Cellulose antibacterial material and preparation method and application thereof
阅读说明：本技术 一种纤维素抗菌材料及其制备方法和应用 (Cellulose antibacterial material and preparation method and application thereof ) 是由 宋文琦 高博 罗晨 訾帅 杨金腾 刘玉琨 于 2020-08-10 设计创作，主要内容包括：本发明公开了一种纤维素抗菌材料及其制备方法和应用,该纤维素抗菌材料是由离子液体单体和抗菌单体经RAFT聚合后,再与经尿素的碱性水溶液低温处理的纤维素加热反应而获得的,其具有良好抗生素吸附能力和抗菌能力,能够作为创伤敷料。本发明的方法,通过离子液体单体结构设计与抗菌单体选择,采用可控聚合技术,获得满足绿色碱溶剂体系下具同时满足该苛刻反应体系中良好水溶性、与羟基反应性和抗菌功能的聚离子液体大分子改性试剂,通过一步法,实现在碱溶剂体系中通过均相反应构建纤维素抗菌材料。(The invention discloses a cellulose antibacterial material and a preparation method and application thereof, the cellulose antibacterial material is obtained by polymerizing an ionic liquid monomer and an antibacterial monomer through RAFT and then heating and reacting with cellulose treated by urea alkaline aqueous solution at low temperature, has good antibiotic adsorption capacity and antibacterial capacity, and can be used as wound dressing. According to the method, through structural design of an ionic liquid monomer and selection of an antibacterial monomer, a controllable polymerization technology is adopted, a polyion liquid macromolecule modification reagent which meets the requirements of good water solubility, reactivity with hydroxyl and an antibacterial function in a green alkali solvent system and simultaneously meets the requirements of a harsh reaction system is obtained, and the cellulose antibacterial material is constructed through a homogeneous reaction in the alkali solvent system through a one-step method.)
1. A cellulose antibacterial material is characterized in that the cellulose antibacterial material is obtained by heating cellulose subjected to low-temperature treatment by urea alkaline aqueous solution to 10-60 ℃ after RAFT polymerization of an ionic liquid monomer shown as a formula (4) and an antibacterial monomer shown as a formula (5);
wherein n is 1-5; y is selected from chlorine, bromine,And CH3COO-Any one of them.
2. The cellulosic antimicrobial material of claim 1, wherein the ionic liquid monomer: the molar ratio of the antibacterial functional monomer is 0.5: 1-1: 0.5.
3. The cellulosic antimicrobial material of claim 1, wherein the cellulosic antimicrobial material has a structure according to formula (1):
in the formula (1), A is a cellulose chain with the structure
4. The cellulose antibacterial material according to claim 1, characterized in that it has a structure represented by formula (2):
5. a polyionic liquid for use in preparing a cellulosic antimicrobial material according to any one of claims 1 to 4, wherein the polyionic liquid has the structure according to formula (3):
wherein stat represents random copolymerization, and n is 1-5; y is selected from chlorine, bromine,And CH3COO-Any one of them.
6. A method for preparing a cellulosic antimicrobial material according to any one of claims 1 to 4, comprising:
mixing a polyionic liquid as described in claim 5 with cellulose treated with an alkaline aqueous solution of urea to control the polyionic liquid: the mass ratio of the cellulose is 1-12: 20, heating to 10-60 ℃ for reaction to obtain the cellulose antibacterial material as claimed in any one of claims 1-4.
7. The method for preparing a cellulose antibacterial material according to claim 6, wherein the alkaline aqueous solution of urea is an aqueous solution containing 7 wt% sodium hydroxide and 12 wt% urea at-12.5 ℃.
8. The method for preparing the cellulose antibacterial material according to claim 6, wherein the method for preparing the polyion liquid comprises the following steps:
synthesizing a PIL random copolymerization macromolecular chain by using an ionic liquid monomer shown as a formula (4), an antibacterial monomer shown as a formula (5) and a chain transfer agent in a polar solvent and initiating polymerization by using an initiator AIBN (AIBN) at 50-80 ℃;
wherein the ionic liquid monomer and the antibacterial monomer: CTA: the molar ratio of AIBN is 50-500: 1: 0.1; the ionic liquid monomer: the molar ratio of the antibacterial functional monomer is 0.5: 1-1: 0.5;
the polar solvent comprises: any one or more than two of N, N-dimethylformamide, dimethyl sulfoxide and water;
the chain transfer agent is 2-mercapto-S-thiobenzoylacetic acid.
9. The method for preparing the cellulose antibacterial material according to claim 8, wherein the ionic liquid monomer is prepared by the following steps:
y is selected from chlorine, bromine and BF4 -、NO3 -、CH3SO3 -And CH3COO-Any one of the above; m is selected from Na+、K+、NH4 +Any one of the above;
b is selected from chlorine, bromine, iodine and
dropwise adding an alkylating reagent with a structure shown in a formula (6) into N-vinyl imidazole or an aprotic polar solvent containing the N-vinyl imidazole according to a molar ratio of 1: 1, and reacting at a reaction temperature of 35-80 ℃ in an inert gas atmosphere to obtain a target ionic liquid monomer;
wherein the aprotic polar solvent comprises: any one or more than two of DMSO, DMF and acetonitrile.
10. Use of a cellulosic antimicrobial material according to any one of claims 1 to 4, as a wound dressing having antimicrobial properties.
Technical Field
The invention relates to an antibacterial material, in particular to a cellulose antibacterial material and a preparation method and application thereof.
Background
The ideal dressing needs to have the advantages of absorbing wound exudate, keeping the temperature and the humidity of a wound contact surface, good air permeability, antibiosis and antiphlogosis, and the like, and the hydrogel dressing is closer to the requirements of the ideal dressing. The hydrogel is a swelling body which is obtained by crosslinking hydrophilic high molecular compounds through covalent bonds, ionic bonds or hydrogen bonds and contains a large amount of water and has a three-dimensional network structure, has certain compressive strength, can provide a moist environment for wounds, and has better compatibility with biological tissues, so the hydrogel has great attention in the biomedical engineering fields of drug controlled release, tissue engineering scaffolds, wound dressings and the like, and has extremely good application prospect. The moist environment is helpful for cell growth and wound healing, but is also beneficial for growth of harmful microorganisms, so that the property of the functional dressing against harmful microorganism infection is particularly important.
The dressing based on the petroleum-based derivative as a raw material can generate secondary pollution to the ecological environment due to the defect that the dressing cannot be naturally degraded. Compared with petroleum-based materials, the plant cellulose is an ideal raw material with abundant resources, biodegradation and low cost, and is used for preparing green sustainable dressings. However, the conventional cellulose gel material is rich in hydroxyl groups, and due to the lack of antibacterial property and effective adsorption for antibiotics, bacterial aggregates are easily formed during the use process, so that the use performance is affected, and the further application of the cellulose fiber is severely limited. Therefore, there is an urgent need and challenge to design and manufacture a functional cellulose-based antimicrobial dressing having both antimicrobial and antibiotic adsorption properties.
Disclosure of Invention
The invention aims to provide a cellulose antibacterial material, a preparation method and application thereof, solves the problems that the existing dressing lacks antibacterial property and has effective adsorbability aiming at antibiotics, and has good antibiotic adsorption capacity and antibacterial capacity.
In order to achieve the aim, the invention provides a cellulose antibacterial material which is obtained by heating cellulose subjected to low-temperature treatment by urea alkaline aqueous solution to 10-60 ℃ for reaction after ionic liquid monomers shown in a formula (4) and antibacterial monomers shown in a formula (5) are subjected to RAFT polymerization;
wherein n is 1-5; y is selected from chlorine, bromine,And CH3COO-Any one of them.
Preferably, the molar ratio of the ionic liquid monomer to the antibacterial functional monomer is 0.5: 1-1: 0.5.
Preferably, the cellulose antibacterial material has a structure as shown in formula (1):
in the formula (1), A is a cellulose chain with the structureWhereinIs a joint with the structure of the formula (1), and a is 300-600; y is selected from chlorine, bromine,
Preferably, the cellulose antibacterial material has a structure as shown in formula (2):
another object of the present invention is to provide a polyion liquid for preparing the cellulose antibacterial material, which has a structure as shown in formula (3):
wherein stat represents random copolymerization, and n is 1-5; y is selected from chlorine, bromine,And CH3COO-Any one of them.
Another object of the present invention is to provide a method for preparing the cellulose antibacterial material, which comprises: mixing the polyion liquid with cellulose treated by urea alkaline aqueous solution, controlling the mass ratio of the polyion liquid to the cellulose to be 1-12: 20, and heating to 10-60 ℃ for reaction to obtain the cellulose antibacterial material.
Preferably, the alkaline aqueous solution of urea is an aqueous solution comprising 7 wt% sodium hydroxide and 12 wt% urea at-12.5 ℃.
Preferably, the preparation method of the polyion liquid comprises the following steps:
synthesizing a PIL random copolymerization macromolecular chain by using an ionic liquid monomer shown as a formula (4), an antibacterial monomer shown as a formula (5) and a chain transfer agent in a polar solvent and initiating polymerization by using an initiator AIBN (AIBN) at 50-80 ℃; wherein the molar ratio of the ionic liquid monomer to the antibacterial monomer to CTA to AIBN is 50-500: 1: 0.1; the molar ratio of the ionic liquid monomer to the antibacterial functional monomer is 0.5: 1-1: 0.5; the polar solvent comprises: any one or more than two of N, N-dimethylformamide, dimethyl sulfoxide and water; the chain transfer agent is 2-mercapto-S-thiobenzoylacetic acid.
Preferably, the preparation method of the ionic liquid monomer comprises the following steps:
y is selected from chlorine, bromine and BF4 -、NO3 -、CH3SO3 -And CH3COO-Any one of the above; m is selected from Na+、K+、NH4 +Any one of the above;
b is selected from chlorine, bromine, iodine andany one of the above; x is selected from any one of chlorine, bromine and iodine; n is 1-5;
dropwise adding an alkylating reagent with a structure shown in a formula (6) into N-vinyl imidazole or an aprotic polar solvent containing the N-vinyl imidazole according to a molar ratio of 1: 1, and reacting at a reaction temperature of 35-80 ℃ in an inert gas atmosphere to obtain a target ionic liquid monomer; wherein the aprotic polar solvent comprises: any one or more than two of DMSO, DMF and acetonitrile.
The invention also aims to provide application of the cellulose antibacterial material, and the cellulose antibacterial material is used as a wound dressing with antibacterial effect.
The cellulose antibacterial material, the preparation method and the application thereof solve the problems that the existing dressing lacks antibacterial property and has effective adsorbability aiming at antibiotics, and have the following advantages:
the cellulose antibacterial material has good antibiotic adsorption capacity and antibacterial capacity, and can be used as wound dressing.
According to the method, through structural design of an ionic liquid monomer and selection of an antibacterial monomer, a controllable polymerization technology is adopted, the polyionic liquid which has good water solubility, reactivity with hydroxyl and application functionality under a green alkali solvent system is obtained, at present, cellulose functionalization is carried out in a heterogeneous environment, and reaction under alkaline environment and homogeneous chemical reaction conditions is difficult to realize. The imidazole ionic liquid in the material can lead bacteria to agglomerate and split by destroying the cell wall structure, thus leading the bacteria to die and obtaining the antibacterial effect.
Drawings
Fig. 1 is a schematic structural diagram of the cellulose antibacterial material of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A cellulose antibacterial material having a structure represented by the following formula (1):
in the formula (1), A is a cellulose chain with the structureWhereinIs a joint with the structure of the formula (1), and a is 300-600; n is 1-5, the value of n cannot be larger than 5, otherwise, hydrophobicity is increased; y is selected from chlorine, bromine,And CH3COO-Any one of them.
More specifically, the cellulose antibacterial material has a structure shown in the following formula (2):
the preparation method of the cellulose antibacterial material comprises the following steps:
(1) ionic liquid monomer synthesis
The synthetic route is as follows:
y is selected from chlorine, bromine and BF4 -、NO3 -、CH3SO3 -And CH3COO-Any one of the above; m is selected from Na+、K+、NH4 +Any one of the above;
b is selected from chlorine, bromine, iodine and
Adding an alkylating reagent with a structure shown in a formula (6) into N-vinyl imidazole or an aprotic polar solvent containing the N-vinyl imidazole dropwise according to a certain molar ratio, heating to the reaction temperature of 35-80 ℃, and introducing an inert gas (such as nitrogen or argon) for reaction for 12-48 hours.
After the reaction is finished, purifying the product by adopting modes of rotary evaporation separation, organic solvent extraction and the like to obtain the ionic liquid monomer.
Wherein the aprotic polar solvent comprises: any one or more than two of DMSO, DMF and acetonitrile. The alkylation reaction reagent is selected from halogenated propylene oxide; chloroepoxybutane, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-diiodoethane, 1, 3-dibromopropane, 1, 3-diiodopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, etc. The halogenated epoxypropane is epichlorohydrin or epibromohydrin.
Further, if other anions are used, ion exchange is required, and the hydrophilicity and hydrophobicity (water solubility) of the monomer is adjusted by the different anions on the ion exchange reaction. Specifically, the ionic liquid monomer is placed in a salt solution containing the needed anions, reacted at normal temperature, and finally washed by deionized water.
(2) Synthesis of PIL macromolecular chain modifying reagent
Synthesizing a PIL random copolymerization macromolecular chain by using an ionic liquid monomer shown as a formula (4), an antibacterial monomer shown as a formula (5) (chlorinated 1-vinyl-3-octyl imidazole) and a Chain Transfer Agent (CTA) in a polar solvent in a manner of initiating polymerization by using an initiator AIBN (acrylonitrile butadiene styrene), wherein the reaction time is determined according to the half-life of the AIBN. Wherein the molar ratio of the ionic liquid monomer to the antibacterial monomer to CTA to AIBN is 50-500: 1:0.1, and the molar ratio of the ionic liquid monomer to the antibacterial functional monomer is 0.5: 1-1: 0.5.
Wherein the chain transfer agent is 2-mercapto-S-thiobenzoylacetic acid; the polar solvent is selected from one or more of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and water.
In the synthesized PIL macromolecular chain modifying reagent, the water solubility of the macromolecular chain modifying reagent can be realized by the imidazole ions in the ionic liquid monomer and the antibacterial monomer part, and the epoxy or halogen in the ionic liquid monomer can realize the reaction with the cellulose hydroxyl, so that the modification of the cellulose is realized, and meanwhile, the antibacterial monomer endows the modified cellulose with the antibacterial function.
(3) Preparation of cellulose antibacterial material
The method is characterized in that cotton fiber is used as a raw material, and an aqueous solution of 7 wt% of sodium hydroxide and 12 wt% of urea which are pre-cooled at the temperature of-12.5 ℃ is used as a solvent to prepare a cellulose solution with a certain concentration. And (3) dissolving the PIL macromolecular modifier prepared in the step (2) into the cellulose solution, controlling the mass ratio of the PIL macromolecular chain to the cellulose to be 1-12: 20, heating to 10-60 ℃ for reaction, and finally obtaining the PIL modified functional cellulose gel material with good antibiotic adsorption capacity and antibacterial capacity.
The following embodiment 1 specifically illustrates a method for preparing a cellulose antibacterial material provided by the present invention.