CN110218358B - Preparation method and application of cellulose/ZnAl hydrotalcite composite membrane - Google Patents
Preparation method and application of cellulose/ZnAl hydrotalcite composite membrane Download PDFInfo
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Abstract
The invention belongs to the technical field of natural polymer chemistry, and particularly discloses a preparation method and application of a cellulose/ZnAl hydrotalcite composite membrane. The basic composition of the material is cellulose and hydrotalcite nano-sheets. The method comprises the steps of using pre-cooled NaOH and thiourea combined aqueous solution as a solvent, pouring cellulose and ZnAl hydrotalcite into the solvent according to different proportions, directly dissolving the cellulose and the dispersed hydrotalcite, then performing centrifugal deaeration, paving to form a film, performing solidification forming through a sodium sulfate solution or an alcohol solidification bath, and drying to obtain the cellulose/ZnAl hydrotalcite blended film. The film has good mechanical property, flame retardance and antibacterial activity, and has the advantages of no toxicity, no harm, high safety and biodegradability. The film has good application prospect in the fields of medicine, food, environmental protection and the like, and the production process is simple, convenient and pollution-free.
Description
Technical Field
The invention belongs to the technical field of natural polymer chemistry, and particularly discloses a preparation method and application of a cellulose/ZnAl hydrotalcite composite membrane.
Background
With the commercial progress, the development of food and medical packaging materials has become a leading hotspot of great interest. At present, the packaging material uses PE, PP, PET and other plastics in a large amount, and although the mechanical properties of the materials are good, the materials are difficult to recover and degrade, have great damage and pollution to the environment, and even have bad influence on human bodies after being used for a long time. Under the background of the decreasing petrochemical resources and the great environmental pollution, the search and development of a natural degradable biological material to replace the traditional plastic packaging material has become a research hotspot in the field of current materials. Cellulose is the most abundant and renewable non-edible biomass resource in the nature, and the structure of the cellulose is a linear high polymer consisting of beta- (1, 4) linked D-glucopyranose monomers. Has the advantages of wide raw material source, good biocompatibility, easy degradation and the like, thereby being used as a good material for food and medical packaging. However, their lack of antibacterial and gas barrier properties limits the use of such materials in food and medical packaging materials. Recently, the preparation of new functional polymer materials by composite nanoparticles has been carried outIs widely regarded. The composite nano particles can keep the functions and characteristics of the original material, introduce new synergistic properties, and are easy to realize industrialization compared with chemical modification. Hydrotalcite (LDHs) is dihydroxy anionic clay with a layered structure, and has the characteristics of large specific surface area, excellent thermal stability and chemical stability and the like. The chemical general formula is [ M ]2+ 1-XM3+ x(OH)2】(An-)x/n·H2O, in the formula M2+、M3+The subscripts X represent M, which represent divalent and trivalent metal cations, respectively3+In an amount of (2), usually 0.2<X<0.33，An-Denotes anions which can be exchanged between layers, due to the LDHs layer plate M2+、M3 +And interlayer anion An-The adjustable property of the hydrotalcite material can effectively adjust the structure and the function of the hydrotalcite material. In recent years, a great deal of literature reports on the research of using the antibacterial composite material as an antibacterial additive to prepare an antibacterial composite material.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention aims to provide a cellulose/ZnAl hydrotalcite composite membrane, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a cellulose/ZnAl hydrotalcite composite membrane is composed of cellulose and ZnAl hydrotalcite nanosheets. Wherein the mass ratio of the cellulose to the ZnAl hydrotalcite is 100: (1-30), preferably 100: (3-20), more preferably 100: (10-20).
Preferably, the cellulose is cotton linter cellulose, and more preferably, the degree of polymerization does not exceed 600.
The invention also provides a preparation method of the cellulose/ZnAl hydrotalcite composite membrane, which comprises the following steps:
adding cellulose and ZnAl hydrotalcite (wherein the mass ratio of the cellulose to the ZnAl hydrotalcite is 100 (1-30), preferably 100 (3-20), more preferably 100 (10-20)) into a mixed aqueous solution of sodium hydroxide and thiourea pre-cooled to 0-15 ℃ (preferably 5 ℃), and fully stirring at room temperature (about 5 minutes) to form a uniform cellulose/hydrotalcite composite solution, wherein the cellulose content in the cellulose/hydrotalcite composite solution is 2-5 wt%, preferably 3.5-4.0 wt%. And (2) performing centrifugal deaeration and tape casting on the cellulose/hydrotalcite composite solution to form a membrane, then performing coagulation regeneration in a sodium sulfate aqueous solution with the concentration of 5-20 wt% in a coagulation bath, industrial alcohol or an ethanol aqueous solution with the concentration of 50-90 v/v%, taking out the membrane, washing the membrane with deionized water until the pH value of an eluate is 7, and drying the membrane to obtain the cellulose/hydrotalcite composite membrane. The reaction mechanism is as follows: the hydrogenolysis binding capacity of the aqueous sodium hydroxide/thiourea solution is enhanced with the decrease of the temperature. Precooling sodium hydroxide/thiourea aqueous solution, and quickly stirring to destroy hydrogen bonds among cellulose molecules and hydrogen bonds among ZnAl hydrotalcite layers, so that the cellulose molecules and the hydrotalcite can be well dispersed to obtain the uniform cellulose/hydrotalcite composite membrane.
Preferably, the mixed aqueous solution of sodium hydroxide and thiourea is a mixed aqueous solution of 9.0-11.0 wt% of sodium hydroxide and 7.0-10.0 wt% of thiourea, and the preparation method is as follows: mixing sodium hydroxide and thiourea, and adding water to obtain the compound; or preparing sodium hydroxide into an aqueous solution, and then adding thiourea to obtain the compound; or preparing the sodium hydroxide and the thiourea into aqueous solutions respectively, and then mixing to obtain the compound.
Compared with the prior art, the invention has the advantages and beneficial effects that:
the invention utilizes the cotton linter cellulose and the hydrotalcite to prepare the cellulose/hydrotalcite composite film, and can be used as a gas barrier, flame retardant and antibacterial packaging material in the fields of chemical industry, food, environmental protection and medical use. Can also be used as medical material.
The method for preparing the cellulose/hydrotalcite composite membrane by adopting the aqueous phase system is simple and easy to implement, has no environmental pollution and low cost, and the prepared composite material has high mechanical strength and antibacterial activity.
Drawings
FIG. 1 is an SEM image of a cellulose/ZnAl hydrotalcite-based composite material according to the present invention;
FIG. 2 is an XPS plot of a cellulose/ZnAl hydrotalcite-based composite material prepared in example 5 of the present invention;
FIG. 3 is a TG diagram of a cellulose/ZnAl hydrotalcite-based composite material according to the present invention;
FIG. 4 is a graph showing the results of the strength test of the composite material based on cellulose/ZnAl hydrotalcite according to the present invention;
FIG. 5 is a diagram of the bacteriostatic effect of the cellulose/ZnAl hydrotalcite-based composite material on Escherichia coli.
FIG. 6 is a diagram of the bacteriostatic effect of the cellulose/ZnAl hydrotalcite-based composite material on Staphylococcus aureus.
Fig. 7 is an XRD pattern of ZnAl hydrotalcite prepared according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples:
in the following examples 1-5, some of the starting materials are as follows:
the used cotton linter cellulose was purchased from Hubei chemical fiber group Co.
The concentrations of two solutes in the mixed solution of sodium hydroxide and thiourea are respectively as follows: 9.0-11.0 wt% of sodium hydroxide, 7.0-10.0 wt% of thiourea and the balance of water.
The preparation method comprises the following steps: firstly preparing sodium hydroxide into an aqueous solution, and then adding thiourea into the aqueous solution to obtain the compound.
The ZnAl hydrotalcite is self-made by the applicant according to the following method: 30mmol of Zn (NO)3)2、10mmol Al(NO3)3And 0.1mol of urea are dissolved in 80g of deionized water, and the mixture is placed in a reaction kettle with a 100ml lining after being uniformly mixed and reacts for 48 hours at the temperature of 110 ℃. And centrifuging the obtained reaction liquid, washing the obtained solid to be neutral by using deionized water, putting the washed solid into an oven at 80 ℃ for overnight drying, and grinding to obtain a white powder sample, namely ZnAl hydrotalcite, which is a ZnAl hydrotalcite nanosheet, wherein an electron microscope diagram of the ZnAl hydrotalcite nanosheet is shown in figure 1, an XRD diagram of the ZnAl hydrotalcite is shown in figure 7, and 2 theta (degree) is 12.7 and 19.4 respectively corresponding to the 003 crystal plane and the 006 crystal plane of the ZnAl hydrotalcite.
Other raw materials are all common commercial products.
Example 1
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (the polymerization degree is 600) is added, and the mixture is rapidly stirred for 5 minutes at room temperature to obtain a uniform cellulose solution. The resulting solution was centrifuged at 7000 rpm with an ultracentrifuge for 20 minutes to remove air bubbles, thereby obtaining a transparent cellulose solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 70 v/v% ethanol water solution. And taking out, washing with deionized water until the pH value is 7, then pasting on an organic glass plate, and naturally airing to obtain a regenerated cellulose membrane marked as Cell-0.
Example 2
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.12g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 70 v/v% ethanol water solution. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain a regenerated cellulose ZnAl hydrotalcite composite membrane marked as Cell-3.
Example 3
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.2g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 70 v/v% ethanol water solution. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain a regenerated cellulose ZnAl hydrotalcite composite membrane marked as Cell-5.
Example 4
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.4g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 70 v/v% ethanol water solution. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain a regenerated cellulose ZnAl hydrotalcite composite membrane marked as Cell-10.
Example 5
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.8g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 70 v/v% ethanol water solution. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain a regenerated cellulose ZnAl hydrotalcite composite membrane marked as Cell-20.
Example 6
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.4g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. Spreading a film on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then solidifying and regenerating in industrial alcohol. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain the regenerated cellulose ZnAl hydrotalcite composite membrane.
Example 7
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.4g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 5 wt% sodium sulfate aqueous solution. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain the regenerated cellulose ZnAl hydrotalcite composite membrane.
Example 8
100 g of a mixed solution of sodium hydroxide and thiourea (the two solute concentrations are respectively 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea) is pre-cooled to 5 ℃, 4g of cotton linter cellulose (with a polymerization degree of 600) and 0.4g of ZnAl hydrotalcite are added, and the mixture is rapidly stirred at room temperature for 5 minutes to obtain a uniform solution. And centrifuging the mixture for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam the mixture to obtain a transparent cellulose hydrotalcite composite solution. The film is spread on a glass rod by a tape casting method by using a glass tube with two ends tied with copper wires (the diameter is 0.5mm), and then the film is solidified and regenerated in 15 wt% sodium sulfate aqueous solution. And taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural drying to obtain the regenerated cellulose ZnAl hydrotalcite composite membrane.
Performance analysis test of the regenerated cellulose membrane obtained in example 1 and the ZnAl hydrotalcite composite membranes of the regenerated celluloses obtained in examples 2 to 5
The SEM image is shown in FIG. 1: with the increase of the content of ZnAl hydrotalcite, the interfacial dispersibility of the hydrotalcite in the composite material is reduced. The ZnAl-hydrotalcite scanning electron microscope picture shows that the ZnAl-hydrotalcite nano-sheet-like flower-shaped particles consist of ZnAl-hydrotalcite nano-sheets with the thickness of about 120 nanometers.
The XPS map is shown in FIG. 2: the four characteristic elements of C, O, Zn and Al are obviously distributed in a spectrogram and have relatively high content.
The TG profile is shown in FIG. 3: because the hydrotalcite has flame retardance, the decomposition temperature of the composite material is higher than that of a pure cellulose film when the hydrotalcite is compounded with cellulose.
Mechanical Properties test the mechanical properties of the composite films were measured using a universal material tester (AI-7000M, 2015-01495). And (3) testing rate: 5 cm/min; spline size: the length is 20cm and the width is 1 cm. As shown in fig. 4, as the content of hydrotalcite increases, the tensile strength of the composite film increases, and the content of hydrotalcite exceeds 3%, and the tensile strength gradually decreases. It is likely that the hydrotalcite content exceeds 3%, and the hydrotalcite aggregates in the composite material, resulting in a decrease in tensile strength. This is consistent with the results of the SEM images.
Antibacterial property test A sterilized solid medium (composed of beef extract, peptone, sodium chloride, agar and water, pH 7.02) was heated to dissolve, cooled to about 50 ℃ and poured into a petri dish (about 2-3mm in height), after solidification, Escherichia coli and Staphylococcus aureus were inoculated to the petri dish by a dilution coating plate method, and the regenerated cellulose film obtained in example 1 and the regenerated cellulose ZnAl hydrotalcite composite film obtained in examples 2-5 were placed in the petri dish using a punch to obtain a 6 cm-diameter film. And (4) after the experiment is finished, inverting and sealing the culture dish, putting the culture dish into a bacterial incubator for constant-temperature culture at 37 ℃ for 24 hours, and observing and recording the experimental phenomenon. FIGS. 5 and 6 are Escherichia coli and Staphylococcus aureus, respectively. As shown in FIGS. 5 and 6, when the ZnAl hydrotalcite content is 10%, the cellulose/ZnAl composite material (Cell-10) has a large inhibition zone and a good antibacterial effect. With the continuous increase of the content of ZnAl hydrotalcite, the antibacterial zone of the composite material (Cell-20) is larger, and the antibacterial effect is better.
Claims (1)
1. The application of the cellulose/ZnAl hydrotalcite composite membrane comprises the following steps:
mixing 100 g of sodium hydroxide and thiourea, wherein the concentrations of two solutes are respectively as follows: 9.3 wt% of sodium hydroxide and 7.4 wt% of thiourea, precooling to 5 ℃, adding 4g of cotton linter cellulose with the polymerization degree of 600 and 0.8g of ZnAl hydrotalcite, quickly stirring for 5 minutes at room temperature to obtain a uniform solution, and centrifuging for 20 minutes at 7000 r/min by using an ultracentrifuge to defoam to obtain a transparent cellulose hydrotalcite composite solution; spreading a film on a glass rod by a tape casting method by using a glass tube with copper wires at two ends, solidifying and regenerating in 70 v/v% ethanol water, taking out, washing with deionized water until the pH value is 7, and then pasting on an organic glass plate for natural airing to obtain a regenerated cellulose ZnAl hydrotalcite composite film; the composite film is used for gas barrier, flame retardant and antibacterial packaging materials in the fields of chemical industry, food, environmental protection and medical use;
the ZnAl hydrotalcite is prepared by the following method: 30mmol of Zn (NO)3)2、10mmol Al(NO3)3Dissolving 0.1mol of urea in 80g of deionized water, uniformly mixing, placing in a reaction kettle with a 100ml lining, and reacting for 48 hours at 110 ℃; and centrifuging the obtained reaction liquid, washing the obtained solid to be neutral by using deionized water, putting the washed solid into an oven at 80 ℃ for overnight drying, and grinding to obtain a white powder sample, namely the ZnAl hydrotalcite nanosheet.
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| CN114130373B (en) * | 2021-12-07 | 2024-04-09 | 合肥乐凯科技产业有限公司 | Nitrocellulose membrane and preparation method thereof |
| CN114649553B (en) * | 2022-02-11 | 2023-04-14 | 南京工业大学 | Porous membrane loaded by zeolite molecular sieve nanosheets, preparation method and application of porous membrane in zinc-based flow battery |
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