CN114874355A - Amino-terminated hyperbranched chitosan quaternary ammonium salt and preparation method thereof - Google Patents
Amino-terminated hyperbranched chitosan quaternary ammonium salt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an amino-terminated hyperbranched chitosan quaternary ammonium salt and a preparation method thereof, wherein chitosan and maleic acid are dissolved in glycine hydrochloride ionic liquid, acylation reaction is carried out on the C2 site of chitosan to obtain maleic acid acylation chitosan, then substitution reaction is carried out on the C6 site of the maleic acid acylation chitosan and 2, 3-epoxypropyltrimethylammonium chloride in alkaline solution to synthesize the maleic acid acylation chitosan quaternary ammonium salt, and after diluted hydrochloric acid ultrasonic substitution treatment, the maleic acid acylation chitosan quaternary ammonium salt and an amino-terminated hyperbranched compound are dissolved in the glycine hydrochloride ionic liquid to carry out amide reaction, so as to prepare the amino-terminated hyperbranched chitosan quaternary ammonium salt. The method has the advantages of high reaction rate, easy control of the substitution degree of the chitosan quaternary ammonium salt, easy separation and high yield of the product, remarkable improvement of the antibacterial activity and water solubility of the prepared amino-terminated hyperbranched chitosan quaternary ammonium salt, good stability of the ionic liquid, strong reaction activity, greenness, environmental protection and easy recycling.
Description
Technical Field
The invention relates to an amino-terminated hyperbranched chitosan quaternary ammonium salt and a preparation method thereof, in particular to a method for preparing the amino-terminated hyperbranched chitosan quaternary ammonium salt with high yield by using an amino-terminated hyperbranched compound to replace C2 amino of chitosan and using ionic liquid as a medium, belonging to the technical field of high polymer materials.
Background
Chitosan, chemical name (1,4) -2-amino-2-deoxy- β -D-glucose, is an alkaline polysaccharide obtained by deacetylation of chitin. Chitosan is widely present in the skeletons of some microorganisms and mollusks such as shrimps, crabs and shells, and is the second largest biological resource with inferior biosynthesis yield to cellulose on earth [ Liu X Q, Zhao Xin-Xin, Liu Y, et al.review on preparation and administration properties of chitosan and chitosan compositions.Polymer Bulletin,2021(2): 1-33; yuan Yue, Qian Ben Xiang, Ling Xinlong, development of modification research of chitosan and application thereof, journal of textile science and engineering, 2019,36(3): 81-87). Chitosan has excellent antibacterial property, can exert antibacterial action by combining negative electrons of bacteria, is nontoxic, degradable and biocompatible, contains a large amount of amino and hydroxyl in the molecule, can form a large amount of hydrogen bonds and salt bonds with gas and metal ions, is used for adsorbing harmful gas, metal ions and the like, and is widely applied in the fields of water treatment, biomedical materials, food engineering, textile printing and dyeing and the like [ Wang Shen, Zhang Ming Yu, Ho Qian, and the like.
The chitosan molecular structure unit contains primary amino, primary hydroxyl and secondary hydroxyl, and the functional groups contain active hydrogen atoms and lone electron pairs, so that nucleophilic reaction can easily occur, and alkylation, quaternization, acylation, halogenation, redox and other reactions can occur under certain conditions. However, the molecules in chitosan have high orientation and strong hydrogen bonding between molecules, so that the crystal structure of the chitosan is compact and is difficult to dissolve in water and most organic solvents, and the chitosan can only be dissolved in acid solutions such as hydrochloric acid, polycarboxylic acid and the like. But the acid solution is easy to volatilize, difficult to recover, strong in corrosivity and pollutes the environment, so that the application of the chitosan is greatly limited. Therefore, the search for green solvents that can efficiently dissolve chitosan has been a hot research direction. Compared with the traditional organic solvent, the ionic liquid is widely applied to the fields of high polymer dissolution, catalytic reaction, chemical synthesis, electrochemical reaction and the like [ Liangsheng, Jinhuang, Lilu, and the like ] because of the characteristics of excellent chemical stability, thermal stability, easy recovery, recyclability, no toxicity, no pollution and the like of the ionic liquid, namely the fused salt which is composed of ions and has a melting point lower than 100 ℃, the ionic liquid is widely applied to the fields of chitosan dissolution, catalytic reaction, chemical synthesis, electrochemical reaction and the like [ Lisheng, Jinhuang, Lilu, and the like ] the influence of the amino acid ionic liquid on the chitosan dissolution performance, the science and engineering of high molecular materials, 2010,26(2): 70-72; chinese patent publication No. CN 107474161A. The ionic liquid can efficiently dissolve the chitosan and the derivatives thereof, the dissolved chitosan and the derivatives thereof do not generate derivatization reaction, and the ionic liquid can be used as a green direct solvent of the chitosan.
The chitosan quaternary ammonium salt is prepared by forming protection at the C2 position of chitosan and grafting 2, 3-epoxypropyl trimethyl ammonium chloride at the C6 position, and compared with the original chitosan, the water solubility and the antibacterial property of the chitosan quaternary ammonium salt derivative are greatly improved, and the application range of the chitosan is enlarged. At present, the scholars use benzaldehyde, salicylaldehyde, cinnamaldehyde and the like to form Schiff base protection on the amino at the C2 position of chitosan, and then graft quaternary ammonium salt on the C6 position to form a chitosan quaternary ammonium salt derivative, but the substitution degree of the quaternary ammonium salt at the C6 position of the chitosan quaternary ammonium salt is low, the preparation process is complex, and the protective agent benzaldehyde also has certain toxicity [ Hanyongxiao, Liuhongmei, Wenhiping, and the like. Schiff base protection is formed at the C2 position of chitosan, quaternary ammonium salt is grafted at the C6 position, and then the Schiff base at the C2 position is removed to obtain the chitosan quaternary ammonium salt with double antibacterial groups, but the chitosan quaternary ammonium salt has the problems of low substitution degree of the quaternary ammonium salt, few reaction groups, poor bonding fastness with fiber, poor water resistance and the like [ Liuxin, Chenhai phase, Chen Uguo, synthesis and characterization of O-quaternary ammonium salt chitosan and antibacterial performance research, academic report of Zhejiang institute of science and technology, 2009,26(5): 677-laid 681 ]. Due to the compact structure of chitosan and the strong hydrogen bonding among molecules, most reactions are carried out in an amorphous region, and water is generated in the quaternization substitution reaction, which is not beneficial to forward reaction, so that the reaction time is long, and the substitution degree and the yield of the chitosan quaternary ammonium salt are low. In recent years, the research and development of a synthesis method of chitosan quaternary ammonium salt which is environment-friendly, fast in reaction and high in degree of substitution is an urgent problem to be solved.
The hyperbranched compound is a polymer with approximate spherical structure, rich end groups, high solubility, low viscosity and high activity, the performance of the hyperbranched compound is greatly influenced by the properties of the end groups, each end group can be further functionalized to prepare a functional hyperbranched compound, and the functionality of the hyperbranched polymer can be improved by adjusting the functionalized positions and the number of the functional groups, so that the application of the hyperbranched polymer in different fields is realized; the synthesis method of the hyperbranched compound is simple and low in cost, is valued and loved by researchers, and becomes a research hotspot [ Zhang Delong, Zhang Feng, Linhong, and the like. The amino-terminated hyperbranched compound is one of hyperbranched compounds, the surface of the amino-terminated hyperbranched compound contains a large amount of amino groups, the amino-terminated hyperbranched compound can be dissolved in water and an organic solvent, the application prospect is wide, quaternary ammonium salt of the amino-terminated hyperbranched compound with excellent antibacterial performance can be obtained by grafting quaternary ammonium salt or quaternizing amino groups on the surface of the amino-terminated hyperbranched compound, but the method uses acid anhydride, monomers containing double bonds and carboxyl or ester groups and polyamino monomers to synthesize the amino-terminated hyperbranched compound firstly, and then uses quaternizing reagents such as glycidol trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and the like to carry out substitution reaction in an aqueous medium, and because the water generated in a reaction product hinders the quaternizing positive reaction, the product yield is low, the reaction process is long (24h), and the reagent dosage is large [ Chinese patent publication No. CN101200544B ].
According to the invention, macromolecular chitosan and maleic acid are dissolved in glycine hydrochloride ionic liquid for acylation reaction, the product water generated in the reaction can be absorbed by the ionic liquid, the amide reaction is facilitated, then the maleic acid acylation chitosan product is separated out by adding absolute ethyl alcohol, and the ionic liquid can be recycled after drying to remove the absolute ethyl alcohol. The maleic acid acylation chitosan reacts with 2, 3-epoxypropyl trimethyl ammonium chloride under the alkaline condition, because the C2 site of the chitosan is protected by maleic acid acylation, the quaternary ammonium salt only carries out nucleophilic substitution reaction at the C6 site of the maleic acid acylation chitosan, the obtained maleic acid acylation chitosan quaternary ammonium salt has high substitution degree and product yield, and the C2 site in the molecule contains carboxyl with stronger activity, thereby enhancing the chemical reaction with the amino-terminated hyperbranched compound. The maleic acid acylation chitosan quaternary ammonium salt and the amino-terminated hyperbranched compound are subjected to an amide reaction in the ionic liquid, the ionic liquid medium is easy to absorb free water generated in the reaction process, the occurrence of reverse reaction is effectively reduced, the yield and the substitution degree of the amino-terminated hyperbranched chitosan quaternary ammonium salt are both remarkably improved, the ionic liquid reaction system is mild in condition, the catalytic reaction rate is high, the substitution degree of the chitosan quaternary ammonium salt is easy to control, the product is easy to separate, the ionic liquid serving as a solvent and the reaction medium is environment-friendly and can be recycled, and the amino-terminated hyperbranched chitosan quaternary ammonium salt product with high yield and substitution degree can be prepared; the amino-terminated hyperbranched chitosan quaternary ammonium salt structure contains quaternary ammonium salt and rich imino and amino groups, still maintains the characteristics of the alkaline chitosan, and has excellent antibacterial property, water solubility and biocompatibility. The amino-terminated hyperbranched chitosan quaternary ammonium salt and the preparation method thereof have not been reported at all.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides an amino-terminated hyperbranched chitosan quaternary ammonium salt and a preparation method thereof. The amino-terminated hyperbranched chitosan quaternary ammonium salt takes macromolecular chitosan as a raw material, the macromolecular chitosan and maleic acid are dissolved in ionic liquid for acylation reaction, and then absolute ethyl alcohol is used for precipitation to prepare maleic acid acylation chitosan; and then substituting hydroxyl at C6 position of the maleic acid acylated chitosan by 2, 3-epoxypropyl trimethyl ammonium chloride under alkaline conditions to synthesize maleic acid acylated chitosan quaternary ammonium salt, carrying out ultrasonic replacement treatment by dilute hydrochloric acid, dissolving the maleic acid acylated chitosan quaternary ammonium salt and an amino-terminated hyperbranched compound in glycine hydrochloride ionic liquid to carry out amide reaction, and thus obtaining the amino-terminated hyperbranched chitosan quaternary ammonium salt. The ionic liquid is used as a solvent and a reaction medium, so that the acylation reaction of maleic acid and chitosan is promoted, the amide reaction of the maleic acid acylation chitosan quaternary ammonium salt and the amino-terminated hyperbranched compound is carried out in an ionic liquid system, free water generated in the reaction can be effectively absorbed by the ionic liquid, the reverse reaction of amide is reduced, and the substitution degree and the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt are improved to a great extent. Compared with the common chitosan quaternary ammonium salt, the amino-terminated hyperbranched chitosan quaternary ammonium salt is rich in a large number of active groups such as quaternary ammonium salt, imino group, amino group and the like, has the advantages of good water solubility, strong antibacterial activity, high biocompatibility and the like, and ionic liquid used as a reaction medium can be recycled and reused, so that the environmental pollution is small.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an amino-terminated hyperbranched chitosan quaternary ammonium salt is characterized in that: the amino-terminated hyperbranched chitosan quaternary ammonium salt is obtained by performing acylation reaction on C2-site amino and maleic acid in chitosan molecules to protect, replacing part or all of C6-site hydroxyl by 2, 3-epoxypropyltrimethylammonium chloride, and performing amide reaction on C2-site carboxyl (which is the carboxyl of the maleic acid obtained after acylation reaction of the C2-site amino of chitosan and the maleic acid) and an amino-terminated hyperbranched compound, wherein the structural formula is shown as a formula (1):
the viscosity average molecular weight of the amino-terminated hyperbranched chitosan quaternary ammonium salt is 32.4-61.2 ten thousand, the substitution degree of the quaternary ammonium salt at the C6 site is 43.57-81.86%, the grafting rate of the amino-terminated hyperbranched compound at the C2 site is 60.47-91.85%, the product yield is 70.38-92.69%, and the solubility in water is more than or equal to 9.43g/100 mL.
As shown in fig. 1, the preparation method of the amino-terminated hyperbranched chitosan quaternary ammonium salt comprises the following steps:
(1) firstly, dissolving macromolecular chitosan with the viscosity-average molecular weight of 72-85 ten thousand and the deacetylation degree of more than or equal to 93.5% in glycine hydrochloride ionic liquid according to the bath ratio of 1: 15-30, then adding maleic acid for dissolving, stirring and reacting at 40-60 ℃ for 1-3 h, immediately adding absolute ethyl alcohol to separate out a precipitate after the reaction is finished, soaking the filtered precipitate in absolute ethyl alcohol for ultrasonic cleaning for 3-5 times, each time for 20-30 min, fully replacing the ionic liquid in the precipitate, and filtering, drying and crushing to obtain maleic acid acylated chitosan;
(2) swelling the maleic acid acylation chitosan in NaOH solution with the mass concentration of 0.1-0.6% for 40-90 min according to the bath ratio of 1: 10-20, adding 2, 3-epoxypropyltrimethylammonium chloride for dissolving, stirring at 60-85 ℃ for substitution reaction for 2-6 h, precipitating and filtering a final product with absolute ethanol, extracting with absolute ethanol for 18-24 h, filtering, and freeze-drying to obtain the maleic acid acylation chitosan quaternary ammonium salt;
(3) carrying out ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt for 40-90 min at 25-40 ℃ by using 0.02mol/L diluted hydrochloric acid, dissolving the maleic acid acylation chitosan quaternary ammonium salt by using glycine hydrochloride ionic liquid at 60-80 ℃, dropwise adding an amino-terminated hyperbranched compound/glycine hydrochloride ionic liquid solution with the mass concentration of 0.5-2%, stirring and reacting for 2-4 h at 45-60 ℃, adding absolute ethyl alcohol to separate out a precipitate, filtering, cleaning with ultrasonic absolute ethyl alcohol, freeze drying, ball milling and crushing to obtain the amino-terminated hyperbranched chitosan quaternary ammonium salt.
In the step (1), the mass ratio of the chitosan to the maleic acid is 1: 0.7-3.
In the step (2), the mass ratio of the maleic acid acylation chitosan to the 2, 3-epoxypropyl trimethyl ammonium chloride is 1: 2-5.
In the step (3), the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the amino-terminated hyperbranched compound is 1: 0.2-1, and the weight average molecular weight of the amino-terminated hyperbranched compound is 4275-6360.
The bath ratio is the ratio of the mass (g) of chitosan to the volume (mL) of the ionic liquid.
By optimizing the reaction time, temperature, alkali concentration, the quantitative proportion of 2, 3-epoxypropyltrimethylammonium chloride to the maleic acid acylated chitosan substance and the quantitative proportion of the maleic acid acylated chitosan quaternary ammonium salt to the amino-terminated hyperbranched compound substance, a series of high-yield amino-terminated hyperbranched chitosan quaternary ammonium salt products with different degrees of substitution can be obtained.
Compared with the prior art, the invention has the beneficial effects that:
1. macromolecular chitosan and maleic acid are dissolved in glycine hydrochloride ionic liquid for acylation reaction, the glycine hydrochloride acidic ionic liquid is a good solvent for chitosan, the chitosan can be rapidly dissolved, the degradation of the chitosan in the ionic liquid due to high-temperature and long-time dissolution is effectively reduced, the good physical and chemical properties of the chitosan are maintained, and the ionic liquid can absorb water generated by acylation reaction in the homogeneous reaction of the chitosan and the maleic acid, so that the forward reaction is promoted; the maleic acid acylation chitosan product is separated out by adding absolute ethyl alcohol, and the ionic liquid can be recycled after the absolute ethyl alcohol is removed by drying. The maleic acid acylation chitosan reacts with 2, 3-epoxypropyl trimethyl ammonium chloride under the alkaline condition, because the C2 site of the chitosan is protected by maleic acid acylation, the quaternary ammonium salt only carries out nucleophilic substitution reaction at the C6 site of the maleic acid acylation chitosan, the maleic acid acylation chitosan quaternary ammonium salt with high substitution degree and product yield can be obtained, and the C2 site in a product molecule contains carboxyl with stronger activity, thereby enhancing the chemical reaction with the amino-terminated hyperbranched compound.
2. The invention adopts the ionic liquid as the solvent and the reaction medium for the amide reaction of the maleic acid acylation chitosan quaternary ammonium salt and the amino-terminated hyperbranched compound, and the free water generated in the reaction can be effectively absorbed by the ionic liquid, thereby preventing the generation of the reverse reaction of amide and greatly improving the substitution degree and the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt. Meanwhile, the glycine hydrochloride ionic liquid acidic ionic liquid can catalyze the amide reaction of the maleic acid acylation chitosan quaternary ammonium salt and the amino-terminated hyperbranched compound, and the glycine hydrochloride acidic ionic liquid can enable a large amount of-NH in the amino-terminated hyperbranched compound molecules 2 With positive charge (-NH) 3 + ) The nucleophilic activity is enhanced, the nucleophilic addition reaction of the amino-terminated hyperbranched compound and-COOH in the maleic acid acylation chitosan quaternary ammonium salt is greatly promoted, and the horse is enabled to beThe grafting rate of the amino-terminated hyperbranched compound on the C2 site of the chitosan quaternary ammonium salt acylated with the maleic acid is obviously improved; the amino-terminated hyperbranched chitosan quaternary ammonium salt contains a large amount of-NH 2 Is liable to form-NH 3 + Meanwhile, the quaternary ammonium salt group with positive charge can damage the bacterial cell membrane to kill bacteria, so that the amino-terminated hyperbranched chitosan quaternary ammonium salt has excellent antibacterial capability and lasting and high-efficiency antibacterial activity.
3. The invention uses the glycine hydrochloride ionic liquid as the solvent of the chitosan quaternary ammonium salt and the medium of the substitution reaction, and the ionic liquid has stable physicochemical property, no toxicity, no pollution, no evaporation pressure, no volatilization and easy separation from the product. After the chitosan ionic liquid solution reacts with maleic acid and the maleic acid acylation chitosan quaternary ammonium salt ionic liquid solution reacts with the amino-terminated hyperbranched compound, anhydrous ethanol is added into the ionic liquid to enable the reactants and the ionic liquid to be separated instantly, the chitosan quaternary ammonium salt product is easy to form precipitate from the ionic liquid and completely separate out, the filtered ionic liquid is dried at high temperature in vacuum to evaporate ethanol, and the ionic liquid can be recycled.
4. The primary hydroxyl at the C6 position of the amino-terminated hyperbranched chitosan quaternary ammonium salt prepared by the invention is replaced by quaternary ammonium salt, the C2 position is grafted with an amino-terminated hyperbranched compound, the characteristics of a chitosan ring framework and chitosan as alkaline polysaccharide are not influenced, and the maleic acid acylation chitosan quaternary ammonium salts with different substitution degrees and the amino-terminated hyperbranched chitosan quaternary ammonium salts with different grafting rates can be prepared by controlling the parameters of reaction time, temperature, reactant concentration and the like in an alkaline environment; meanwhile, the maleic acid acylation chitosan quaternary ammonium salt not only has the typical antibacterial, moisture absorption, moisture retention and other performances of the quaternary ammonium salt, but also keeps the characteristics of biocompatibility, degradability and the like of the chitosan, and the amino-terminated hyperbranched chitosan quaternary ammonium salt contains polar groups such as quaternary ammonium salt, amino, imino and the like in a molecular chain, has the typical characteristics of cationic polymers, has excellent and lasting antibacterial property, and solves the limitation that the chitosan is antibacterial only under an acidic condition. In addition, after long-term use by human, the irritation, the anaphylaxis, the chronic toxicity, the subacute toxicity and the acute toxicity of the chitosan quaternary ammonium salt are proved to be qualified by experiments, can be safely used, cannot cause secondary pollution to the environment, and accords with the concept of a green antibacterial agent. Therefore, the amino-terminated hyperbranched chitosan quaternary ammonium salt can be used as a water-soluble green antibacterial agent and is easy to popularize and apply.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the amino-terminated hyperbranched chitosan quaternary ammonium salt of the invention;
FIG. 2 is a scanning electron microscope image of the maleic acid acylated chitosan quaternary ammonium salt and amino-terminated hyperbranched chitosan quaternary ammonium salt samples in test item 1 of the present invention.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and examples, which are given for the purpose of illustration only and are not intended to be limiting in any way.
Preparation of amino-terminated hyperbranched chitosan quaternary ammonium salt
Example 1
Weighing 2.0g of chitosan with viscosity-average molecular weight of 75 ten thousand and deacetylation degree of 95% according to a bath ratio of 1:20(w/v) and dissolving in 40mL of glycine hydrochloride ionic liquid, adding 4.0g of maleic acid to dissolve, stirring at 45 ℃ to react for 2h, immediately adding 80mL of absolute ethanol after the reaction is finished to separate out a precipitate, soaking the filtered precipitate in absolute ethanol for ultrasonic cleaning for 3 times, 30min each time, fully replacing ionic liquid in the precipitate, and then filtering, drying and crushing to obtain the maleic acid acylated chitosan.
Swelling the dried maleic acid acylation chitosan in 0.3 mass percent NaOH solution for 60min according to a bath ratio of 1:20(w/v), adding 2, 3-epoxypropyltrimethylammonium chloride according to a mass ratio of 1:3 of the maleic acid acylation chitosan to the 2, 3-epoxypropyltrimethylammonium chloride, dissolving, stirring at 60 ℃ for substitution reaction for 4h, precipitating and filtering a final product by absolute ethyl alcohol, extracting for 20h by absolute ethyl alcohol, filtering, freeze-drying and crushing to obtain the maleic acid acylation chitosan quaternary ammonium salt.
Performing ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt by using 0.02mol/L diluted hydrochloric acid at 30 ℃ for 60min, then dissolving maleic acid acylation chitosan quaternary ammonium salt by using glycine hydrochloride ionic liquid at 70 ℃, dropwise adding 0.8 mass percent of amino-terminated hyperbranched compound (weight average molecular weight is 4805)/glycine hydrochloride ionic liquid solution to ensure that the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the amino-terminated hyperbranched compound is 1:0.4, stirring and reacting for 3h at 50 ℃, adding absolute ethyl alcohol to separate out a precipitate, filtering, cleaning with ultrasonic absolute ethyl alcohol, freeze drying, ball milling and crushing, the obtained light yellow amino-terminated hyperbranched chitosan quaternary ammonium salt A has the viscosity average molecular weight of 40.8 ten thousand, the substitution degree of the quaternary ammonium salt at the C6 site of 49.03 percent and the grafting rate of the amino-terminated hyperbranched compound at the C2 site of 71.24 percent, and is bagged and stored for later use at the temperature of 4 ℃. According to tests, the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt A obtained in the embodiment is 90.51%, and the solubility in water is 13.86g/100 mL.
Example 2
Weighing 2.0g of chitosan with viscosity-average molecular weight of 75 ten thousand and deacetylation degree of 95% according to a bath ratio of 1:20(w/v) and dissolving in 40mL of glycine hydrochloride ionic liquid, adding 5.0g of maleic acid to dissolve, stirring at 50 ℃ to react for 2h, immediately adding 80mL of absolute ethanol after the reaction is finished to separate out a precipitate, soaking the filtered precipitate in absolute ethanol for ultrasonic cleaning for 3 times, 30min each time, fully replacing ionic liquid in the precipitate, and then filtering, drying and crushing to obtain the maleic acid acylated chitosan.
Swelling the dried maleic acid acylation chitosan in 0.4% NaOH solution according to a bath ratio of 1:20(w/v) for 60min, adding 2, 3-epoxypropyltrimethylammonium chloride according to a mass ratio of 1:3 of the maleic acid acylation chitosan to the 2, 3-epoxypropyltrimethylammonium chloride, dissolving, stirring at 70 ℃ for carrying out substitution reaction for 5h, precipitating and filtering a final product by using absolute ethanol, extracting for 24h by using the absolute ethanol, and filtering, freeze-drying and crushing to obtain the maleic acid acylation chitosan quaternary ammonium salt.
Performing ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt by using 0.02mol/L diluted hydrochloric acid at 30 ℃ for 80min, then dissolving maleic acid acylation chitosan quaternary ammonium salt by using glycine hydrochloride ionic liquid at 70 ℃, dropwise adding amino-terminated hyperbranched compound (weight average molecular weight is 4805)/glycine hydrochloride ionic liquid solution with the mass concentration of 1.5% to ensure that the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the amino-terminated hyperbranched compound is 1:0.4, stirring and reacting for 3h at 60 ℃, adding absolute ethyl alcohol to separate out a precipitate, filtering, cleaning with ultrasonic absolute ethyl alcohol, freeze drying, ball milling and crushing, the obtained yellow amino-terminated hyperbranched chitosan quaternary ammonium salt B has the viscosity average molecular weight of 47.6 ten thousand, the substitution degree of the C6-site quaternary ammonium salt of 60.95 percent and the grafting rate of the C2-site amino-terminated hyperbranched compound of 78.76 percent, and is bagged and stored for later use at 4 ℃. According to tests, the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt B obtained in the embodiment is 85.28%, and the solubility in water is 17.44g/100 mL.
Example 3
Weighing 2.0g of chitosan with viscosity-average molecular weight of 75 ten thousand and deacetylation degree of 95% according to a bath ratio of 1:20(w/v) and dissolving in 40mL of glycine hydrochloride ionic liquid, adding 6.0g of maleic acid to dissolve, stirring at 60 ℃ to react for 2h, immediately adding 80mL of absolute ethanol after the reaction is finished to separate out a precipitate, soaking the filtered precipitate in absolute ethanol for ultrasonic cleaning for 4 times, 30min each time, fully replacing ionic liquid in the precipitate, and then filtering, drying and crushing to obtain the maleic acid acylated chitosan.
Swelling the dried maleic acid acylation chitosan in 0.5 mass percent NaOH solution for 90min according to a bath ratio of 1:20(w/v), adding 2, 3-epoxypropyltrimethylammonium chloride according to a mass ratio of 1:4 of the maleic acid acylation chitosan to the 2, 3-epoxypropyltrimethylammonium chloride, dissolving, stirring at 80 ℃ for substitution reaction for 5h, precipitating and filtering a final product by absolute ethyl alcohol, extracting for 24h by absolute ethyl alcohol, filtering, freeze-drying and crushing to obtain the maleic acid acylation chitosan quaternary ammonium salt.
Performing ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt by using 0.02mol/L diluted hydrochloric acid at 40 ℃ for 80min, then dissolving maleic acid acylation chitosan quaternary ammonium salt by using glycine hydrochloride ionic liquid at 70 ℃, dropwise adding amino-terminated hyperbranched compound (weight-average molecular weight is 5690)/glycine hydrochloride ionic liquid solution with the mass concentration of 2.0% to ensure that the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the amino-terminated hyperbranched compound is 1:0.6, stirring and reacting for 3h at 60 ℃, adding absolute ethyl alcohol to separate out a precipitate, filtering, cleaning with ultrasonic absolute ethyl alcohol, freeze drying, ball milling and crushing, the obtained deep yellow amino-terminated hyperbranched chitosan quaternary ammonium salt C has the viscosity average molecular weight of 52.9 ten thousand, the substitution degree of the quaternary ammonium salt at the C6 site of 71.65 percent and the grafting rate of the amino-terminated hyperbranched compound at the C2 site of 85.49 percent, and is bagged and stored for later use at the temperature of 4 ℃. According to tests, the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt C obtained in the embodiment is 81.30%, and the solubility in water is 20.47g/100 mL.
Example 4
Weighing 2.0g of chitosan with viscosity-average molecular weight of 75 ten thousand and deacetylation degree of 95% according to a bath ratio of 1:20(w/v) and dissolving in 40mL of glycine hydrochloride ionic liquid, adding 6.0g of maleic acid to dissolve, stirring at 60 ℃ to react for 3h, immediately adding 80mL of anhydrous ethanol after the reaction is finished to separate out a precipitate, soaking the filtered precipitate in anhydrous ethanol for ultrasonic cleaning for 5 times, each time for 30min, fully replacing ionic liquid in the precipitate, and then filtering, drying and crushing to obtain the maleic acid acylated chitosan.
Swelling the dried maleic acid acylation chitosan in 0.5 mass percent NaOH solution for 90min according to a bath ratio of 1:20(w/v), adding 2, 3-epoxypropyltrimethylammonium chloride according to a mass ratio of 1:5 of the maleic acid acylation chitosan to the 2, 3-epoxypropyltrimethylammonium chloride, dissolving, stirring at 80 ℃ for substitution reaction for 6h, precipitating and filtering a final product by absolute ethyl alcohol, extracting for 24h by absolute ethyl alcohol, filtering, freeze-drying and crushing to obtain the maleic acid acylation chitosan quaternary ammonium salt.
Performing ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt for 90min at 40 ℃ by using 0.02mol/L diluted hydrochloric acid, then dissolving maleic acid acylation chitosan quaternary ammonium salt with glycinate hydrochloride ionic liquid at 78 ℃, dripping terminal amino hyperbranched compound (weight average molecular weight is 5690)/glycinate hydrochloride ionic liquid solution with mass concentration of 2.0% to ensure that the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the terminal amino hyperbranched compound is 1:0.8, stirring and reacting for 4h at 60 ℃, adding absolute ethyl alcohol to separate out a precipitate, filtering, cleaning with ultrasonic absolute ethyl alcohol, freeze drying, ball milling and crushing, the obtained brown yellow amino-terminated hyperbranched chitosan quaternary ammonium salt D has the viscosity average molecular weight of 56.3 ten thousand, the substitution degree of the quaternary ammonium salt at the C6 site of 78.92 percent and the grafting rate of the amino-terminated hyperbranched compound at the C2 site of 90.36 percent, and is bagged and stored for later use at 4 ℃. The product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt D obtained in the example is 76.13% and the solubility in water is 27.14g/100 mL.
Comparative example
Preparing amino-terminated hyperbranched chitosan quaternary ammonium salt in an aqueous medium:
weighing 2.0g of chitosan with the viscosity-average molecular weight of 75 ten thousand and the deacetylation degree of 95 percent, dissolving the chitosan in 40mL of 2 percent acetic acid solution according to the bath ratio of 1:20(w/v), adding 6.0g of maleic acid, dissolving, stirring at 60 ℃ for reaction for 3 hours, immediately dropwise adding 0.5mol/LNaOH solution after the reaction is finished until precipitates are completely separated out, soaking the filtered precipitates in absolute ethyl alcohol, carrying out ultrasonic cleaning for 5 times for 30min each time, and then carrying out suction filtration, drying and crushing to obtain the maleic acid acylated chitosan.
Swelling the dried maleic acid acylation chitosan in 0.5 mass percent NaOH solution for 90min according to a bath ratio of 1:20(w/v), adding 2, 3-epoxypropyltrimethylammonium chloride according to a mass ratio of 1:5 of the maleic acid acylation chitosan to the 2, 3-epoxypropyltrimethylammonium chloride, dissolving, stirring at 80 ℃ for substitution reaction for 6h, precipitating and filtering a final product by absolute ethyl alcohol, extracting for 24h by absolute ethyl alcohol, filtering, freeze-drying and crushing to obtain the maleic acid acylation chitosan quaternary ammonium salt.
Performing ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt for 90min at 40 ℃ by using 0.02mol/L diluted hydrochloric acid, then dissolving maleic acid acylation chitosan quaternary ammonium salt with the mass concentration of 2% in acetic acid solution at 78 ℃, then dripping terminal amino hyperbranched compound (with the weight average molecular weight of 5690) solution with the mass concentration of 2.0% to ensure that the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the terminal amino hyperbranched compound is 1:0.8, stirring and reacting for 4h at 60 ℃, dropwise adding 0.5mol/LNaOH solution after the reaction is finished until precipitation is completely separated out, then washing with ultrasonic absolute ethyl alcohol, filtering, freeze drying, ball milling and crushing, the obtained light yellow amino-terminated hyperbranched chitosan quaternary ammonium salt E has the viscosity-average molecular weight of 30.7 ten thousand, the substitution degree of the quaternary ammonium salt at the C6 site of 37.63 percent and the grafting rate of the amino-terminated hyperbranched compound at the C2 site of 49.22 percent, and is bagged and stored at 4 ℃ for later use. According to tests, the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt E obtained in the embodiment is 58.26%, and the solubility in water is 8.54g/100 mL.
Secondly, the samples obtained in the above embodiments are tested
Test item 1: scanning electron microscope analysis of amino-terminated hyperbranched chitosan quaternary ammonium salt
And observing the surface appearance conditions of the chitosan and the amino-terminated hyperbranched chitosan quaternary ammonium salt by using a scanning electron microscope (2000 x). 4 parts of chitosan sample, 1 part of blank sample without any treatment (chitosan with viscosity average molecular weight of 75 ten thousand and degree of deacetylation of 95%) and 2 to 4 parts of terminal amino hyperbranched chitosan quaternary ammonium salt with different degrees of substitution obtained by the method of examples 2 to 4 are taken, and the test results are sequentially shown in FIGS. 2(a) to (d).
As can be seen from FIG. 2, the blank sample macromolecular chitosan (a) is monoclinic beta-chitosan, each unit cell contains a disaccharide repeating unit with a molecular chain, the microfibril structure formed by the parallel arrangement of the molecular chains is clear and visible, the chitosan surface is smooth, and the crystal structure is complete. From fig. 2(b) - (d), it can be found that, as the substitution degree of the quaternary ammonium salt and the grafting ratio of the amino-terminated hyperbranched compound are increased, the particle boundaries of the amino-terminated hyperbranched chitosan quaternary ammonium salt become fuzzy, the surface of the amino-terminated hyperbranched chitosan quaternary ammonium salt is collapsed, and partial regions of the amino-terminated hyperbranched chitosan quaternary ammonium salt are in a dispersed state; particularly, under the conditions of high substitution degree of 78.92% and high grafting rate of 90.36%, more ravine hole structures appear on the surface of the amino-terminated hyperbranched chitosan quaternary ammonium salt particles, and the loose degree of the whole surface structure is increased (see fig. 2d), which indicates that as the substitution degree of the quaternary ammonium salt and the grafting rate of the amino-terminated hyperbranched compound are increased, the crystal structure of the original chitosan is damaged, the side chains of the quaternary ammonium salt molecules are increased, the distance between macromolecular chains is increased, and the amorphous form of the amino-terminated hyperbranched chitosan quaternary ammonium salt is more obvious, so that loose hole structures appear on the surface of the chitosan.
Test item 2: analysis of antibacterial activity of amino-terminated hyperbranched chitosan quaternary ammonium salt
The Minimum Inhibitory Concentration (MIC) is the lowest concentration at which the antimicrobial agent inhibits the growth of microorganisms, and is often used as an indicator of the antimicrobial activity of the antimicrobial agent, with lower MIC values having greater antimicrobial activity. Taking chitosan with viscosity-average molecular weight of 75 ten thousand and deacetylation degree of 95%, preparing culture solutions containing different concentrations of amino-terminated hyperbranched chitosan quaternary ammonium salt by adopting a sesquidilution method according to the chitosan quaternary ammonium salt samples with different substitution degrees obtained by the methods of examples 3 and 4 and the comparative example, adding bacterial liquid for oscillation culture, and determining MIC by measuring absorbance at 600nm by taking the culture solution with the same concentration of the chitosan quaternary ammonium salt sample and without the bacterial liquid as a control, wherein the test results are shown in Table 1.
As can be seen from the analysis of the data in Table 1, chitosan exhibited antibacterial activity only in an acidic medium at pH 5.0, and the minimum inhibitory concentrations against Staphylococcus aureus and Escherichia coli were 0.5mg/mL and 1.0mg/mL, respectively. The amino-terminated hyperbranched chitosan quaternary ammonium salt has excellent antibacterial performance under the alkalescent condition that the pH value is 7.2, the MIC value is 0.0313-2.0 mg/mL, and the application range is wider; especially, MICs of the amino-terminated hyperbranched chitosan quaternary ammonium salt solution with high substitution degree of 78.92% and high grafting rate of 90.36% to staphylococcus aureus and escherichia coli are 0.0313mg/mL and 0.0625mg/mL respectively, and the bacteriostatic ability of the amino-terminated hyperbranched chitosan quaternary ammonium salt solution is 16 times that of chitosan. Meanwhile, compared with gram-negative bacteria E.coli, the antibacterial activity of chitosan and the amino-terminated hyperbranched chitosan quaternary ammonium salt on gram-positive bacteria S.aureus is stronger, and when the antibacterial activity is obviously higher than pH 7.2 when the pH is 5.0, the amino and imino groups of the chitosan and the amino-terminated hyperbranched chitosan quaternary ammonium salt can both carry positive charges under an acidic condition to form polycation to act on the surface of bacteria, and the polycation and the phospholipid membrane of the bacterial cell membrane have strong and rapid reaction, wherein the reaction is caused by a compound generated by the amino and imino positive ions of the chitosan and the amino-terminated hyperbranched chitosan quaternary ammonium salt and phosphate groups on the phospholipid membrane through electrostatic attraction, so that the cell membrane is broken to cause the outflow of contents and finally die. Therefore, the amino-terminated hyperbranched chitosan quaternary ammonium salt prepared by the method contains various antibacterial groups such as quaternary ammonium salt, amino, imino and the like, so that the positive charge is greatly enhanced, the antibacterial performance is excellent, and the antibacterial efficiency is enhanced along with the improvement of the substitution degree of the C6 site and the grafting rate of the C2 site of the quaternary ammonium salt.
TABLE 1 minimum inhibitory concentrations of chitosan and amino-terminated hyperbranched chitosan quaternary ammonium salts of different degrees of substitution
In conclusion, chitosan and maleic acid are dissolved in glycine hydrochloride ionic liquid, acylation reaction is carried out on the C2 site of chitosan to obtain maleic acid acylation chitosan, then substitution reaction is carried out on the C6 site of the maleic acid acylation chitosan and 2, 3-epoxypropyl trimethyl ammonium chloride in alkaline solution to synthesize maleic acid acylation chitosan quaternary ammonium salt, and after ultrasonic substitution treatment by dilute hydrochloric acid, the maleic acid acylation chitosan quaternary ammonium salt and amino-terminated hyperbranched compound are dissolved in the glycine hydrochloride ionic liquid to carry out amide reaction, so as to obtain the amino-terminated hyperbranched chitosan quaternary ammonium salt. The method has the advantages of high reaction rate, easy control of the degree of substitution of the chitosan quaternary ammonium salt, easy separation and high yield of the product, good stability of the ionic liquid, strong reaction activity, environmental protection and easy recycling. The prepared amino-terminated hyperbranched chitosan quaternary ammonium salt contains a large amount of amino groups and imino groups, is easy to form polycation, contains a quaternary ammonium salt group with positive charge, has excellent lasting antibacterial ability, is biocompatible, degradable, non-irritant, non-toxic, and has wide application prospects in the fields of chemical industry, antibacterial materials, biology, medicine, food, packaging and the like.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. An amino-terminated hyperbranched chitosan quaternary ammonium salt is characterized in that: the structural formula of the amino-terminated hyperbranched chitosan quaternary ammonium salt is shown as the formula (1):
2. the amino-terminated hyperbranched chitosan quaternary ammonium salt of claim 1, wherein: the amino-terminated hyperbranched chitosan quaternary ammonium salt is obtained by acylation reaction of C2-site amino and maleic acid in chitosan molecules to be protected, partial or all of C6-site hydroxyl is replaced by 2, 3-epoxypropyl trimethyl ammonium chloride, and then amide reaction of C2-site carboxyl and an amino-terminated hyperbranched compound.
3. The amino-terminated hyperbranched chitosan quaternary ammonium salt of claim 1 or 2, wherein: the viscosity average molecular weight of the amino-terminated hyperbranched chitosan quaternary ammonium salt is 32.4-61.2 ten thousand, the substitution degree of the quaternary ammonium salt at the C6 site is 43.57-81.86%, and the grafting ratio of the amino-terminated hyperbranched compound at the C2 site is 60.47-91.85%.
4. The amino-terminated hyperbranched chitosan quaternary ammonium salt of claim 1 or 2, wherein: the product yield of the amino-terminated hyperbranched chitosan quaternary ammonium salt is 70.38-92.69%, and the solubility of the amino-terminated hyperbranched chitosan quaternary ammonium salt in water is more than or equal to 9.43g/100 mL.
5. A preparation method of the amino-terminated hyperbranched chitosan quaternary ammonium salt as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
(1) firstly, dissolving macromolecular chitosan with the viscosity-average molecular weight of 72-85 ten thousand and the deacetylation degree of more than or equal to 93.5% in glycine hydrochloride ionic liquid according to the bath ratio of 1: 15-30, then adding maleic acid for dissolving, stirring and reacting at 40-60 ℃ for 1-3 h, immediately adding absolute ethyl alcohol to separate out a precipitate after the reaction is finished, soaking the filtered precipitate in absolute ethyl alcohol for ultrasonic cleaning for 3-5 times, each time for 20-30 min, fully replacing the ionic liquid in the precipitate, and filtering, drying and crushing to obtain maleic acid acylated chitosan;
(2) swelling the maleic acid acylation chitosan in a NaOH solution with the mass concentration of 0.1-0.6% for 40-90 min according to the bath ratio of 1: 10-20, adding 2, 3-epoxypropyltrimethylammonium chloride for dissolving, stirring at 60-85 ℃ for substitution reaction for 2-6 h, precipitating and filtering a final product by using absolute ethanol, extracting for 18-24 h by using absolute ethanol, filtering, and freeze-drying to obtain the maleic acid acylation chitosan quaternary ammonium salt;
(3) carrying out ion replacement treatment on the maleic acid acylation chitosan quaternary ammonium salt for 40-90 min at 25-40 ℃ by using 0.02mol/L diluted hydrochloric acid, dissolving the maleic acid acylation chitosan quaternary ammonium salt by using glycine hydrochloride ionic liquid at 60-80 ℃, dropwise adding an amino-terminated hyperbranched compound/glycine hydrochloride ionic liquid solution with the mass concentration of 0.5-2%, stirring and reacting for 2-4 h at 45-60 ℃, adding absolute ethyl alcohol to separate out a precipitate, filtering, cleaning with ultrasonic absolute ethyl alcohol, freeze drying, ball milling and crushing to obtain the amino-terminated hyperbranched chitosan quaternary ammonium salt.
6. The method of claim 5, wherein: in the step (1), the mass ratio of the chitosan to the maleic acid is 1: 0.7-3.
7. The method of claim 5, wherein: in the step (2), the mass ratio of the maleic acid acylation chitosan to the 2, 3-epoxypropyl trimethyl ammonium chloride is 1: 2-5.
8. The method of claim 5, wherein: in the step (3), the mass ratio of the maleic acid acylation chitosan quaternary ammonium salt to the amino-terminated hyperbranched compound is 1: 0.2-1, and the weight average molecular weight of the amino-terminated hyperbranched compound is 4275-6360.
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