CN117624535A - Difunctional polyurethane material with self-repairing performance and antibacterial performance and preparation method and application thereof - Google Patents
Difunctional polyurethane material with self-repairing performance and antibacterial performance and preparation method and application thereof Download PDFInfo
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- CN117624535A CN117624535A CN202211000319.5A CN202211000319A CN117624535A CN 117624535 A CN117624535 A CN 117624535A CN 202211000319 A CN202211000319 A CN 202211000319A CN 117624535 A CN117624535 A CN 117624535A
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- polyurethane
- self
- antibacterial
- repairing
- performance
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- 239000000463 material Substances 0.000 title claims abstract description 160
- 239000004814 polyurethane Substances 0.000 title claims abstract description 159
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 154
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 230000001588 bifunctional effect Effects 0.000 claims description 28
- 150000001350 alkyl halides Chemical class 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 16
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical group CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005956 quaternization reaction Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical group 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 7
- -1 polytetramethylene Polymers 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
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- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
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- 238000006116 polymerization reaction Methods 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
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- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- PJDVXCKTCFPZQA-UHFFFAOYSA-N dodecane;hydrobromide Chemical compound Br.CCCCCCCCCCCC PJDVXCKTCFPZQA-UHFFFAOYSA-N 0.000 claims description 2
- WTVNABTWDZCYCN-UHFFFAOYSA-N hexane;hydrobromide Chemical compound Br.CCCCCC WTVNABTWDZCYCN-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
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- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
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- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
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- 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
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Abstract
The invention belongs to the field of polyurethane materials, and discloses a difunctional polyurethane material with self-repairing performance and antibacterial performance, and a preparation method and application thereof. Compared with the existing polyurethane catheter material, the dual-functional polyurethane material prepared by the invention has the self-repairing performance and the antibacterial performance, and can solve the problems of bacterial infection and puncture damage in catheter application; different block copolymer structures are designed by changing the molecular weight of the polyurethane part, the ratio of an initiator to a monomer, a quaternizing agent and the like, and a large number of quaternary ammonium structure repeating units enable the block copolymer to have stronger and stable antibacterial performance; the prepared double-function polyurethane material can be used as a conduit material alone or as an additive of the polyurethane conduit material, and tertiary amine group molecular chains can migrate to the surface when the polyurethane conduit material is used as the material additive, so that the effect of enriching the surface of an antibacterial component is achieved.
Description
Technical Field
The invention belongs to the field of polyurethane materials, and particularly relates to a difunctional polyurethane material with self-repairing performance and antibacterial performance, and a preparation method and application thereof.
Background
Intravenous catheters are the main dependent routes of therapeutic approaches such as safe infusion, intravenous nutrition support, hemodialysis, etc. The venous indwelling catheter mainly comprises a central venous catheter, a peripherally inserted central venous catheter, a long-term intravenous catheter, a peripherally inserted intravenous catheter and the like. Venous indwelling needle cannulas are the most common and simplest venous catheters, which avoid repeated venipuncture, and are widely used for patients requiring long-term, continuous or intermittent intravenous infusion therapy.
The clinical intravenous catheter materials are mostly medical polymer materials, the medical polymer materials are materials which are applied to a large number of biomedical materials, have good comprehensive performance, can meet the requirements of preparing various biological materials, are mainly applied to human bodies, are mainly applied to aspects of medical appliances, disease diagnosis, treatment, artificial organs and the like, not only relate to the life and health of human beings, but also have very important influence on social development. Common polymeric materials used for intravenous catheters are silicone rubber, polytetrafluoroethylene and polyurethane.
The medical polyurethane is a thermoplastic elastomer with a block structure, and the structural main body of the medical polyurethane is divided into a soft section and a hard section. Wherein the soft segment is generally a longer segment, such as polyethylene glycol, polyethylene oxide, polycaprolactone, etc. with low polymerization degree, and the segment has certain flexibility relatively; the hard segment is a relatively short diisocyanate and a chain extender, and has certain rigidity relatively. Polyurethane materials meeting different performance requirements can be obtained by selecting different hard and soft segment materials and composition ratios. The structure of the polyurethane has unique microphase separation structure of soft segment and hard segment, so that thrombosis can be inhibited, and the higher microphase separation degree is, the better the blood compatibility of the polyurethane is, and the wide physical and chemical properties can be obtained by changing the structure of the polyurethane. And thus are used in large numbers for the fabrication of various medical devices such as medical catheters, adhesives, cardiovascular stents, etc. used in interventional procedures.
The traditional polyurethane material has no antibacterial function, and the hydrophobic surface is extremely easy to adhere bacteria to cause wound infection and various complications, so that the biocompatibility and the antibacterial function of the polyurethane material need to be further researched and improved. In addition, when the medical polyurethane catheter is used for interventional therapy and is used as an indwelling catheter or a drainage catheter, the catheter sealing and repairing problem of the catheter after the puncture device is used exists.
Therefore, it is necessary to study a polyurethane material having dual functions of self-repairing property and antibacterial property and having good biocompatibility.
Disclosure of Invention
Aiming at the defects in the application process of the existing polyurethane catheter, the invention aims to provide a difunctional polyurethane material with self-repairing performance and antibacterial performance.
The invention further aims to provide a preparation method of the difunctional polyurethane material with the self-repairing performance and the antibacterial performance.
The invention also aims to provide the application of the double-function polyurethane material with self-repairing performance and antibacterial performance in polyurethane catheter materials, which can be used as a catheter material alone or as an additive of the polyurethane catheter material to solve the problems of microorganism infection and remaining holes after pipeline puncture in the application process of the catheter.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a double-functional polyurethane material with self-repairing performance and antibacterial performance comprises the following characteristics:
the difunctional polyurethane material with the self-repairing performance and the antibacterial performance is of a block polyurethane copolymer structure, the middle part is a polyurethane block, and the two ends are repeat units with tertiary amine structures;
disulfide bond self-repairing structures are added in the blocks to realize the self-repairing performance of the material;
the repeated units at the two ends and different haloalkanes are subjected to quaternization reaction, so that a large number of quaternary ammonium structures are generated, and efficient antibacterial effect is realized.
The preparation method of the difunctional polyurethane material with the self-repairing performance and the antibacterial performance comprises the following steps:
(1) Weighing dehydrated polyether glycol under the nitrogen atmosphere, adding diisocyanate, and performing prepolymerization under the action of a catalyst; dissolving a chain extender in a solvent A, adding the solvent A into a reaction system for reaction, and obtaining a reaction mixture which is an isocyanate terminated polyurethane intermediate with a disulfide bond self-repairing structure;
(2) Adding the homopolymer into the reaction mixture in the step (1), and continuing to react for 5-8 hours; then the reaction temperature is increased to carry out curing; after curing, dropwise adding the reaction mixture into the solvent B, collecting a product, and drying to obtain a polyurethane block copolymerization product;
(3) And (3) dissolving the polyurethane block copolymer product in the step (2) in the solvent A, adding haloalkane for reaction, dripping the reaction mixture into the solvent B, collecting precipitate, and drying to obtain the self-repairable antibacterial polyurethane material.
The polyether glycol in the step (1) is any one of polytetramethylene glycol (PTMG), polyethylene glycol (PEG) and polypropylene glycol (PPG), and the molecular weight is 1000-3000;
the diisocyanate in the step (1) is any one of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and diphenylmethane diisocyanate (MDI);
the catalyst in the step (1) is any one of bismuth neodecanoate, dibutyl tin dilaurate and stannous isooctanoate, and the dosage is about 1-5 per mill of the mass fraction of the reaction raw materials;
the prepolymerization condition in the step (1) is that the prepolymerization is carried out for 4 to 6 hours at the temperature of between 60 and 70 ℃;
the chain extender in step (1) is preferably 4,4' -diaminodiphenyl disulfide (SS); the solvent A is any one of N, N-dimethylformamide, dioxane and dimethyl sulfoxide; the chain extender is dissolved in a small amount of solvent, and the solvent is only used as a medium and only needs a small amount of solvent for dissolving the chain extender;
the molar ratio of the polyether glycol, the diisocyanate and the chain extender in the step (1) is 1.5 (3.0-3.1) (1.4-1.45);
the reaction condition in the step (1) means that the reaction is carried out for 5 to 6 hours at the temperature of 70 to 80 ℃;
observing the state of a reactant in the reaction process, and adding a proper amount of super-dry solvent to dilute and promote the reaction when the reactant is adhered to a stirring rod due to the increase of viscosity;
the homopolymer in step (2) is preferably poly (dimethylaminoethyl methacrylate) (PDMAEMA);
the homopolymer monomer side chain should have a tertiary amine structure and can react with haloalkane to generate quaternary ammonium salt, preferably dimethylaminoethyl methacrylate (DMAEMA), and has the chemical structure:
the preparation method of the poly (dimethylaminoethyl methacrylate) (PDMAEMA) comprises the steps of weighing dimethylaminoethyl methacrylate (DMAEMA) with a tertiary amine structure and 2,2' -azo (2-methyl-N- (2-hydroxyethyl) propionamide) (VA-086) in a single-neck flask, wherein the molar ratio of the two is 40:1-100:1, adding anhydrous N, N-dimethylformamide with the dosage of about 2 times to 2.5 times of reactants for dissolution, and introducing nitrogen into the system for polymerization;
the poly (dimethylaminoethyl methacrylate) (PDMAEMA) uses 2,2' -azo (2-methyl-N- (2-hydroxyethyl) propionamide) (VA-086) as an initiator, so that two ends of a synthesized homopolymer are provided with hydroxyl groups to react with an isocyanate terminated polyurethane intermediate with a disulfide bond self-repairing structure in the step (1) to synthesize a block copolymer;
the curing in the step (2) is curing for 1-2 hours at 80-90 ℃; the solvent B is any one of diethyl ether, methanol or n-hexane, and is preferably a cold-stored solvent B at the temperature of 4 ℃; the drying condition is that the materials are dried in an oven at 60-65 ℃;
the haloalkane in the step (3) is any one of long-chain haloalkane and short-chain haloalkane; the alkyl halide is preferably any one of n-hexane bromide and dodecane bromide;
the polyurethane block copolymer and haloalkane are used in an amount of 1g in step (3): 900-2000 mu L;
when the haloalkane is bromo-n-hexane, the dosage of the polyurethane block copolymer and bromo-n-hexane is preferably 1 g:900-1000 mu L;
when the haloalkane is bromon-hexane, the dosage of the polyurethane block copolymerization product and bromododecane is preferably 1 g:1500-2000 mu L;
the reaction in the step (3) is carried out for 20-24 hours at 65-70 ℃ under the condition of nitrogen; and the drying is carried out by putting the dried materials into an oven at 60-65 ℃.
The application of the difunctional polyurethane material with the self-repairing performance and the antibacterial performance in the polyurethane catheter material is directly used as a medical antibacterial polyurethane catheter material or as an antibacterial additive of the polyurethane catheter material;
the preparation method comprises the steps of taking a bifunctional polyurethane material with self-repairing performance and antibacterial performance as an antibacterial additive of a polyurethane catheter material, dissolving the bifunctional polyurethane material and commercial polyurethane in a mass ratio of 1:10-1:15 in a solvent, blending, drying to obtain a blended material, and carrying out quaternization with haloalkane to enable the surface of the blended material to be provided with antibacterial groups; after the self-repairable antibacterial polyurethane material and the commercial polyurethane form a blending material, the migration of tertiary amine molecular chains in the self-repairable antibacterial polyurethane material to the surface of the blending material is promoted due to thermodynamic incompatibility, so that the surface of the blending material is quaternized and then is provided with a large number of antibacterial groups;
preferably, the difunctional polyurethane material with self-repairing performance and antibacterial performance and commercial polyurethane are dissolved in N, N-dimethylformamide according to the mass ratio of 1:10, and then are blended and dried to obtain a blended material, and then the blended material is quaternized with haloalkane to lead the surface of the blended material to be provided with antibacterial groups.
Compared with the prior art, the invention has the following advantages:
compared with the existing polyurethane catheter material, the material has the self-repairing performance and the antibacterial performance, and can solve the problems of bacterial infection and puncture damage in catheter application; the method can design different block copolymer structures by changing the molecular weight of the polyurethane part, the ratio of an initiator to a monomer, a quaternizing agent and the like, and a large number of quaternary ammonium structure repeating units enable the block copolymer to have stronger and stable antibacterial performance; when the copolymer is used as a material additive, the tertiary amine group molecular chain can migrate to the surface, so that the effect of enriching the surface of the antibacterial component is achieved.
Drawings
FIG. 1 is an infrared spectrum of a bifunctional polyurethane material (copolymer) having self-healing properties and antibacterial properties and a quaternary ammonium salt thereof in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of the bifunctional polyurethane material having self-repairing property and antibacterial property of example 1.
Fig. 3 is a puncture picture of the case of the dual-functional polyurethane material having the self-repairing property and the antibacterial property of example 1 as a pipe, the left drawing is a front view of the puncture hole, and the right drawing is a side view of the puncture hole.
Fig. 4 is a graph of self-repairing after the puncture of the polyurethane material pipe, the left graph is a graph of non-self-repairing after the puncture of the common polyurethane pipe, and the right graph is a graph of self-repairing after the puncture of the dual-function polyurethane material pipe having self-repairing performance and antibacterial performance in example 1.
FIG. 5 is the results of the minimum antimicrobial effective concentration of a difunctional polyurethane material with self-healing and antimicrobial properties against E.coli; wherein 1-6, 2-6, 3-6 represent the bifunctional polyurethane materials with self-repairing property and antibacterial property synthesized by using bromohexane for the polyurethane block copolymers in examples 1, 2 and 3, respectively.
FIG. 6 is a graph showing the results of minimum antimicrobial effective concentration of a difunctional polyurethane material having self-healing and antimicrobial properties against Staphylococcus aureus; wherein 1-6, 2-6, 3-6 represent the bifunctional polyurethane materials with self-repairing property and antibacterial property synthesized by using bromohexane for the polyurethane block copolymers in examples 1, 2 and 3, respectively.
FIG. 7 is the results of the lowest effective antimicrobial concentration of the bifunctional polyurethane material having self-healing and antimicrobial properties of example 4 against E.coli, wherein 1-12, 2-12, 3-12 represent the bifunctional polyurethane materials having self-healing and antimicrobial properties synthesized from the polyurethane block copolymers of examples 1, 2, 3 using bromododecane, respectively.
Fig. 8 is the results of the lowest effective antimicrobial concentration of the dual-functional polyurethane material with self-healing and antimicrobial properties of example 4 against staphylococcus aureus, wherein 1-12, 2-12, 3-12 represent the dual-functional polyurethane materials with self-healing and antimicrobial properties synthesized from the polyurethane block copolymers of example 1, example 2, example 3 using bromododecane, respectively.
Fig. 9 is a graph of the surface and interior XPS elemental analysis results of the dual functional polyurethane material and polyurethane blend material having self-healing and antibacterial properties of example 5.
Fig. 10 is a graph showing the antibacterial effect against e.coli of the blend material of the bifunctional polyurethane material having self-repairing property and antibacterial property with the commercial polyurethane in example 5.
Fig. 11 is a graph of the antimicrobial effect of the blend material of the dual function polyurethane material having self-healing and antimicrobial properties with the commercial polyurethane of example 5 against staphylococcus aureus.
FIG. 12 is the cytotoxicity test results of the cell co-culture of the blend material of the self-repairing antimicrobial structural polyurethane material and the commercial polyurethane in example 5.
FIG. 13 is a graph showing the results of a blood compatibility test of a blend material of the self-repairing antimicrobial polyurethane material and the commercial polyurethane in example 5, wherein (a) is a graph showing the results of the hemolysis of the blend material, and (b) is a value of the hemolysis measured by absorbance.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The antibacterial test method of the bifunctional polyurethane material with the self-repairing performance and the antibacterial performance in the embodiment comprises the following steps: preparing the material into suspension, taking 24-well plate, sequentially adding 500uL of suspensions with different concentrations (2 mg/mL, 1mg/mL, 0.5mg/mL, 0.25mg/mL, 0.125mg/mL, 0.0625mg/mL, 0.03125 mg/mL), 400uL of sterile normal saline and 100uL of sterile normal saline with concentration of about 1×10 6 The concentration of quaternary ammonium salt in the final bacterial solution of CFU/mL staphylococcus aureus (S.aureus) (or escherichia coli (E.coli) bacterial suspension) was 1mg/mL, 0.5mg/mL, 0.25mg/mL, 0.125mg/mL, 0.0625mg/mL, 0.03125mg/mL, 0.015625mg/mL, and finally the well plate was incubated on a thermostatic shaker at 37℃and 120rpm for 6 hours. Blowing the incubated bacterial suspension evenly, directly taking 10uL of bacterial suspension, uniformly coating on the surface of LB agar, placing three parallel agar plates of each bacterial liquid at 37 ℃ CO 2 Culturing in an incubator for a period of time (about S.aureus 18h, about E.coli 12 h), and observing the colony quantity change in each plate.
The antibacterial test method of the blend material of the difunctional polyurethane material with the self-repairing performance and the antibacterial performance and the commercial polyurethane comprises the following step of ultraviolet sterilization of the front side and the back side of a PU film with the diameter of 10mm and a surface quaternized blend material film for 24 hours for later use. Taking 24-well plates, sequentially adding 900uL of sterile physiological saline and 100uL of 1×10 concentration into each well plate 6 CFU/mL s.aureus (or e.coli suspension), PU membrane and surface quaternization blend material discs were added separately, and finally the well plate was placed in a shaker at 37 ℃ and 120rpm for 6h incubation. Blowing the incubated bacterial suspension evenly, taking 100uL of bacterial suspension, diluting by a certain multiple with sterile normal saline, taking 10uL of diluted bacterial suspension, evenly coating on the surface of LB agar,three parallel plates were incubated in an incubator at 37℃for a period of time (about S.aureus 18h, about E.coli 12 h) and the number of colonies in each plate was observed for changes.
Example 1
(1) Weighing 16g of polytetramethylene glycol (Mn=1000) (PTMG) in a 100mL single-neck flask, vacuumizing and dewatering for 1h under magnetic stirring at 110 ℃, weighing 15g of polytetramethylene glycol (Mn=1000) after dewatering in a 250mL three-neck flask, and vacuumizing and dewatering for 30min under mechanical stirring at 110 ℃; adding 5.218g of Hexamethylene Diisocyanate (HDI) and 150 mu L of 0.3g/mL of N, N-dimethylformamide solution of bismuth neodecanoate into the polytetramethylene glycol subjected to secondary water removal under the nitrogen atmosphere at 70 ℃ for pre-polymerization for 4 hours; raising the reaction temperature to 80 ℃, dissolving 3.601g of 4,4' -diaminodiphenyl disulfide (SS) in 5mL of N, N-dimethylformamide, adding the mixture into a reaction system, reacting for 5h, and respectively adding 5mL of ultra-dry N, N-dimethylformamide into the 1 st and 3 rd h after the reaction to reduce the viscosity of a reaction mixture;
(2) Adding the PDMAEMA solution prepared in advance into a three-mouth bottle, and continuing to react for 5 hours; raising the reaction temperature to 90 ℃ and curing for 1h; 1mL of methanol was added to terminate the reaction; dropwise adding the reaction mixture into cold methanol, and collecting a product; the mixture is poured into 4 polytetrafluoroethylene moulds with the average length of 10cm multiplied by 10cm, and the mixture is placed in a baking oven at the temperature of 60 ℃ for baking.
The PDMAEMA solution in the example reaction was prepared one day in advance: 3.144g of dimethylaminoethyl methacrylate (DMAEMA) and 0.1442g of 2,2' -azo (2-methyl-N- (2-hydroxyethyl) propionamide) (VA-086) were weighed into a 50mL single-neck flask, 10mL of anhydrous N, N-dimethylformamide was added to dissolve, nitrogen was introduced into the system for 30min, and the mixture was reacted at 86℃for 12h.
(3) 1g of polyurethane block copolymerization product is weighed into a 50mL single-neck flask, 20mL of N, N-dimethylformamide is added for dissolution, 900 mu L of bromon-hexane is added, nitrogen is introduced into the flask for 30min, the reaction is carried out for 24h at 70 ℃, the reaction mixture is dripped into cold N-hexane, the precipitate is collected, and the precipitate is put into a 60 ℃ oven for drying, and the sign of the product is 1-6.
FIG. 1 is a (co) polymer of a bifunctional polyurethane material having self-healing properties and antibacterial properties and a quaternary ammonium salt thereof in example 1Infrared spectrum. As can be seen from FIG. 1, 2822cm of the copolymer pattern -1 And 2771cm -1 The peak at which is DMAEMA molecular chain-N (CH 3 ) 2 Characteristic peaks, and disappeared after quaternization, 1640cm -1 The new peak corresponds to the symmetrical deformation of the quaternary ammonium salt, and the quaternary ammonium structure is easy to absorb water in the air to cause 3420cm -1 Broad peak in the vicinity, 2940cm -1 The distance between the two parts is 2850cm -1 The ratio of the intensity of the C-H absorption peak at the position also changes along with the reaction of bromoalkane.
FIG. 2 is a nuclear magnetic resonance spectrum of the bifunctional polyurethane material with self-repairing property and antibacterial property of example 1, which appears in the figure 1 H NMR(400MHz,CDCl 3 δ): 0.78-0.97ppm (e), 1.80-1.90ppm (f), 2.14-2.51ppm (i), 2.52-2.74ppm (h), 3.98-4.19ppm (h) prove the PDMAEMA structure at both ends of the block copolymer.
Fig. 3 is a puncture picture of the dual-functional polyurethane material with self-repairing and antibacterial properties of example 1 as a pipeline, respectively, in front view (left) and side view (right) of the puncture hole, and it can be seen that a significant hole remains in the pipeline after puncture.
Fig. 4 is a graph of self-repairing after puncture of a polyurethane material pipeline, and is a graph of self-repairing (left) failure after puncture of a common polyurethane pipeline and self-repairing after puncture of a double-functional polyurethane material pipeline (right) with self-repairing performance and antibacterial performance in example 1, respectively, wherein the damaged part of the common polyurethane pipeline has no obvious change, and the hollow of the double-functional polyurethane material pipeline with self-repairing performance and antibacterial performance is obviously repaired, which proves the self-repairing performance of the material.
Example 2
The difference between this example and example 1 is that the PDMAEMA solution in step (2) of this example was prepared by one day in advance: 4.7160g of dimethylaminoethyl methacrylate (DMAEMA) and 0.1442g of 2,2' -azo (2-methyl-N- (2-hydroxyethyl) propionamide) (VA-086) are weighed into a 50mL single-neck flask, 15mL of anhydrous N, N-dimethylformamide is added for dissolution, nitrogen is introduced into the system for 30min, and the reaction is carried out for 12h at 86 ℃, and the product symbol is 2-6.
Example 3
The difference between this example and example 1 is that the PDMAEMA solution in step (2) of this example was prepared by one day in advance: 7.074g of dimethylaminoethyl methacrylate (DMAEMA) and 0.1442g of 2,2' -azo (2-methyl-N- (2-hydroxyethyl) propionamide) (VA-086) are weighed into a 50mL single-neck flask, 20mL of anhydrous N, N-dimethylformamide is added for dissolution, nitrogen is introduced into the system for 30min, and the reaction is carried out for 12h at 86 ℃, and the product symbol is 3-6.
FIG. 5 is the results of the minimum antimicrobial effective concentration of the bifunctional polyurethane materials having self-healing properties and antimicrobial properties for E.coli in examples 1, 2 and 3, respectively; in the figures, 1-6, 2-6 and 3-6 respectively represent bifunctional polyurethane materials which are synthesized by using bromohexane and have self-repairing performance and antibacterial performance in the polyurethane block copolymers in examples 1, 2 and 3, and the results show that the polyurethane materials have stronger sterilizing effect on escherichia coli under lower concentration (0.5 mg/mL).
FIG. 6 is a graph showing the results of the lowest antimicrobial effective concentration of the bifunctional polyurethane materials with self-repairing and antimicrobial properties in examples 1, 2 and 3 against Staphylococcus aureus, wherein 1-6, 2-6 and 3-6 respectively represent the bifunctional polyurethane materials with self-repairing and antimicrobial properties synthesized by using bromohexane for the polyurethane block copolymers in examples 1, 2 and 3, and the results show that the bifunctional polyurethane materials have stronger bactericidal effect against Staphylococcus aureus compared with Escherichia coli.
Example 4
1g of the polyurethane block copolymer obtained in example 1, example 2 and example 3 was weighed into a 50mL single-neck flask, 20mL of N, N-dimethylformamide was added to dissolve the polyurethane block copolymer, 1680. Mu.L of bromododecane was added to the flask, nitrogen was introduced into the flask for 30min, the mixture was allowed to react at 70℃for 24h, the reaction mixture was added dropwise to cold N-hexane, the precipitate was collected, and the mixture was dried in an oven at 60℃to give the product symbols 1 to 12, 2 to 12 and 3 to 12, respectively.
Fig. 7 is a graph showing the results of the lowest effective antibacterial concentration of the bifunctional polyurethane material having self-repairing property and antibacterial property against escherichia coli in example 4, and the results show that the antibacterial polyurethane material synthesized by using bromododecane has a stronger sterilizing effect than the polyurethane material obtained by using bromon-hexane.
Example 5
Each of 0.3g of the block copolymers of example 1, example 2 and example 3 was dissolved in 18.7g of N, N-dimethylformamide, and the mixture was stirred at room temperature for 2 hours, 3g of commercial polyurethane was further added thereto, and stirring was continued at room temperature for 24 hours to obtain a mixed solution having a mass fraction of 15%, and the mixed solution was dried at 60℃for 48 hours to obtain a blend material having a thickness of about 300. Mu.m. In a penicillin bottle, a blend material disc with the diameter of 10mm is immersed in 10mL of ethanol, 200uL of bromon-hexane or 300uL of bromododecane is added, nitrogen is introduced into the solution for 30min, and the reaction is carried out for 24h at the temperature of 60 ℃. And (3) repeatedly cleaning the material with ethanol and n-hexane for three times after taking out the material to remove the residual bromon-hexane or bromododecane on the surface, and drying the material in a vacuum drying oven at 50 ℃ for 24 hours.
The product symbols are given in table 1, based on the blended block copolymer and the quaternizing agent used.
TABLE 1
Fig. 9 is a graph of the surface and internal XPS elemental analysis results of the bifunctional polyurethane material and polyurethane blend material having self-healing properties and antibacterial properties of example 5, in which absorption peaks of C, N, O, which occur near 284.8eV, 400.0eV, 531.9eV, are observed in the full spectrum, and characteristic absorption peaks of bromine element exist at 67.61eV in the film surface full spectrum.
Table 2 is a surface to internal element ratio table for the self-healing antimicrobial polyurethane material and polyurethane blend material of example 5, and it can be seen that the material surface has a ratio of C, N elements greater than the inner cross section and a ratio of O elements less than the inner cross section, with the material surface having increased Br elements relative to the inner cross section, as 0.03% of the Br elements of the inner cross section can be considered to be absent. The increase in surface C is due in part to the long alkyl chain of bromododecane used for quaternization, while the grafting of bromododecane provides Br element to the membrane surface, while the substantial increase in N element on the membrane surface is due to the enrichment of PDMAEMA molecular chains in the copolymer at the surface, and the substantial increase in N element due to the substantial DMAEMA structure.
TABLE 2
Fig. 10 is a graph showing the antibacterial effect against e.coli of the blend material of the bifunctional polyurethane material having self-repairing property and antibacterial property with the commercial polyurethane in example 5. Many E.coli colonies can be obviously observed on the pure PU film coated agar plate, and a small amount of colony growth exists on the surface of the surface quaternized blending material after co-incubation, especially, the surface of the material which is quaternized by C12 (namely, quaternized by bromododecane) has almost no colony, which indicates that the blending material has stronger sterilizing effect on E.coli.
Fig. 11 is a graph of the antimicrobial effect of the blend material of the dual function polyurethane material having self-healing and antimicrobial properties with the commercial polyurethane of example 5 against staphylococcus aureus. A large number of colonies grow on the agar plates corresponding to the PU films, and no colonies are observed on the agar surfaces corresponding to the surface quaternized blending materials, which indicates that the blending materials have stronger killing effect on staphylococcus aureus.
FIG. 12 is a graph showing the toxicity test results of cell CCK8 co-cultured with cells of the blend material of the self-repairing antimicrobial polyurethane material and the commercial polyurethane of example 5, showing that the blend material of the pure PU film and the quaternized surface has no obvious cytotoxicity, and the material has good cell compatibility.
FIG. 13 is a blood compatibility test result of the blend material of the self-repairing antimicrobial structural polyurethane material and the commercial polyurethane in example 5 with the hemolysis rate as an index. The graph (a) is a graph of the hemolysis result of the blend material, and the graph (b) is a hemolysis value measured by absorbance, and the hemolysis rate of the blend material is found to be lower than 2%, which meets the international standard requirement (< 5%), which indicates that all blend materials have good blood compatibility.
Finally, the following description: the above embodiments are preferred embodiments of the present invention, but the implementation of the present invention is not limited by the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention are equivalent.
Claims (10)
1. A double-functional polyurethane material with self-repairing performance and antibacterial performance comprises the following characteristics:
the difunctional polyurethane material with the self-repairing performance and the antibacterial performance is of a block polyurethane copolymer structure, the middle part is a polyurethane block, and the two ends are repeat units with tertiary amine structures;
disulfide bond self-repairing structures are added in the blocks to realize the self-repairing performance of the material;
and the repeated units at the two ends and different haloalkanes are subjected to quaternization reaction, so that a quaternary ammonium structure is generated, and the antibacterial effect is realized.
2. The method for preparing the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 1, which is characterized by comprising the following steps:
(1) Weighing dehydrated polyether glycol under the nitrogen atmosphere, adding diisocyanate, and performing prepolymerization under the action of a catalyst; dissolving a chain extender in a solvent A, adding the solvent A into a reaction system for reaction, and obtaining a reaction mixture which is an isocyanate terminated polyurethane intermediate with a disulfide bond self-repairing structure;
(2) Adding the homopolymer into the reaction mixture in the step (1), and continuing to react for 5-8 hours; then the reaction temperature is increased to carry out curing; after curing, dropwise adding the reaction mixture into the solvent B, collecting a product, and drying to obtain a polyurethane block copolymerization product;
(3) And (3) dissolving the polyurethane block copolymer product in the step (2) in the solvent A, adding haloalkane for reaction, dripping the reaction mixture into the solvent B, collecting precipitate, and drying to obtain the self-repairable antibacterial polyurethane material.
3. The method for preparing the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 2, wherein the method comprises the following steps:
the polyether glycol in the step (1) is any one of polytetramethylene glycol, polyethylene glycol and polypropylene glycol, and the molecular weight is 1000-3000;
the diisocyanate in the step (1) is any one of hexamethylene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate;
the catalyst in the step (1) is any one of bismuth neodecanoate, dibutyl tin dilaurate and stannous isooctanoate, and the dosage of the catalyst accounts for 1-5 per mill of the mass fraction of the reaction raw materials;
the prepolymerization condition in the step (1) is that the prepolymerization is carried out for 4-6 hours at the temperature of 60-70 ℃.
4. The method for preparing the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 2, wherein the method comprises the following steps:
the chain extender in step (1) is preferably 4,4' -diaminodiphenyl disulfide; the solvent A is any one of N, N-dimethylformamide, dioxane and dimethyl sulfoxide;
the molar ratio of the polyether glycol, the diisocyanate and the chain extender in the step (1) is 1.5 (3.0-3.1) (1.4-1.45);
the reaction condition in the step (1) is that the reaction is carried out for 5 to 6 hours at the temperature of 70 to 80 ℃.
5. The method for preparing the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 2, wherein the method comprises the following steps:
the homopolymer in step (2) is preferably poly (dimethylaminoethyl methacrylate); the homopolymer monomer side chain is provided with a tertiary amine structure and reacts with haloalkane to generate quaternary ammonium salt, preferably dimethylaminoethyl methacrylate;
the preparation method of the poly (dimethylaminoethyl methacrylate) comprises the steps of weighing the dimethylaminoethyl methacrylate with a tertiary amine structure and 2,2' -azo (2-methyl-N- (2-hydroxyethyl) propionamide) in a single-neck flask, adding anhydrous N, N-dimethylformamide with the volume of 2 times to 2.5 times into the single-neck flask for dissolution, and introducing nitrogen into the system for polymerization, wherein the molar ratio of the two is 40:1-100:1.
6. The method for preparing the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 2, wherein the method comprises the following steps:
the curing in the step (2) is curing for 1-2 hours at 80-90 ℃; the solvent B is any one of diethyl ether, methanol or n-hexane, and is preferably a cold-stored solvent B at the temperature of 4 ℃; the drying condition is that the material is dried in an oven at 60-65 ℃.
7. The method for preparing the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 2, wherein the method comprises the following steps:
the haloalkane in the step (3) is any one of long-chain haloalkane and short-chain haloalkane; the alkyl halide is preferably any one of n-hexane bromide and dodecane bromide;
the polyurethane block copolymer and haloalkane are used in an amount of 1g in step (3): 900-2000 mu L;
when the haloalkane is bromo-n-hexane, the polyurethane block copolymer is preferably used in an amount of 1g with bromo-n-hexane: 900-1000 mu L;
when the haloalkane is bromon-hexane, the dosage of the polyurethane block copolymerization product and bromododecane is preferably 1 g:1500-2000 mu L;
the reaction in the step (3) is carried out for 20-24 hours at 65-70 ℃ under the condition of nitrogen; and the drying is carried out by putting the dried materials into an oven at 60-65 ℃.
8. The application of the difunctional polyurethane material with self-repairing performance and antibacterial performance in the polyurethane catheter material is characterized in that: the double-functional polyurethane material with self-repairing property and antibacterial property is directly used as medical antibacterial polyurethane catheter material or as antibacterial additive of polyurethane catheter material.
9. The use of the bifunctional polyurethane material with self-repairing property and antibacterial property as claimed in claim 8 in polyurethane catheter material, wherein: the double-functional polyurethane material with self-repairing performance and antibacterial performance is taken as an antibacterial additive of a polyurethane catheter material, is dissolved in a solvent with a mass ratio of 1:10-1:15 with commercial polyurethane, is dried to obtain a blending material, and is subjected to surface quaternization by reacting with haloalkane to lead the surface of the blending material to be provided with antibacterial groups.
10. The use of the bifunctional polyurethane material having self-repairing properties and antibacterial properties as claimed in claim 9 in polyurethane catheter materials, wherein: the preparation method comprises the steps of dissolving a difunctional polyurethane material with self-repairing performance and antibacterial performance and commercial polyurethane in N, N-dimethylformamide in a mass ratio of 1:10, blending, drying to obtain a blended material, and carrying out surface quaternization on the blended material by reacting with haloalkane to enable the surface of the blended material to be provided with antibacterial groups.
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