CN114805915B - Cellulose composite aerogel and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a cellulose composite aerogel and a preparation method and application thereof, wherein the preparation of the cellulose composite aerogel comprises the following steps: s1, dispersing microcrystalline cellulose in a solvent, freezing at the temperature of minus 10 ℃ to minus 20 ℃ and then thawing to obtain a microcrystalline cellulose solution; s2, taking microcrystalline cellulose solution and aqueous solution of a modified material as raw materials, adding a cross-linking agent, and performing a cross-linking reaction to obtain a cellulose composite hydrogel crude product; s3, cleaning the crude product of the cellulose composite hydrogel with a cleaning solution, and swelling and balancing in the cleaning solution to obtain the cellulose composite hydrogel; s4, freezing the cellulose composite hydrogel at the temperature of minus 20 to minus 30 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying at the temperature of minus 50 to minus 70 ℃ and the pressure of less than or equal to 23Pa to obtain cellulose composite aerogel; the modified material is polyvinyl alcohol or polyethylene glycol, and the obtained cellulose composite aerogel has good mechanical property and excellent sound absorption performance when used as a sound absorption material.
Description
Technical Field
The invention relates to the field of sound absorption materials, in particular to a cellulose composite aerogel and a preparation method and application thereof.
Background
Noise pollution has become a concern beyond water pollution, atmospheric pollution, and soil pollution. Because of different production environments, the noise can be divided into industrial noise, traffic noise, building noise and living noise, and the normal life of people is disturbed to different degrees.
The aerogel is a solid substance form, and is an ideal acoustic delay or high-efficiency sound insulation material due to the low sound velocity characteristic, the inside of the aerogel is filled with nano holes with both ends open and communicated with the surface, so when sound propagates in the aerogel, sound energy is greatly consumed by the walls of the holes where the sound exists in a large quantity, the aerogel has a sound absorption effect which is tens of times higher than that of a common porous material, the aerogel is used as a novel sound absorption material, the sound absorption effect is better, the aerogel is ultra-light and pollution-free, the application of the aerogel is very wide, and particularly the cellulose aerogel has the characteristics of high porosity, large specific surface area, low density, high insulativity, low thermal conductivity, sustainability, biodegradability, low cost and the like, and is a runner in a biopolymer material. Thus, the special open cell structure of cellulose aerogel makes it also commonly used in acoustic design of buildings and aircraft to absorb sound waves, and the abundant pores can increase the propagation path of sound energy in the material, so that more sound energy is dissipated.
However, as the cellulose chain has the characteristic of rigidity, the prepared cellulose aerogel is brittle, the pore size distribution is uneven, the mechanical property is poor, the cellulose aerogel needs to be modified to enhance the mechanical property of the cellulose aerogel, the internal porous structure can be better maintained, and the sound absorption property of the cellulose aerogel is improved.
Disclosure of Invention
The invention aims to provide a cellulose composite aerogel, a preparation method and application thereof, and the cellulose composite aerogel has good mechanical properties and excellent sound absorption properties.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing a cellulose composite aerogel, comprising the steps of:
s1, dispersing microcrystalline cellulose in a solvent, freezing at the temperature of minus 10 ℃ to minus 20 ℃ and then thawing to obtain a microcrystalline cellulose solution;
s2, taking microcrystalline cellulose solution and aqueous solution of a modified material as raw materials, adding a cross-linking agent, and performing a cross-linking reaction to obtain a cellulose composite hydrogel crude product;
s3, cleaning the crude product of the cellulose composite hydrogel with a cleaning solution, and swelling and balancing in the cleaning solution to obtain the cellulose composite hydrogel;
s4, freezing the cellulose composite hydrogel at the temperature of minus 20 to minus 30 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying at the temperature of minus 50 to minus 70 ℃ and the pressure of less than or equal to 23Pa to obtain cellulose composite aerogel;
wherein the modifying material is polyvinyl alcohol or polyethylene glycol, and preferably, the modifying material is polyvinyl alcohol.
Preferably, in step S1, the solvent is a mixture of NaOH, urea and deionized water.
Preferably, in step S3, the cleaning solution is an aqueous solution of ethanol.
Preferably, in step S4, the pressure is 23Pa.
Preferably, the microcrystalline cellulose has a particle size of 50.+ -.5. Mu.m.
Preferably, the cross-linking agent comprises one or more of N, N-dimethyl bisacrylamide, butanediol diglycidyl ether, glutaraldehyde and epichlorohydrin.
Preferably, the mass ratio of the microcrystalline cellulose to the modified material is 1-4:1-2, more preferably, the mass ratio of the microcrystalline cellulose to the modified material is 1:2.
Preferably, the microcrystalline cellulose is present in the microcrystalline cellulose solution in an amount of 2 to 8% by mass, more preferably 4% by mass.
Preferably, the volume ratio of microcrystalline cellulose solution to cross-linking agent is 1:10-20, more preferably, the volume ratio of microcrystalline cellulose solution to cross-linking agent is 1:10.
In a second aspect, the present application provides a cellulose composite aerogel.
In a third aspect, the present application provides the use of a cellulose composite aerogel as a sound absorbing material, in an acoustic frequency range of 1000Hz to 6300Hz, preferably in an acoustic frequency range of 1000Hz to 1500Hz or 3500Hz to 5000Hz.
Preferably, the thickness of the cellulose composite aerogel is 18 to 20mm, more preferably, the thickness of the cellulose composite aerogel is 20mm.
The beneficial effects of the invention are as follows: the cellulose aerogel prepared by the method has good mechanical property and good compression recovery property through modification of microcrystalline cellulose, the internal porous structure of the cellulose composite aerogel is kept stable and is not easy to collapse, and the cellulose aerogel has excellent sound absorption performance, wide sound frequency range of sound absorption and high sound absorption coefficient; the preparation method is simple, the reaction system is mild, the preparation period is short, the process is controllable, no other pollutants are discharged in the preparation process, the green chemistry is complex, the raw materials are rich in storage in the nature, the environment is not polluted, the materials are degradable, and the green chemistry is complex.
Drawings
FIG. 1 is a SEM electron microscope scanning contrast diagram of a cellulose composite aerogel;
FIG. 2 is a graph comparing the sound absorption curves of cellulose composite aerogel at a thickness of 20mm.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The inventors have unexpectedly found that the mechanical property and pore structure of the cellulose aerogel can be regulated and controlled by increasing the entanglement degree of cellulose molecules, so that the aim of improving the sound absorption property of the cellulose aerogel is fulfilled, and based on the method, the invention is created.
The embodiment of the application provides a preparation method of cellulose composite aerogel, which comprises the following steps:
s1, weighing a certain amount of dry microcrystalline cellulose, adding the microcrystalline cellulose into a solvent, mechanically stirring for 20-30 min, freezing at-10 to-20 ℃ for 8-10 h, thawing at normal temperature, and stirring for 10-20 min to obtain a transparent microcrystalline cellulose solution;
s2, adding a cross-linking agent into the microcrystalline cellulose solution, adding an aqueous solution of polyvinyl alcohol or polyethylene glycol, magnetically stirring uniformly, performing ultrasonic treatment to obtain a cellulose composite hydrogel solution, pouring the cellulose composite hydrogel solution into a prepared mold, standing for 5-8h at room temperature, and taking out solids to obtain a cellulose composite hydrogel crude product;
wherein, polyvinyl alcohol or polyethylene glycol is used as a modifying material to modify microcrystalline cellulose, and the mass ratio of the microcrystalline cellulose to the modifying material is 1-4:1-2; the volume ratio of the microcrystalline cellulose solution to the cross-linking agent is 1:10-20, and the mass ratio of the microcrystalline cellulose in the microcrystalline cellulose solution is 2-8%.
S3, placing the crude cellulose composite hydrogel product in a cleaning solution, changing the cleaning solution every 2 hours, removing redundant solvents and impurities until the pH value of the surface of the crude cellulose composite hydrogel product reaches neutrality, standing for 3-5 hours at normal temperature after swelling and balancing in the cleaning solution, and removing redundant water on the surface to achieve the purpose of solvent replacement, thereby obtaining the cellulose composite hydrogel;
s4, freezing the cellulose composite hydrogel at the temperature of minus 20 to minus 30 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying at the temperature of minus 50 to minus 70 ℃ and the pressure of less than or equal to 23Pa to obtain cellulose composite aerogel;
in step S1, the solvent includes: 6-10wt% of NaOH, 10-15wt% of urea and the balance of deionized water.
In step S3, the cleaning liquid is an aqueous solution of ethanol.
In some embodiments, the microcrystalline cellulose has a particle size of 50±5 μm.
In other embodiments, the cross-linking agent comprises one or more of N, N-dimethyl bisacrylamide, butanediol diglycidyl ether, glutaraldehyde, epichlorohydrin.
As used herein, a "mold" is a hydrogel material forming mold, such as polytetrafluoroethylene mold manufactured by tetrafluoroplastic articles, inc. In guangzhou; the microcrystalline cellulose is a commercial chemical preparation, and the CAS number is 9004-34-6.
In the scheme, the polyvinyl alcohol and the polyethylene glycol are water-soluble polymers, a large number of hydroxyl groups are easy to modify, the structure of the polymers is similar to that of cellulose, the polymers have good compatibility with cellulose, after the cellulose is dissolved, the polymers form hydrogen bonds with cellulose molecules through the action of chemical cross-linking agents such as epichlorohydrin which can form strong interaction with the cellulose molecules, so that the entanglement degree of the cellulose molecules is increased, the mechanical properties and pore structure regulation of the reinforced cellulose composite aerogel are realized, for example, the pore size and pore size distribution of the cellulose composite aerogel are regulated, the pore pile structure in the cellulose composite aerogel is kept stable, is not easy to collapse, has good compression recovery, has good mechanical properties, and further improves the sound absorption performance of the cellulose composite aerogel, and meanwhile shortens the time of cellulose solution gel, and the preparation method is simple and efficient; on the other hand, the modified material in the application has good physical and chemical properties and good biodegradability, and can be degraded into H by microorganisms 2 O and CO 2 The microcrystalline cellulose is also a degradable material, the obtained cellulose composite aerogel is harmless to the environment, the material is degradable, the reaction system is mild in the preparation process, the preparation period is short, the process is controllable, other pollutant emission is avoided, and the environment is protected.
In a second aspect, the present application also provides a cellulose composite aerogel.
In a third aspect, the present application also provides the use of a cellulose composite aerogel as a sound absorbing material, in which the acoustic frequency range of the use is 1000Hz to 6300Hz, in some embodiments in the acoustic frequency range of 1000Hz to 1500Hz or 3500Hz to 5000Hz, the thickness of the cellulose composite aerogel is 18 to 20mm, in some embodiments the thickness of the cellulose composite aerogel is 20mm.
Example 1
Preparing a solvent: 6.5g of sodium hydroxide and 13.5g of urea are weighed, added into 80g of deionized water and stirred for 15min to obtain a solvent.
Preparing a cleaning solution: and mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:10 to obtain the cleaning liquid.
Preparing an aqueous solution of a modified material: 4g of dried polyethylene glycol powder is weighed and added into 96g of deionized water, and the mixture is stirred uniformly to obtain 4wt% polyethylene glycol solution serving as an aqueous solution of a modified material.
The preparation method of the cellulose composite aerogel comprises the following steps:
s1, adding 4g of microcrystalline cellulose which is dried at 60 ℃ into a solvent, stirring the microcrystalline cellulose with magnetic force at room temperature, and thawing and stirring the solution for 15min after freezing the solution at-20 ℃ for 8h to obtain a transparent microcrystalline cellulose solution.
S2, taking 10ml of microcrystalline cellulose solution, adding 100ml of epichlorohydrin serving as a cross-linking agent and 20ml of aqueous solution of a modified material, uniformly mixing, magnetically stirring for 30min, performing ultrasonic dispersion for 1h to obtain a cellulose composite hydrogel solution, pouring the cellulose composite hydrogel solution into a prepared mold, standing for 8h at room temperature, and taking solids to obtain a cellulose composite hydrogel crude product;
s3, placing the crude cellulose composite hydrogel product in a cleaning solution, changing the cleaning solution every 2 hours, removing redundant solvents and impurities until the pH value of the surface of the crude cellulose composite hydrogel product reaches neutrality, and standing for 5 hours at normal temperature after swelling and balancing in the cleaning solution to remove redundant water on the surface, so as to achieve the purpose of solvent replacement, thereby obtaining the cellulose composite hydrogel;
s4, freezing the cellulose composite hydrogel at the temperature of minus 25 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying the cellulose composite hydrogel jelly for 48 hours at the temperature of minus 60 ℃ and the pressure of 23Pa to obtain the cellulose composite aerogel.
Example 2
The preparation method of the cellulose composite aerogel is the same as in example 1, except that the modified material polyethylene glycol is replaced by polyvinyl alcohol, and the scanning image of the obtained cellulose composite aerogel is shown in figure 1b.
Example 3
Preparing a solvent: 6g of sodium hydroxide and 15g of urea are weighed, added into 79g of deionized water and stirred for 105min to obtain a solvent.
Preparing a cleaning solution: and mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:5 to obtain the cleaning liquid.
Preparing an aqueous solution of a modified material: 2g of the dried polyethylene glycol powder is weighed and added into 96g of deionized water, and the mixture is stirred uniformly to obtain a 2wt% polyethylene glycol solution serving as an aqueous solution of the modified material.
The preparation method of the cellulose composite aerogel comprises the following steps:
s1, adding 4g of microcrystalline cellulose which is dried at 60 ℃ into a solvent, stirring the microcrystalline cellulose with magnetic force at room temperature, and thawing and stirring the solution for 15min after freezing the solution at-10 ℃ for 8h to obtain a transparent microcrystalline cellulose solution.
S2, taking 10ml of microcrystalline cellulose solution, adding 200ml of N, N-dimethyl bisacrylamide serving as a cross-linking agent and 20ml of aqueous solution of a modified material, uniformly mixing, magnetically stirring for 30min, performing ultrasonic dispersion for 1h to obtain a cellulose composite hydrogel solution, pouring the cellulose composite hydrogel solution into a prepared mold, standing for 6h at room temperature, and taking a solid to obtain a cellulose composite hydrogel crude product;
s3, placing the crude cellulose composite hydrogel product in a cleaning solution, changing the cleaning solution every 2 hours, removing redundant solvents and impurities until the pH value of the surface of the crude cellulose composite hydrogel product reaches neutrality, and standing for 3 hours at normal temperature after swelling and balancing in the cleaning solution to remove redundant water on the surface, so as to achieve the purpose of solvent replacement, thereby obtaining the cellulose composite hydrogel;
s4, freezing the cellulose composite hydrogel at the temperature of minus 20 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying for 48 hours at the temperature of minus 70 ℃ and the pressure of 10Pa to obtain the cellulose composite aerogel.
Example 4
Preparing a solvent: 6.5g of sodium hydroxide and 13.5g of urea are weighed, added into 80g of deionized water and stirred for 15min to obtain a solvent.
Preparing a cleaning solution: and mixing absolute ethyl alcohol and deionized water according to the volume ratio of 1:10 to obtain the cleaning liquid.
Preparing an aqueous solution of a modified material: 2g of dried polyethylene alcohol powder is weighed and added into 96g of deionized water, and the mixture is stirred uniformly to obtain a 2wt% polyethylene glycol solution serving as an aqueous solution of the modified material.
The preparation method of the cellulose composite aerogel comprises the following steps:
s1, adding 8g of microcrystalline cellulose which is dried at 60 ℃ into a solvent, stirring the microcrystalline cellulose with magnetic force at room temperature, freezing the solution at-15 ℃ for 8 hours, thawing and stirring for 15 minutes to obtain a transparent microcrystalline cellulose solution.
S2, taking 10ml of microcrystalline cellulose solution, adding 120ml of butanediol diglycidyl ether as a cross-linking agent and 20ml of aqueous solution of a modified material, uniformly mixing, magnetically stirring for 30min, performing ultrasonic dispersion for 1h to obtain a cellulose composite hydrogel solution, pouring the cellulose composite hydrogel solution into a prepared mold, standing for 5h at room temperature, and taking solids to obtain a cellulose composite hydrogel crude product;
s3, placing the crude cellulose composite hydrogel product in a cleaning solution, changing the cleaning solution every 2 hours, removing redundant solvents and impurities until the pH value of the surface of the crude cellulose composite hydrogel product reaches neutrality, and standing for 4 hours at normal temperature after swelling and balancing in the cleaning solution to remove redundant water on the surface, so as to achieve the purpose of solvent replacement, thereby obtaining the cellulose composite hydrogel;
s4, freezing the cellulose composite hydrogel at the temperature of minus 30 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying for 48 hours at the temperature of minus 50 ℃ and the pressure of 18Pa to obtain the cellulose composite aerogel.
Comparative example 1
A method for producing a cellulose composite aerogel was the same as in example 1, except that in step S2, an aqueous solution of a modifying material was not added, and a cellulose composite aerogel was obtained.
Testing and analysis
Scanning the cellulose composite aerogels obtained in example 1, example 2 and comparative example 1 by electron microscopy, wherein an SEM image of the cellulose composite aerogel obtained in example 1 is shown in FIG. 1c, an SEM image of the cellulose composite aerogel obtained in example 2 is shown in FIG. 1b, and an SEM image of the cellulose composite aerogel obtained in comparative example 2 is shown in FIG. 1a, and thus, the entanglement degree of cellulose molecules of the cellulose composite aerogel obtained in the present application is increased.
The sound absorption curves of the cellulose composite aerogels obtained in example 1, example 2 and comparative example 1 were measured according to GB/T18696.1-2004, and as shown in FIG. 2, it was found that the sound absorption coefficient of example 1 was increased by 45% at the maximum compared to the cellulose composite aerogel of comparative example 1 and the sound absorption coefficient of example 2 was increased by 50% at the maximum compared to the cellulose composite aerogel of comparative example 1 under the condition that the thicknesses of the cellulose composite aerogels were 20mm.
It should be noted that, the foregoing embodiments all belong to the same inventive concept, and the descriptions of the embodiments have emphasis, and where the descriptions of the individual embodiments are not exhaustive, reference may be made to the descriptions of the other embodiments.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The preparation method of the cellulose composite aerogel is characterized by comprising the following steps of:
s1, dispersing microcrystalline cellulose in a solvent, freezing at the temperature of minus 10 ℃ to minus 20 ℃ and then thawing to obtain a microcrystalline cellulose solution;
s2, taking the microcrystalline cellulose solution and the aqueous solution of the modified material as raw materials, adding a cross-linking agent, and performing a cross-linking reaction to obtain a cellulose composite hydrogel crude product;
s3, cleaning the crude cellulose composite hydrogel with a cleaning solution, and swelling and balancing in the cleaning solution to obtain the cellulose composite hydrogel;
s4, freezing the cellulose composite hydrogel at the temperature of minus 20 ℃ to minus 30 ℃ to form cellulose composite hydrogel jelly, and then freeze-drying at the temperature of minus 50 ℃ to minus 70 ℃ and the pressure of less than or equal to 23Pa to obtain cellulose composite aerogel;
wherein the modifying material is polyethylene glycol;
the thickness of the cellulose composite aerogel is 20mm; the acoustic frequency range of the application of the cellulose composite aerogel as the sound absorption material is 1000 Hz-1500 Hz or 3500 Hz-5000 Hz.
2. The cellulose composite aerogel according to claim 1, wherein in step S1, the solvent is a mixture of NaOH, urea and deionized water.
3. The cellulose composite aerogel of claim 1, wherein in step S3, the purging liquid is an aqueous solution of ethanol.
4. The cellulose composite aerogel of claim 1, wherein the microcrystalline cellulose has a particle size of 50±5 μm.
5. The cellulose composite aerogel according to claim 1, wherein the cross-linking agent comprises one or more of N, N-dimethyl bisacrylamide, butanediol diglycidyl ether, glutaraldehyde, epichlorohydrin.
6. The cellulose composite aerogel according to claim 1, wherein in step S2, the mass ratio of the microcrystalline cellulose to the modifying material is 1-4:1-2.
7. The cellulose composite aerogel according to claim 6, wherein in step S2, the mass ratio of the microcrystalline cellulose to the modifying material is 1:2.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786642A (en) * | 2012-08-10 | 2012-11-21 | 南京林业大学 | Nanometer cellulose/polyvinyl alcohol gel composite material |
| CN103709435A (en) * | 2013-12-19 | 2014-04-09 | 东北林业大学 | Preparation method of light-weight high-intensity cellulose aerogel |
| CN106009031A (en) * | 2016-07-15 | 2016-10-12 | 东北林业大学 | Method for improving mechanical strength of cellulose aerogel |
| CN108579626A (en) * | 2018-04-26 | 2018-09-28 | 南京林业大学 | The preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge |
| CN109796634A (en) * | 2017-11-17 | 2019-05-24 | 范佳晨 | A kind of preparation method of cellulose aerogels-polyvinyl alcohol composite material |
-
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- 2022-05-25 CN CN202210576725.XA patent/CN114805915B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786642A (en) * | 2012-08-10 | 2012-11-21 | 南京林业大学 | Nanometer cellulose/polyvinyl alcohol gel composite material |
| CN103709435A (en) * | 2013-12-19 | 2014-04-09 | 东北林业大学 | Preparation method of light-weight high-intensity cellulose aerogel |
| CN106009031A (en) * | 2016-07-15 | 2016-10-12 | 东北林业大学 | Method for improving mechanical strength of cellulose aerogel |
| CN109796634A (en) * | 2017-11-17 | 2019-05-24 | 范佳晨 | A kind of preparation method of cellulose aerogels-polyvinyl alcohol composite material |
| CN108579626A (en) * | 2018-04-26 | 2018-09-28 | 南京林业大学 | The preparation method of Cellulose nanocrystal body/graphene/polyvinyl alcohol aeroge |
Non-Patent Citations (1)
| Title |
|---|
| 唐桂江等.聚乙烯醇 / 纤维素复合气凝胶材料的制备及其声学性能.胶体与聚合物.2022,第40卷(第40期),要，实验部分第1.1-1.2节，第2.2-2.5节，结语. * |
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