CN109232953B

CN109232953B - Polyvinimidyl chloramine type antibacterial cellulose membrane, preparation method and application

Info

Publication number: CN109232953B
Application number: CN201810897797.8A
Authority: CN
Inventors: 张胜利; 凯橙橙; 刘伯芳; 张思略; 周祚万; 姜曼; 王群; 李勇
Original assignee: Southwest Jiaotong University
Current assignee: Southwest Jiaotong University
Priority date: 2018-08-08
Filing date: 2018-08-08
Publication date: 2020-11-03
Anticipated expiration: 2038-08-08
Also published as: CN109232953A

Abstract

The invention discloses a polyethyleneimine chloramine type antibacterial cellulose membrane, a preparation method and application thereof, wherein the preparation process comprises the following steps: step 1: preparing a cellulose solution with a mass concentration of 5 wt%; step 2: defoaming the cellulose solution, casting the cellulose solution on a substrate to form a film, solidifying and washing to obtain a regenerated cellulose gel film; and step 3: oxidizing the regenerated cellulose gel film by using a sodium periodate aqueous solution to obtain a dialdehyde cellulose gel film with the aldehyde amount of 1-3 mmol/g; and 4, step 4: immersing a dialdehyde cellulose gel film into a polyethyleneimine water solution for grafting reaction to obtain a polyethyleneimine grafted cellulose film; and 5: chloridizing the polyethyleneimine grafted cellulose membrane to obtain a polyethyleneimine chloroamine type antibacterial cellulose membrane; the method is carried out in aqueous solution, the reaction condition is mild, the process operation is simple, and the preparation process is environment-friendly; the prepared antibacterial cellulose membrane has good biocompatibility and air permeability, and excellent antibacterial and bactericidal properties.

Description

Polyvinimidyl chloramine type antibacterial cellulose membrane, preparation method and application

Technical Field

The invention relates to the field of preparation of high polymer materials, in particular to a polyethyleneimine chloramine type antibacterial cellulose membrane, a preparation method and application.

Background

In recent years, various bacterial diseases caused by microorganisms bring great harm and panic to human beings; therefore, the antibacterial agent with high efficiency and broad spectrum is in need of development and application; among a plurality of antibacterial agents, the N-halamine antibacterial agent has the advantages of high efficiency, durability, broad spectrum, reproducibility, no toxicity and the like as a novel antibacterial agent; n-halamine refers to a compound containing an N-X bond (X can be Cl, Br, I), which can be obtained by reacting a precursor compound containing an amine, amide or imide group with an oxidizing agent (such as hypochlorite); the antibacterial mechanism is that N-halamine releases halogen cation with strong oxidizing property, which breaks down cell membrane by contact and enters into the body of microorganism to interfere the activity and metabolic process of cell enzyme, thus leading to the death of bacteria, virus and other microorganisms.

The cellulose membrane has a series of excellent properties, such as strong hygroscopicity, good air permeability, good biocompatibility and biodegradability; in addition, the raw materials are easy to obtain, green, environment-friendly and renewable, and the composite material is widely applied to the aspects of water treatment, air purification, food packaging, medical materials and the like in recent years. But cellulose has no antibacterial property, and saccharides in the cellulose can provide energy for the propagation of microorganisms under certain conditions, so that germs are more easily bred; therefore, antibacterial cellulose containing a halamine antibacterial agent has attracted attention as a novel class of antibacterial materials. Patent No. cn201310206616.x uses cotton cloth as a carrier, firstly grafts haloalkylsilane, then introduces a cyclic halamine precursor through a quaternization reaction between a tertiary amine functional group and a haloalkyl group, and finally obtains quaternized halamine antibacterial cotton cloth through a halogenation reaction; in patent CN201410769240.8, macromolecular heterocyclic N-halamine is compounded on the surface of the nano bacterial cellulose by chemical oxidative polymerization. The patent CN201510059668.8 adopts a layer-by-layer self-assembly technology, and utilizes quaternized halamine modified chitosan and hydroxymethyl hydantoin to prepare the antibacterial cotton fabric. Patent 201410769240.8 discloses initiating polymerization of heterocyclic N-halamine antibacterial monomer on the surface of nano-bacterial cellulose by chemical oxidative polymerization, and finally obtaining a polymer halamine antibacterial composite nano-cellulose film by halogenation; however, the halamine precursor described in the above patent is a cyclic compound, and the amine to be subjected to chlorination reaction is a secondary amine.

Patent 201711273187.2 provides a PEI modified cellulose membrane adsorbent and a method for preparing the same. In the heavy metal ion adsorption process, primary amine, secondary amine and tertiary amine can become adsorption sites; the set range of the influence factors of the invention patent aims at preparing the adsorbent, and does not pay attention to the retention amount of primary amine and secondary amine in a final sample, but N-H of the primary amine and the secondary amine can be substituted in the chlorination process to generate N-Cl. Furthermore, polyethyleneimine is a chain-like flexible macromolecule, and the curling degree of the polyethyleneimine is not only influenced by the concentration of the polyethyleneimine but also related to the amount of aldehyde groups, and meanwhile, the amount of aldehyde groups directly influences the retention amount of primary amine and secondary amine.

"Development of inorganic Stable Steel wire via Surface modification with N-Halamine" A silane coupling agent GOPTS is deposited on Stainless Steel by layer-by-layer deposition technique, then polyethylene imine is grafted, then polyacrylic acid is grafted, and finally Chlorination is carried out. The grafting process of polyethyleneimine involves condensing agent EDC and coupling agent NHS; layer-by-layer deposition techniques consume primary amines and therefore chlorination occurs only on secondary amines.

Disclosure of Invention

The invention provides a polyethyleneimine chloramine type antibacterial cellulose membrane with good biocompatibility and antibacterial property, a preparation method and application thereof.

The technical scheme adopted by the invention is as follows: a preparation method of a polyethyleneimine chloramine type antibacterial cellulose membrane comprises the following steps:

step 1: preparing a cellulose solution with a mass concentration of 5 wt%;

step 2: defoaming the cellulose solution prepared in the step 1, casting the solution on a substrate to form a film, and washing the film after solidification to obtain a regenerated cellulose gel film;

and step 3: oxidizing the regenerated cellulose gel film obtained in the step (2) by using a sodium periodate aqueous solution to obtain a dialdehyde cellulose gel film with the aldehyde amount of 1-3 mmol/g;

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a polyethyleneimine water solution for grafting reaction to obtain a polyethyleneimine grafted cellulose film;

and 5: and (4) chlorinating the polyethyleneimine grafted cellulose membrane obtained in the step (4) to obtain the polyethyleneimine chloroamine type antibacterial cellulose membrane.

Further, the cellulose solution in step 1 is prepared by adding cellulose into a solvent, stirring and dissolving, wherein the solvent is one of TBAH/DMSO, TBAH/urea, LiCl/DMAC solvent and NMMO solution.

Further, in the step 3, the concentration of sodium periodate in the sodium periodate aqueous solution is 0.5-4 g/L, and the pH value is 3-6; the oxidation time is 1-48 h, and the oxidation temperature is 15-40 ℃.

Further, the mass concentration of the polyethyleneimine in the polyethyleneimine water solution in the step 4 is 0.05% -1%, the pH value is 9-11, and the reaction time is 15 min-4 h.

Further, in the step 4, the polyethyleneimine has a branched structure, and the molecular weight of the polyethyleneimine is less than 2000.

Further, after the grafting reaction in the step 4 is completed, washing and drying at 50 ℃ are carried out, so as to obtain the polyethyleneimine grafted cellulose membrane.

Further, in the step 5, chlorination is carried out by adopting one of a sodium hypochlorite solution or a calcium hypochlorite solution, the effective chlorine content is more than 2%, the pH value is 3-7, and the chlorination time is 15 min-4 h.

Further, after the chlorination reaction in the step 5 is completed, washing and drying are carried out at 35 ℃ to obtain the polyethyleneimine chloramine type antibacterial cellulose membrane.

A polyvinyl imido chloramine type antibacterial cellulose film.

The application of the polyethyleneimine chloramine-type antibacterial cellulose membrane can be used for resisting gram-negative bacteria and gram-positive bacteria.

The invention has the beneficial effects that:

(1) the invention breaks through the limitation of a cyclic halamine precursor and secondary amine, uses water-soluble high-molecular polyethyleneimine as an N-halamine precursor, contains primary amine, secondary amine and tertiary amine in a flexible macromolecular chain, and is beneficial to improving the density of antibacterial functional groups after chlorination treatment;

(2) the whole reaction process is carried out in aqueous solution, the reaction condition is mild, the process operation is simple, the preparation process is environment-friendly, and no toxic cross-linking agent is used;

(3) the antibacterial cellulose membrane prepared by the invention has good biocompatibility and air permeability, excellent antibacterial and bactericidal properties, is environment-friendly and can be recycled.

Drawings

FIG. 1 is an attenuated reflectance infrared (ATR-FTIR) spectrum of the product of each preparation of example 1 of the present invention.

FIG. 2 is an XPS chart showing the products obtained in each preparation process in example 1 of the present invention.

FIG. 3 is a schematic diagram of the inhibition zones of CM, DCM, PEI-DCM and Cl-PEI-DCM on gram-negative bacteria.

FIG. 4 is a schematic diagram of the inhibition zones of CM, DCM, PEI-DCM and Cl-PEI-DCM on gram-positive bacteria.

Detailed Description

A preparation method of a polyethyleneimine chloramine type antibacterial cellulose membrane comprises the following steps:

step 1: preparing a cellulose solution with a mass concentration of 5 wt%;

step 2: defoaming the cellulose solution prepared in the step 1, casting the solution on a substrate to form a film, solidifying the film and washing the film to obtain a regenerated cellulose gel film;

The preparation of the cellulose solution in the step 1 is obtained by adding cellulose into a solvent, stirring and dissolving, wherein the solvent is one of TBAH/DMSO, TBAH/urea, LiCl/DMAC solvent and NMMO solution.

Step 3, the concentration of sodium periodate in the sodium periodate aqueous solution is 0.5-4 g/L, and the pH value is 3-6; the oxidation time is 1-48 h, and the oxidation temperature is 15-40 ℃.

And 4, the mass concentration of the polyethyleneimine in the polyethyleneimine water solution is 0.05-1%, the pH value is 9-11, and the reaction time is 15 min-4 h.

In the step 4, the polyethyleneimine is in a branched structure, and the molecular weight of the polyethyleneimine is less than 2000.

And (4) after the grafting reaction is finished in the step (4), washing, and drying at the temperature of 50 ℃ to obtain the polyethyleneimine grafted cellulose membrane.

And 5, chlorinating by adopting one of a sodium hypochlorite solution or a calcium hypochlorite solution, wherein the effective chlorine content is more than 2.0%, the pH value is 3-7, and the chlorination time is 15 min-4 h.

And (5) after the chlorination reaction is finished, washing, and drying at 35 ℃ to obtain the polyethyleneimine chloramine type antibacterial cellulose membrane.

Example 1

Preparing a polyethyleneimine chloramine type antibacterial cellulose membrane according to the following steps:

step 1: adding 5g of cellulose into 95g of TBAH/DMSO solvent, and stirring and dissolving to obtain a 5wt% cellulose solution; TBAH/DMSO solvent is a mixed solution of 50 wt% TBAH aqueous solution and DMSO in a mass ratio of 1: 4;

step 2: defoaming the cellulose solution prepared in the step 1, carrying out tape casting on a substrate to form a film, placing the film in the air for gelation, and eluting the solvent with water to obtain a regenerated cellulose gel film (CM);

and step 3: putting 2g of the regenerated cellulose gel film obtained in the step 2 into a sodium periodate solution with the concentration of 1g/L, pH =5, oxidizing for 6h at 25 ℃, and then washing with water to obtain a dialdehyde cellulose gel film (DCM);

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a PEI solution with the concentration of 0.05% and the pH =10, carrying out grafting reaction at room temperature, washing with water after 2h, and drying at 50 ℃ to obtain a polyethyleneimine grafted cellulose film (PEI-DCM);

and 5: and (3) placing the polyethyleneimine grafted cellulose membrane obtained in the step (4) in a sodium hypochlorite aqueous solution with the pH =6 and the concentration of 2.5%, chlorinating at room temperature for 1h, and drying at 35 ℃ to obtain the polyethyleneimine chloroamine type antibacterial cellulose membrane (Cl-PEI-DCM).

The content of active chlorine in the polyethyleneimine chloroamine-type antibacterial cellulose membrane obtained in step 5 was measured to be 1.33wt% by a sodium thiosulfate-iodometry method.

CM, DCM and PEI-DCM in the figure represent samples obtained by drying the products obtained in step 2, step 3 and step 4 at 50 deg.C, respectively; in the figure, Cl-PEI-DCM represents a sample obtained by drying the product obtained in step 5 at 35 ℃.

In FIG. 1, a, b, c and d respectively represent CM, DCM, PEI-DCM and Cl-PEI-DCM. As can be seen from FIG. 1, 1738 cm of regenerated cellulose after selective oxidation with sodium periodate^-1A stretching vibration peak of carbonyl group appears, which indicates that hydroxyl group in the regenerated fiber membrane is oxidized into aldehyde group. In comparison, the dialdehyde cellulose membrane was treated with PEI at 3345 cm^-1The absorption peak of (2) is shifted to 3352 cm toward a high wavenumber^-1And the broadening becomes strong as a result of partial overlapping of the O-H stretching vibration absorption peak and the N-H stretching vibration absorption peak. At the same time, 1575 and 1542cm^-1Two new absorption peaks, corresponding to the N-H bending vibration of primary and secondary amines, respectively, were present, which all indicated that PEI molecules were successfully grafted onto dialdehyde cellulose films. After chlorination, 1575 and 1542cm were clearly observed^-1The absorption peak at (A) disappeared, which was attributed to the conversion of the N-H bond into the N-Cl bond.

Respectively representing the element composition of the sample prepared at each stage of the embodiment by an X-ray photoelectron spectrum analyzer; the results are shown in FIG. 2. As can be seen from FIG. 2, the XPS pattern of the PEI-grafted cellulose film showed a diffraction peak for the N element, compared to DCM, which further confirms that PEI molecules were successfully grafted onto the cellulose film. After PEI-DCM is chloridized, obvious diffraction peaks of Cl element are observed on an XPS graph of antibacterial membrane Cl-PEI-DCM due to the conversion of N-H bonds into oxidative N-Cl bonds in chlorination reaction.

FIG. 3 is a schematic diagram showing the inhibition zones of CM, DCM, PEI-DCM and Cl-PEI-DCM against gram-negative bacteria (E.coli); FIG. 4 is a schematic diagram showing the inhibition zones of CM, DCM, PEI-DCM and Cl-PEI-DCM against gram-positive bacteria (Staphylococcus aureus); as can be seen from FIGS. 3 and 4, Cl-PEI-DCM has excellent antibacterial activity against both gram-negative bacteria (E.coli) and gram-positive bacteria (Staphylococcus aureus).

Example 2

step 2: after the cellulose solution prepared in the step 1 is defoamed, a film is cast on a substrate to form a film, the film is placed in air for gelation, and then the solvent is eluted by water to obtain a regenerated cellulose gel film;

and step 3: putting 2g of the regenerated cellulose gel film obtained in the step 2 into a sodium periodate solution with the concentration of 1g/L, pH =5, oxidizing for 6h at 25 ℃, and then washing with water to obtain a dialdehyde cellulose gel film;

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a PEI solution with the concentration of 1% and the pH =9, carrying out grafting reaction at room temperature, washing with water after 4h, and drying at 50 ℃ to obtain a polyethyleneimine grafted cellulose film;

and 5: and (3) placing the polyethyleneimine grafted cellulose membrane obtained in the step (4) in a sodium hypochlorite aqueous solution with the pH =6 and the concentration of 2.5%, chlorinating at room temperature for 1h, and drying at 35 ℃ to obtain the polyethyleneimine chloroamine type antibacterial cellulose membrane.

Example 3

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a PEI solution with the concentration of 0.5% and the pH =11, carrying out grafting reaction at room temperature, washing with water after 1h, and drying at 50 ℃ to obtain a polyethyleneimine grafted cellulose film;

and 5: and (3) placing the polyethyleneimine grafted cellulose membrane obtained in the step (4) in a sodium hypochlorite aqueous solution with the pH =6 and the concentration of 5%, chlorinating at room temperature for 1h, and drying at 35 ℃ to obtain the polyethyleneimine chloroamine type antibacterial cellulose membrane.

Example 4

and step 3: putting 2g of the regenerated cellulose gel film obtained in the step 2 into a sodium periodate solution with the concentration of 4g/L, pH =5, oxidizing for 2h at 25 ℃, and then washing with water to obtain a dialdehyde cellulose gel film;

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a PEI solution with the concentration of 0.1% and the pH =10, carrying out grafting reaction at room temperature, washing with water after 2h, and drying at 50 ℃ to obtain a polyethyleneimine grafted cellulose film;

and 5: and (3) placing the polyethyleneimine grafted cellulose membrane obtained in the step (4) in a sodium hypochlorite aqueous solution with the pH =7 and the concentration of 2%, chlorinating at room temperature for 4h, and drying at 35 ℃ to obtain the polyethyleneimine chloroamine type antibacterial cellulose membrane.

Example 5

and step 3: putting 2g of the regenerated cellulose gel film obtained in the step 2 into a sodium periodate solution with the concentration of 1g/L, pH =5, oxidizing for 4h at 40 ℃, and then washing with water to obtain a dialdehyde cellulose gel film;

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a PEI solution with the concentration of 0.05% and the pH =10, carrying out grafting reaction at room temperature, washing with water after 15min, and drying at 50 ℃ to obtain a polyethyleneimine grafted cellulose film;

Example 6

and 4, step 4: immersing the dialdehyde cellulose gel film obtained in the step 3 into a PEI solution with the concentration of 0.05% and the pH =10, carrying out grafting reaction at room temperature, washing with water after 2h, and drying at 50 ℃ to obtain a polyethyleneimine grafted cellulose film;

and 5: and (3) placing the polyethyleneimine grafted cellulose membrane obtained in the step (4) in a sodium hypochlorite aqueous solution with the pH =7 and the concentration of 5%, chlorinating at room temperature for 1h, and drying at 35 ℃ to obtain the polyethyleneimine chloroamine type antibacterial cellulose membrane.

The invention can control the aldehyde group amount of the dialdehyde cellulose gel film by adjusting the concentration of the sodium periodate solution, the pH value, the oxidation time and the matching value of the oxidation temperature.

The invention breaks through the limitation of a cyclic halamine precursor and secondary amine, uses water-soluble branched polyethyleneimine as an N-halamine precursor, contains primary amine, secondary amine and tertiary amine in a flexible macromolecular chain, and is beneficial to improving the density of antibacterial functional groups after chlorination treatment; the whole reaction is carried out in aqueous solution, the reaction condition is mild, the process operation is simple, the preparation process is environment-friendly, and no toxic cross-linking agent is used; the prepared antibacterial cellulose membrane has good biocompatibility and air permeability, excellent antibacterial and bactericidal performance, environmental friendliness and recyclability.

Compared with the existing preparation method, the low molecular weight branched polyethyleneimine not only has good biocompatibility and water solubility, but also contains a large amount of primary amine, secondary amine and tertiary amine in the structure, and is an N-halamine precursor with a very promising prospect.

Claims

1. A preparation method of a polyethyleneimine chloramine type antibacterial cellulose membrane is characterized by comprising the following steps: step 1: preparing a cellulose solution with a mass concentration of 5 wt%;

and 5: chloridizing the polyethyleneimine grafted cellulose membrane obtained in the step (4) to obtain a polyethyleneimine chloroamine type antibacterial cellulose membrane;

the preparation of the cellulose solution in the step 1 is to add cellulose into a solvent, stir and dissolve the cellulose to obtain the cellulose solution, wherein the solvent is one of TBAH/DMSO, TBAH/urea, LiCl/DMAC solvent and NMMO solution;

in the step 3, the concentration of sodium periodate in the sodium periodate aqueous solution is 0.5-4 g/L, and the pH value is 3-6; the oxidation time is 1-48 h, and the oxidation temperature is 15-40 ℃;

in the step 4, the mass concentration of the polyethyleneimine in the polyethyleneimine water solution is 0.05-1%, the pH value is 9-11, and the reaction time is 15 min-4 h;

in the step 4, polyethyleneimine is in a branched structure, and the molecular weight of the polyethyleneimine is less than 2000;

after the grafting reaction in the step 4 is finished, washing and drying at 50 ℃ to obtain the polyethyleneimine grafted cellulose membrane;

in the step 5, one of a sodium hypochlorite solution and a calcium hypochlorite solution is adopted for chlorination, the effective chlorine content is more than 2%, the pH value is 3-7, and the chlorination time is 15 min-4 h;

and (3) after the chlorination reaction in the step (5) is finished, washing, and drying at 35 ℃ to obtain the polyethyleneimine chloramine type antibacterial cellulose membrane.

2. A polyethyleneimine chloroamine-type antibacterial cellulose membrane obtained by the preparation method according to claim 1.