CN113134111A - Polyion liquid/polyurethane composite antibacterial film and preparation and application methods thereof - Google Patents
Polyion liquid/polyurethane composite antibacterial film and preparation and application methods thereof Download PDFInfo
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Abstract
The invention relates to a polyion liquid/polyurethane composite antibacterial film and preparation and application thereof, belonging to the technical field of antibacterial materials. The polyion liquid/polyurethane composite antibacterial membrane is prepared by polymerizing imidazole organic matters and halogenated normal alkyl serving as raw materials to prepare alkyl imidazolium salt ionic liquid, polymerizing to synthesize an anion framework, grafting and introducing imidazolium salt to prepare imidazole polyion liquid, and mixing and dissolving the imidazole polyion liquid and polyurethane to prepare the composite antibacterial membrane. The cation in the imidazole ionic liquid has a broad-spectrum antibacterial effect, so that the prepared composite antibacterial film has good biocompatibility and blood compatibility, and has excellent antibacterial performance and long-acting property. Because the polyurethane is mixed and dissolved, the polyurethane contains soft segment and hard segment structures which are not compatible thermodynamically, so that the polyurethane has excellent mechanical property. The preparation method is simple and easy to implement, is convenient for industrial popularization and application, and can be applied to the fields of clinical medical instruments and antibacterial materials.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to a polyion liquid/polyurethane composite antibacterial film and preparation and application methods thereof.
Background
In recent years, with the emergence of bacterial resistance due to the use of a large amount of antibiotics, the effects of traditional antibacterial drugs are greatly reduced, and therefore, research and manufacture of novel antibacterial drugs or materials become problems to be solved at present. Tracheotomy is an effective way to improve the ventilation state of a patient, but belongs to invasive operation, increases the risk of lung infection of the patient and increases the treatment burden of the patient. The previous research shows that the change of respiratory flora after tracheotomy can increase the risk of lung infection, so the novel composite antibacterial material has positive effect on ensuring the safety of patients.
Ionic liquids have been widely reported as an antibacterial material, and the antibacterial mechanism thereof is mainly that cations are combined with electronegative cell membranes of bacteria through electrostatic interaction, and meanwhile, hydrophobic alkyl chains are inserted into phospholipid bilayers to cause cell membrane rupture and finally cause bacterial death.
Polyionic liquids are a class of materials that incorporate ionic liquid units into the polymer structure to achieve both ionic liquid and polymer properties. The polyion liquid has a designable structure, controllable adjustment of polymer molecular weight, glass transition temperature, hydrophilic-hydrophobic water balance, charge density and counter ions can be realized by changing the species of ionic liquid groups, polyion liquids with different physical and chemical properties are obtained, and the polyion liquid has a wide application prospect in the antibacterial field. However, systematic research on the influence of the structure of polyionic liquid, including the type of cation, the configuration of antibacterial group and the type of chemical bond on the antibacterial activity of polymer is the focus and difficulty of research and discussion at home and abroad.
For the polyion liquid, the antibacterial performance is in certain connection with a substituent group at the N3 position, when the substituent group at the N3 position is an alkyl chain, the antibacterial performance of the imidazolium salt can be influenced by the length of the alkyl chain, and within a certain range, the longer the alkyl chain is, the stronger the antibacterial performance is. The imidazole polyionic liquid substituted by long carbon chains is gathered in suspension, and hydrophobic end groups (carbon chains) tend to be inserted into hydrophobic cell walls, so that the antibacterial activity is increased; and the charge density of the imidazolium salt is increased, so that the antibacterial performance of the imidazole-based ionic liquid is stronger.
The polyurethane film is a material with a porous structure in the compact surface layer, has the characteristics of high elasticity, high strength, wear resistance, heat resistance, chemical resistance and the like due to the unique chemical structure, can be used for industrial filtering materials, textile coatings and the like, has good biocompatibility and blood compatibility, has excellent air permeability, waterproof moisture permeability, excellent strength and toughness and certain hydrophilicity, and overcomes the defect that sweat generated by metabolism of a human body cannot be timely discharged out of the body by polyvinyl chloride, chloroprene rubber and various synthetic rubber coatings, so that the polyurethane film is attracted attention as a novel film-making material.
The polyurethane contains soft segment and hard segment structures which are not compatible with thermodynamics, so that the polyurethane has a unique micro-phase separation structure and excellent mechanical properties; the polyion liquid is combined with the polyurethane soft and hard segment branched chain by grafting of different branched chains, so that the combination between the polyion liquid and the polyurethane soft and hard segment branched chain is improved, meanwhile, the toughness and the mechanical strength of the polyurethane can be changed by adjusting the proportion of the soft segment to the hard segment, the film-forming aperture size of the polyurethane is influenced, and the degradation of the composite material is realized by utilizing different characteristics of the branched chains.
The Chinese invention patent CN104693777A discloses a scratch-resistant polyurethane film and a preparation method thereof, which increases the hardness of the surface of the polyurethane film and reduces the surface tension thereof, but because the surface is only modified, the relative influence on other performances of the polyurethane film is little, and the application range of the polyurethane is not favorably expanded; chinese patent CN111534922A discloses a preparation process of a high-hydrophobicity antibacterial polyurethane film, the fiber film has excellent hydrophobicity, but has moisture permeability when in use, so that the material for film packaging is wet, and the use is influenced; chinese patent CN110917381A discloses a bacterial cellulose/polyion liquid antibacterial film and a preparation method thereof, the composite film has low toxicity and good degradability, but the antibacterial performance of the composite film is relatively weak. Therefore, there is an urgent need to develop a novel green antibacterial material which is easily degradable and has good antibacterial properties.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polyion liquid/polyurethane composite membrane and a preparation and application method thereof. The prepared polyion liquid/polyurethane composite membrane has good mechanical property, biocompatibility and blood compatibility, excellent antibacterial property and long-acting property, and can be widely applied to the fields of clinical medical instruments and antibacterial materials as the antibacterial material.
In order to realize the purpose of the invention, the invention is realized by adopting the following technical route:
the polyion liquid/polyurethane composite antibacterial film is a composite film prepared by mixing and dissolving an imidazole polyion liquid prepared by grafting alkyl imidazole salt onto an anionic polymer serving as a framework and polyurethane, wherein the mass ratio of the imidazole polyion liquid to the polyurethane is 0.1-10: 1.
The preparation method of the polyion liquid/polyurethane composite antibacterial film comprises the following steps:
(1) mixing imidazole organic matters and halogenated normal alkyl uniformly, and reacting and refluxing; cooling after the reaction is finished to obtain alkyl imidazolium salt ionic liquid for later use;
(2) dissolving the alkyl imidazolium salt ionic liquid prepared in the step (1) and an anionic polymer monomer serving as a framework, an initiator and a cross-linking agent in a solvent, uniformly mixing by ultrasonic waves, polymerizing, washing and drying to obtain an imidazole ionic liquid;
(3) and (3) dissolving the imidazole polyionic liquid prepared in the step (2) in an organic solvent, uniformly mixing with a polyurethane organic solution to obtain a composite membrane material, and pouring to form a membrane to obtain the polyionic liquid/polyurethane composite antibacterial membrane.
Preferably, the molar ratio of the imidazole organic compound to the halogenated n-alkyl in the step (1) is 1-10: 1.
Preferably, the carbon chain length of the halogenated n-alkyl in the step (1) is 1-12.
Preferably, the reaction time of the imidazole organic compound and the halogenated n-alkyl in the step (1) is 1-24 hours, the reflux time is 24-96 hours, and the reaction temperature is 20-200 ℃.
Preferably, the anionic polymer monomer as a backbone in the step (2) is any one or two of amino acid, vinylbenzene, 2-acrylamido-2-methylpropanesulfonic acid, vinylamino acid, divinylbenzene and isopropylnitrile.
Preferably, the molar ratio of the alkyl imidazolium salt ionic liquid to the anionic polymer monomer used as the framework in the step (2) is 0.1-10: 1.
Preferably, the initiator in the step (2) is azobisisobutyronitrile or benzoin ether, and the using amount of the initiator is 0.1-50% of the total mass of the polymerized monomers.
Preferably, the amount of the cross-linking agent in the step (2) is 0.1-50% of the total mass of the polymerized monomers.
Preferably, the polymerization time in the step (2) is 4-8 h, and the vacuum drying time is 10-15 h.
Preferably, in the step (3), the film forming time is 1-24 hours, and the film forming temperature is 10-100 ℃.
The polyion liquid/polyurethane composite antibacterial film is applied to clinical medical instruments and daily life article antibacterial material products.
The invention has the advantages of
The polyion liquid/polyurethane composite antibacterial membrane is prepared by polymerizing imidazole organic matters and halogenated normal alkyl serving as raw materials to prepare alkyl imidazole salt ionic liquid, grafting the alkyl imidazole salt ionic liquid by taking an anionic polymer as a framework to prepare imidazole ionic liquid with antibacterial performance, and mixing and dissolving the imidazole ionic liquid and polyurethane to prepare the imidazole ionic liquid functional group-containing modified composite antibacterial membrane. The cation in the imidazole ionic liquid has a broad-spectrum antibacterial effect, so that the modified composite antibacterial film has good biocompatibility and blood compatibility, excellent antibacterial performance and long-acting property. Meanwhile, because the polyurethane is mixed and dissolved and contains soft segment and hard segment structures which are not compatible with thermodynamics, the polyurethane has excellent mechanical property. The preparation method of the imidazole ionic liquid modified fine polyion liquid/polyurethane composite antibacterial film prepared by the invention is simple and easy to implement, is convenient for industrial popularization and application, and provides a new choice for clinical medical instruments and antibacterial materials.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1:
the polyion liquid/polyurethane composite membrane described in this embodiment 1 uses 2-acrylamide-2-methylpropanesulfonic acid as a framework, and alkyl imidazole is grafted, where the mass ratio of polyion liquid to polyurethane is 1: 1.
3.0g of 1-butylimidazole and 6.1g of 1-bromobutane were dissolved in 25mL of acetonitrile; after being mixed evenly, 5.0g of potassium hydroxide is added for reflux reaction for 4 hours; cooling to room temperature after the reaction is finished, and removing the solvent by rotary evaporation; purifying the crude product by column chromatography with ethyl acetate/methanol as mobile phase; finally, a yellow oily liquid is obtained. 1-butylimidazole.
Dissolving 2g of acrylamide-2-methylpropanesulfonic acid and 0.465g of azobisisobutyronitrile in a proper amount of dimethyl sulfoxide, ultrasonically mixing, uniformly hooking, sealing, polymerizing for 6 hours at 60 ℃, washing with acetone after the reaction is finished, and drying to obtain the poly-2-acrylamide-2-methylpropanesulfonic acid. Dissolving the prepared poly (2-acrylamide-2-methylpropanesulfonic acid) and equimolar 1-butylimidazole in a proper amount of methanol, uniformly mixing, stirring at normal temperature for 24 hours, washing with diethyl ether for three times, and drying in a vacuum oven for 12 hours to obtain a product imidazole polyion liquid;
and then, dissolving 15% polyurethane in acetone under heating and stirring, adding 10g of polyion liquid, stirring and mixing, pouring into a film forming mold for forming, and placing in a vacuum drying oven to dry and form a film under the condition of 60 ℃ to obtain the polyion liquid/polyurethane composite antibacterial film.
Example 2:
the mass ratio of the polyion liquid to the polyurethane is 1: 1.
The procedure for preparing the polyion liquid/polyurethane composite antibacterial film was the same as in example 1 except that 1-bromobutane in example 1 was changed to 1-bromopentane.
Example 3:
the mass ratio of the polyion liquid to the polyurethane is 1: 2.
The remaining steps for preparing the polyion liquid/polyurethane composite antibacterial film are the same as in example 1.
Example 4:
1.8g of 1-vinylimidazole and 2.74g of n-butyl bromide were reacted at 25 ℃ with stirring for 72 h. After the reaction is finished, the mixture is respectively washed for 1 time by using ethyl acetate and anhydrous ether, and finally the mixture is put into a vacuum drying oven to be dried for 24 hours at the temperature of 30 ℃.
2g of prepared brominated 1-vinyl-3-butylimidazole, 1.5g of styrene, 6.5g of acrylonitrile, 0.1g of azobisisobutyronitrile and 0.12g of divinylbenzene were mixed and shaken with ultrasound to give a homogeneous solution; the mixed solution was then spread evenly on a glass plate and polymerized for 6 hours. Soaking and washing the polymerized polyion liquid with ethanol, and drying for 6 h. And then 2g of polyurethane with the content of 18 percent is dissolved in acetone under the condition of heating and stirring, then 1g of polyion liquid is added and mixed under the condition of stirring, the mixture is poured into a film forming mold for forming, and the film forming is carried out in a vacuum drying oven under the condition of 60 ℃ to obtain the polyion liquid/polyurethane composite antibacterial film.
Example 5:
the mass ratio of the polyion liquid to the polyurethane is 1: 2.
The remaining steps for preparing the polyion liquid/polyurethane composite antibacterial film are the same as in example 1.
Example 6:
the mass ratio of the polyion liquid to the polyurethane is 1: 1.
The procedure for preparing the polyion liquid/polyurethane composite antibacterial film was the same as in example 1 except that 1-bromobutane in example 1 was changed to 1-bromopentane.
And (3) performance testing:
the polyion liquid/polyurethane composite antibacterial film prepared in the above examples 1 to 6 was subjected to antibacterial performance and mechanical performance tests:
and (3) antibacterial property test: mixing the bacterial liquid with PET film and polyion liquid film (area of 1.5 × 1.5 cm)2) After the culture is carried out for 4h at 37 ℃, 10 mu L of the bacterial liquid is sucked and transferred to an LB solid agar plate, the bacterial liquid is evenly spread and put into a constant temperature incubator at 37 ℃ for 24h, and the number of macroscopic colonies is counted. Triplicate experiments were repeated for each well plate test. The antibacterial rate was calculated according to the following formula (A and B represent the number of colonies in the control group and the experimental group, respectively):
the test results were as follows:
table-antibacterial property comparison data table
Table two mechanical property comparison data table
The detection result shows that: the cation in the imidazole ionic liquid in the polyion liquid/polyurethane composite antibacterial film has a broad-spectrum antibacterial effect, so that the prepared composite antibacterial film has good biocompatibility and blood compatibility, and is excellent in antibacterial performance and long-acting. Meanwhile, the polyurethane is mixed and dissolved, so that the polyurethane has excellent mechanical properties.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (10)
1. A polyion liquid/polyurethane composite antibacterial film is characterized in that: the composite antibacterial membrane is prepared by mixing and dissolving imidazole ionic liquid prepared by grafting alkyl imidazole salt on an anionic polymer serving as a framework and polyurethane, wherein the mass ratio of the imidazole ionic liquid to the polyurethane is 0.1-10: 1.
2. A method for preparing the polyion liquid/polyurethane composite antibacterial film according to claim 1, which comprises the steps of:
1) mixing imidazole organic matters and halogenated normal alkyl uniformly, and reacting and refluxing; cooling after the reaction is finished to obtain alkyl imidazolium salt ionic liquid;
2) dissolving the alkyl imidazolium salt ionic liquid prepared in the step 1) and an anionic polymer monomer serving as a framework, an initiator and a cross-linking agent in a solvent, uniformly mixing by ultrasonic waves, polymerizing, washing and drying to obtain an imidazole ionic liquid;
3) dissolving the imidazole polyionic liquid prepared in the step 2) in an organic solvent, uniformly mixing with a polyurethane organic solution to obtain a composite membrane material, and pouring to form a membrane to obtain the polyionic liquid/polyurethane composite antibacterial membrane.
3. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the molar ratio of the imidazole organic matter to the halogenated n-alkyl in the step 1) is 1-10: 1.
4. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the carbon chain length of the halogenated n-alkyl in the step 1) is 1-12.
5. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the reaction time of the imidazole organic compound and the halogenated normal alkyl in the step 1) is 1-24 hours, the reflux time is 24-96 hours, and the reaction temperature is 20-200 ℃.
6. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the anionic polymer monomer used as the skeleton in the step 2) is any one or two of amino acid, vinyl benzene, 2-acrylamide-2-methyl propane sulfonic acid, vinyl amino acid, divinyl benzene and isopropyl nitrile.
7. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the molar ratio of the alkyl imidazolium salt ionic liquid to the anionic polymer monomer used as the framework in the step 2) is 0.1-10: 1.
8. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the initiator in the step 2) is azobisisobutyronitrile or benzoin ether, and the amount of the initiator is 0.1-50% of the total mass of the polymerized monomers; the dosage of the cross-linking agent is 0.1-50% of the total mass of the polymerized monomers.
9. The method for preparing polyion liquid/polyurethane composite antibacterial film as claimed in claim 2, wherein: the polymerization time in the step 2) is 4-8 h, and the vacuum drying time is 10-15 h; in the step 3), the film forming time is 1-24 hours, and the film forming temperature is 10-100 ℃.
10. The use of the polyion liquid/polyurethane composite antibacterial film as claimed in any one of claims 1 to 9 in clinical medical instruments and antibacterial materials.
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