacterial functional groups immobilized on the surface of the polymer material.
3. The mixed-charge polymer coating of claim 1, wherein: the solution is a mixed solution of water and isopropanol solution; the anionic monomer is an anionic monomer containing a polymerizable double bond.
4. The mixed-charge polymer coating of claim 1, wherein: the cationic monomer is a cationic monomer containing polymerizable double bonds.
5. A method of coating a mixed charge polymer, comprising: the mixed charge polymer coating method comprises the following coating steps:
cleaning the surface of a polymer material to be grafted, and then carrying out vacuum drying treatment;
step two, after vacuum drying, using ozone gas to treat the surface of the polymer material;
step three, putting the polymer material treated by the ozone gas into a vacuum box for extraction to remove the ozone gas and the oxygen on the surface of the polymer material and diffused into the polymer material;
soaking the treated polymer material in a mixed solution of an anionic monomer and a cationic monomer, and introducing inert gas into the solution;
and step five, adding reducing ions to initiate polymerization reaction after introducing inert gas.
6. The method of mixed charge polymer coating of claim 5, wherein: in step one, the surface of the polymer material to be grafted is washed with methanol and distilled water, respectively.
7. The method of mixed charge polymer coating of claim 5, wherein: and in the second step, after vacuum drying, the surface of the polymer material is treated by ozone gas, and an ozone generator is adopted for treatment.
8. The method of mixed charge polymer coating of claim 5, wherein: in the third step, the polymer material treated by the ozone gas is put into a vacuum box to be extracted so as to remove the ozone gas and the oxygen gas on the surface of the polymer material and diffused into the polymer material.
9. The method of mixed charge polymer coating of claim 5, wherein: the inert gas in the fourth step is preferably nitrogen or argon.
10. The method of mixed charge polymer coating of claim 5, wherein: in the fifth step, the added reducing ions are ferrous ions, preferably ammonium ferrous sulfate hexahydrate or ferrous sulfate, after the polymerization reaction at room temperature, the polymer material is taken out, the inner surface and the outer surface of the polymer material are respectively and repeatedly cleaned by methanol and distilled water to remove unreacted monomers and non-grafted polymers, and the polymer is dried in vacuum.
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