CN108424538B - Preparation method of cellulose/nano-attapulgite composite barrier film - Google Patents
Preparation method of cellulose/nano-attapulgite composite barrier film Download PDFInfo
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- 239000004202 carbamide Substances 0.000 claims description 22
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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Abstract
The invention relates to a preparation method of a cellulose/nano attapulgite composite barrier film, belonging to the technical field of natural polymer-based packaging materials. Firstly, acidizing nano attapulgite to obtain acidized nano attapulgite, dispersing the acidized nano attapulgite in water to obtain nano attapulgite suspension, mixing the nano attapulgite suspension with an alkaline solution to obtain a mixed solution, dissolving 4-8 wt% of cellulose in the mixed solution at-30 ℃, freezing, unfreezing, stirring, centrifuging, defoaming, carrying out casting film formation, regenerating in a solidification solution to obtain hydrogel, washing with water to be neutral, and drying to obtain the nano attapulgite hydrogel. The preparation method is green and environment-friendly, and is simple to operate and high in process stability. The tensile strength of the prepared composite barrier film is not less than 110MPa, and the composite barrier film not only has good transparency and biodegradability, but also has excellent mechanical property and gas barrier property, and is particularly suitable for being used as a food packaging material.
Description
Technical Field
The invention relates to a preparation method of a cellulose/nano attapulgite composite barrier film, belonging to the technical field of natural polymer-based packaging materials.
Background
With the increasing petroleum crisis and the increasing awareness of "green, low-carbon and environmental protection", it has become an urgent task to seek efficient, cheap and renewable alternative raw materials to prepare environment-friendly polymer materials. Among the packaging materials, packaging films of polyethylene, polypropylene, polystyrene, polyester, and the like have high transparency, good dimensional stability, excellent mechanical properties and gas barrier properties, but are not biodegradable. The packaging material made of biodegradable material has positive significance for reducing environmental pollution.
Cellulose is a natural polymer substance which is widely distributed and has the largest reserve in nature, has the advantages of low price, easy obtainment, no toxicity, good reproducibility, environmental friendliness and the like, is considered as an important raw material for developing new energy and new materials in the future, and receives more and more attention. However, packaging films made with cellulose generally have poor mechanical properties and gas barrier properties.
Disclosure of Invention
The invention aims to provide a preparation method of a cellulose/nano attapulgite composite barrier film, and the prepared barrier film is safe and environment-friendly and has excellent mechanical property and gas barrier property.
Technical scheme
The inventor prepares the regenerated cellulose organic-inorganic composite film by adding inorganic nano-filler into a cellulose solution and adopting a unique proportion and a unique process, the composite film not only has biodegradability, but also has excellent mechanical properties, heat resistance, gas barrier and other properties, and the application of the composite film in the fields of sustainable packaging materials, bio-based functional materials and the like is widened. The specific scheme is as follows:
a preparation method of a cellulose/nano attapulgite composite barrier film comprises the following steps:
(1) acidizing nano attapulgite to obtain nano acidized attapulgite, dispersing the nano acidized attapulgite in water to obtain nano attapulgite suspension, and uniformly mixing the nano attapulgite suspension with an alkaline solution to obtain a mixed solution;
(2) freezing the mixed solution obtained in the step (1) at-30 ℃ for 1-5h, then thawing at room temperature, adding cellulose under stirring to obtain a clear cellulose/nano-attapulgite mixed solution, and freezing the cellulose/nano-attapulgite mixed solution at-30 ℃ for 20-30 h;
(3) unfreezing the frozen cellulose/nano-attapulgite mixed solution at room temperature, uniformly stirring, performing centrifugal defoaming, removing precipitates, performing tape casting to form a film, then soaking the film into a solidification solution for 0.5-6 h for regeneration to obtain cellulose/nano-attapulgite composite hydrogel, washing the hydrogel to be neutral, and drying to obtain the cellulose/nano-attapulgite composite hydrogel;
in the step (1), the alkaline solution is a mixed solution of urea and LiOH or NaOH. When the urea/alkali solution is used as the solvent, the molecules of the urea and the alkali solvent can form hydrogen bonds with the cellulose, and the hydrogen bonds are more stable at low temperature, so that the hydrogen bonds among the cellulose molecules are broken, and the cellulose is dissolved in the urea/alkali solution at low temperature.
Further, in the step (1), the preparation process of the nano acidified attapulgite clay comprises the following steps: adding nano-attapulgite into 1mol/L hydrochloric acid solution, performing ultrasonic treatment at room temperature for 80-120min, activating, washing with water to neutrality, washing with acetone, vacuum drying the filter cake at 120 deg.C, and grinding to obtain acidified attapulgite.
Further, in the step (1), the mass concentration of the nano-attapulgite suspension is 5 wt%.
Further, in the step (1), the concentration of urea in the alkaline solution is 10-22 wt%, and the concentration of LiOH or NaOH is 4-12 wt%.
Further, in the step (1), the mass concentration of the nano-attapulgite in the mixed solution is 0.27-1.35 wt%. (calculation method: two endpoints: 5.26X0.05/95,25X0.05/95, respectively)
Further, in the step (2), the concentration of the cellulose in the cellulose/nano attapulgite mixed solution is 4-8 wt%.
In the step (3), the casting film formation is performed by adopting a traditional casting method, specifically, copper wires are wound on two sides of a test tube to form a gap with the thickness of 1mm with a glass plate, and a layer of cellulose/nano-attapulgite mixed solution with the thickness of 1mm is cast on the glass plate.
Further, in the step (3), the rotating speed of the centrifugation is 8000r/min, and the centrifugation time is 10 min.
Further, in the step (3), the coagulating liquid is selected from any one of a sulfuric acid solution, a sulfuric acid/sodium sulfate solution, a sodium sulfate solution, and an ammonium sulfate solution. The concentration of the sulfuric acid solution is preferably 5 wt%, the concentration of sulfuric acid in the sulfuric acid/sodium sulfate solution is preferably 7 wt%, the concentration of sodium sulfate is preferably 9%, the concentration of the sodium sulfate solution is preferably 9 wt%, and the concentration of ammonium sulfate is preferably 12 wt%. The regeneration mechanism of the solidification liquid is to reduce and destroy hydrogen bonds formed by urea molecules, alkali and cellulose, promote the recombination of the hydrogen bonds among cellulose molecules, enable the cellulose to be condensed out of the solution and further obtain the cellulose/nano attapulgite composite hydrogel.
The cellulose/nano attapulgite composite barrier film prepared by the method is applied to food packaging materials.
The invention has the beneficial effects that: the invention takes cellulose as raw material, utilizes nano attapulgite as reinforcing filler, dissolves the cellulose at low temperature through a urea/alkali solution system, and is frozen, thawed, stirred at high speed and defoamed in a centrifugal way, and then is subjected to casting to form a film; regenerating in the solidification liquid to obtain composite hydrogel, finally washing to neutrality, and drying to obtain the cellulose/nano-attapulgite composite membrane. The preparation method disclosed by the invention is environment-friendly, simple to operate and high in process stability. The prepared cellulose/nano-attapulgite composite barrier film has the tensile strength of more than or equal to 110MPa, not only has good transparency and biodegradability, but also has the advantages of high strength, excellent gas barrier property, safety, environmental protection and the like, and the composite membrane can be applied to the fields of sustainable packaging materials, bio-based functional materials and the like, and is particularly suitable for being used as food packaging materials.
Drawings
FIG. 1 is a scanning electron microscope image of the cross section of the cellulose/nano attapulgite composite barrier film prepared in examples 1-4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Weighing 20g of nano attapulgitePerforming ultrasonic treatment on soil in 200mL of 1mol/L hydrochloric acid solution at room temperature for 90min (power of 100W), activating, washing with water to be neutral, washing with acetone, performing vacuum drying on a filter cake at 120 ℃ for 12h, grinding to obtain acidified attapulgite, weighing 5g of acidified nano attapulgite, and performing ultrasonic dispersion on the acidified nano attapulgite in 95g of water to obtain a 5% nano attapulgite suspension; 5.26g of the nano-attapulgite suspension was mixed with a urea/LiOH solution (15.0g of urea and 8.0g of LiOH. H)2Dissolving O in 66.74g of water, and uniformly stirring to obtain a urea/LiOH solution) and uniformly mixing to obtain a mixed solution;
(2) freezing the mixed solution obtained in the step (1) at-30 ℃ for 2h, then thawing at room temperature, adding 5g of cellulose at a stirring speed of 1200r/min to obtain a clear cellulose/nano-attapulgite mixed solution, and freezing the cellulose/nano-attapulgite mixed solution at-30 ℃ for 24 h;
(3) thawing the frozen cellulose/nano-attapulgite mixed solution at room temperature, uniformly stirring, performing centrifugal defoaming (the centrifugal temperature is 0 ℃, the centrifugal speed is 8000r/min, and the centrifugal time is 10min), performing tape casting to form a film, immersing the film into a solidification solution (5% sulfuric acid solution) for 0.5h for regeneration to obtain cellulose/nano-attapulgite composite hydrogel, washing the hydrogel to be neutral, and drying to obtain the composite barrier film.
Example 2
Essentially the same as example 2, except that: in the step (1), the using amount of the nano attapulgite suspension is 11.11 g; the preparation method of the urea/LiOH solution comprises the following steps: 15.0g of urea and 8.0g of LiOH H2O was dissolved in 60.89g of water.
Example 3
Essentially the same as example 2, except that: the dosage of the nano attapulgite suspension is 17.65g, and the preparation method of the urea/LiOH solution comprises the following steps: 15.0g of urea and 8.0g of LiOH H2O was dissolved in 54.35g of water.
Example 4
Essentially the same as example 2, except that: the dosage of the nano attapulgite suspension is 25g, and the preparation method of the urea/LiOH solution comprises the following steps: 15.0g of urea and 8.0g of LiOH H2O was dissolved in 47.0g of water.
Comparative example 1
A preparation method of a cellulose barrier film comprises the following steps:
(1) preparing urea/LiOH solution, weighing 15.0g of urea and 8.0g of LiOH H2Dissolving O in 72.0g of water, and uniformly stirring to obtain a urea/LiOH solution;
(2) freezing the urea/LiOH solution obtained in the step (1) at-30 ℃ for 2h, then thawing at room temperature, adding 5g of cellulose at a stirring speed of 1200r/min to obtain a clear cellulose solution, and freezing the cellulose mixed solution at-30 ℃ for 24 h;
(3) thawing the frozen cellulose solution at room temperature, stirring uniformly, performing centrifugal defoaming (the centrifugal temperature is 0 ℃, the centrifugal speed is 8000r/min, the centrifugal time is 10min), performing tape casting to form a film, then immersing the film into a coagulating liquid (5% sulfuric acid solution) for 0.5h for regeneration to obtain cellulose hydrogel, washing the hydrogel to be neutral, and drying to obtain the cellulose barrier film.
Performance testing
1. The cross-sectional shapes of the cellulose/nano-attapulgite composite barrier films prepared in examples 1 to 4 were measured by a Nova NanoSEM 450 type scanning electron microscope, and the results are shown in fig. 1.
As can be seen from fig. 1, the cross-section of the cellulose/nano-attapulgite composite membranes prepared in examples 1 to 4 has a rough surface, and the nano-attapulgite is uniformly distributed in the cellulose matrix, thereby significantly enhancing the cellulose matrix.
2. The mechanical strength and oxygen transmission rate of the cellulose/nano-attapulgite composite films prepared in examples 1 to 5 were measured, respectively, according to ASTM D638, and according to GB/T1038-2000, the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, example 1 of the present invention-4, the tensile strength of the prepared composite barrier film is higher than 110MPa, the Young modulus of the prepared composite barrier film is higher than 5.0GPa, and the tensile strength is obviously higher than the mechanical strength of the blank cellulose film in the comparative example 1, which shows that the nano attapulgite has obvious enhancement effect on the cellulose substrate, the oxygen transmission rate of the cellulose/nano attapulgite composite barrier film is continuously reduced along with the continuous increase of the content of the nano attapulgite, and the oxygen transmission rate of the cellulose/nano attapulgite composite membrane is 0.32-0.36cm under the conditions of 23 ℃ and 50% of humidity3·m/d·m2kPa, which shows that the composite barrier film of the present invention has not only good transparency and biodegradability, but also excellent mechanical properties and gas barrier properties.
In conclusion, the invention provides the preparation method of the high-strength cellulose/nano attapulgite composite barrier film, and the preparation method is environment-friendly, simple to operate, high in process stability, low in equipment requirement and suitable for industrial application. The cellulose/nano attapulgite composite barrier film prepared by the preparation method has the tensile strength of more than or equal to 110MPa, and the oxygen transmission rate of the composite film is 0.32-0.36cm under the conditions of 23 ℃ and 50% of humidity3·μm/d·m2kPa, the composite barrier film not only has good transparency and biodegradability, but also has the advantages of high strength, excellent gas barrier performance, safety, environmental protection and the like. Based on the advantages, the composite membrane prepared by the method can be applied to the fields of sustainable packaging materials, bio-based functional materials and the like.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. 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.
Claims (7)
1. A preparation method of a cellulose/nano attapulgite composite barrier film is characterized by comprising the following steps:
(1) acidizing nano attapulgite to obtain nano acidized attapulgite, dispersing the nano acidized attapulgite in water to obtain nano attapulgite suspension, and uniformly mixing the nano attapulgite suspension with an alkaline solution to obtain a mixed solution;
(2) freezing the mixed solution obtained in the step (1) at-30 ℃ for 1-5h, then thawing at room temperature, adding cellulose under stirring to obtain a clear cellulose/nano-attapulgite mixed solution, and freezing the cellulose/nano-attapulgite mixed solution at-30 ℃ for 20-30 h;
(3) unfreezing the frozen cellulose/nano-attapulgite mixed solution at room temperature, uniformly stirring, performing centrifugal defoaming, removing precipitates, performing tape casting to form a film, then soaking the film into a solidification solution for 0.5-6 h for regeneration to obtain cellulose/nano-attapulgite composite hydrogel, washing the hydrogel to be neutral, and drying to obtain the cellulose/nano-attapulgite composite hydrogel;
in the step (1), the alkaline solution is a mixed solution of urea and LiOH or NaOH;
in the step (1), in the alkaline solution, the concentration of urea is 10-22 wt%, and the concentration of LiOH or NaOH is 4-12 wt%;
in the step (1), the mass concentration of the nano-attapulgite in the mixed solution is 0.27-1.35 wt%.
2. The method for preparing a cellulose/nano-attapulgite composite barrier film according to claim 1, wherein in the step (1), the nano-acidified attapulgite is prepared by: adding nano-attapulgite into 1mol/L hydrochloric acid solution, performing ultrasonic treatment at room temperature for 80-120min, activating, washing with water to neutrality, washing with acetone, vacuum drying the filter cake at 120 deg.C, and grinding to obtain acidified attapulgite.
3. The method for preparing a cellulose/nano-attapulgite composite barrier film according to claim 1, wherein the nano-attapulgite suspension in the step (1) has a mass concentration of 5 wt%.
4. The method for preparing a cellulose/nano-attapulgite composite barrier film according to claim 1, wherein in the step (2), the concentration of the cellulose in the cellulose/nano-attapulgite mixed solution is 4 to 8 wt%.
5. The method for preparing the cellulose/nano attapulgite composite barrier film according to any one of claims 1 to 4, wherein in the step (3), the rotating speed of the centrifugation is 8000r/min, and the centrifugation time is 10 min.
6. The method for preparing a cellulose/nano-attapulgite composite barrier film according to claim 5, wherein in the step (3), the coagulating liquid is selected from any one of a sulfuric acid solution, a sulfuric acid/sodium sulfate solution, a sodium sulfate solution and an ammonium sulfate solution.
7. Use of the cellulose/nano-attapulgite composite barrier film prepared by the method of any one of claims 1 to 6 in food packaging materials.
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| CN113788966B (en) * | 2021-09-29 | 2023-09-19 | 武汉理工大学 | Cellulose-based oxygen-resistant moisture-permeable antibacterial preservative film and preparation method thereof |
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| CN104497362B (en) * | 2014-12-12 | 2017-03-08 | 江南大学 | A kind of preparation method of cellulose/nanometer silicon nitride composite membrane |
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