CN111944178B - Preparation method of nano holocellulose reinforced composite membrane and prepared composite membrane - Google Patents
Preparation method of nano holocellulose reinforced composite membrane and prepared composite membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 35
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- 238000000034 method Methods 0.000 claims abstract description 20
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- 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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/14—Hemicellulose; Derivatives thereof
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/14—Hemicellulose; Derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
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Abstract
The invention discloses a preparation method of a nano holocellulose reinforced composite membrane, relates to the application field of biomass lignocellulose, and is provided based on the problems of poor mechanical property and poor heat resistance of the existing composite membrane. The invention comprises the following steps: (1) preparing holocellulose; (2) preparing nano holocellulose; (3) preparing a composite membrane: preparing solution from hemicellulose, chitosan and epoxy chloropropane, mixing the obtained nano holocellulose according to a certain volume ratio, stirring for a period of time, and then air-drying to obtain the composite membrane. The invention also provides a composite membrane prepared by the preparation method of the nano holocellulose reinforced composite membrane. According to the invention, the nano holocellulose solution, the hemicellulose solution and the chitosan solution are fully mixed, and then the casting film forming method is adopted to form the composite film, the prepared composite film has the characteristics of high strength, good heat resistance and the like, and the tensile strength of the prepared composite film can reach 34.93MPa to the maximum.
Description
Technical Field
The invention relates to the application field of biomass lignocellulose, in particular to a preparation method of a nano holocellulose reinforced composite membrane and the prepared composite membrane.
Background
In recent years, renewable biomass resources replacing stone resources such as petroleum and the like have become the preferential development theme of various countries in the world, wherein lignocellulose resources such as agricultural straws, forest processing residues, cellulose-rich industrial processing wastes and natural plants are important raw materials for replacing petroleum. The nano material is always reproducible, has a high specific surface area, has higher catalytic activity and chemical reaction activity, is small in expansion degree, high in strength and hardness, light in weight, easy to modify surface hydroxyl and wide in application. The nano material can be generally used as a reinforcing agent, and is an effective way for improving the mechanical property and the service performance of the material.
The holocellulose is a polysaccharide compound except lignin and an extract in natural biomass, and mainly comprises cellulose and hemicellulose. The research and the utilization of cellulose are extremely wide, but the comprehensive utilization of the holocellulose is very little. The physical and chemical properties of the holocellulose are similar to those of cellulose, but the preparation process is simpler and more convenient than the cellulose. Therefore, the method for directly preparing the holocellulose into the nano material has important significance.
Patent CN104693464B discloses a preparation method of a lignin nanocellulose reinforced polylactic acid composite membrane, the raw materials include polylactic acid, lignin nanocellulose and N, N-dimethylacetamide, the lignin-containing nanocellulose is compounded with polylactic acid, and the polylactic acid is reinforced by nano materials. Patent CN108610517A discloses a method for preparing a nano-cellulose reinforced hemicellulose-based composite membrane, which comprises the steps of respectively dissolving and uniformly mixing hemicellulose, isolated soy protein and nano-cellulose according to a proportion, adding a plasticizer, fully and uniformly mixing, adding water to prepare a solution with the concentration of 2-6%, ultrasonically degassing, forming a membrane by adopting a tape casting method, placing the membrane in a constant temperature oven at 40-60 ℃ for 4-7 hours, drying and then uncovering the membrane to obtain the nano-cellulose reinforced hemicellulose-based composite membrane. Document "preparation and application of composite membrane with reinforced function of nano-cellulose" discloses a method for preparing composite membrane with reinforced function of nano-cellulose by mixing nano-cellulose and chitosan.
The problems with the above technique are as follows: the prepared composite film has poor mechanical property and heat resistance.
Disclosure of Invention
The invention aims to provide a preparation method of a nano holocellulose reinforced composite membrane with high strength and good heat resistance.
The invention adopts the following technical scheme to solve the technical problems:
the invention provides a preparation method of a nano holocellulose reinforced composite membrane, which comprises the following steps:
(1) crushing and sieving a wheat straw raw material to obtain wheat straw powder for later use;
(2) adding the wheat straw powder obtained in the step (1) into a benzene-alcohol mixed solution according to a bath ratio of w/v to 1:25, and heating and extracting in a constant-temperature water bath kettle at 80-90 ℃ to obtain an extract-free sample;
(3) adding the sample without the extract prepared in the step (2) and sodium chlorite into glacial acetic acid according to a bath ratio of w/w/v being 4:1.2:1, heating for 1-3h in a constant-temperature water bath kettle at 60-80 ℃, filtering the mixture after the reaction is finished, washing the mixture to be neutral by distilled water, and drying for 4-8h at 103-;
(4) ball-milling the holocellulose prepared in the step (3), swelling the ball-milled holocellulose with deionized water, adjusting the swollen holocellulose to a suspension with the concentration of 0.5-2.0% of the holocellulose solution, treating the obtained suspension with an ultramicron disc mill, and repeatedly disc-milling for multiple times at the disc mill rotation speed of 1000-3000r/min for 10-30min to prepare the nano holocellulose;
(5) mixing a hemicellulose solution and a chitosan solution according to a volume ratio of 50:50:1:5-50:50:6:5, stirring for 1-2h to fully mix, adding nano holocellulose and epoxy chloropropane into the mixed solution respectively, then stirring continuously, reacting for 1-3h at 60-80 ℃, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain the composite film sample.
According to the invention, the nano holocellulose solution, the hemicellulose solution and the chitosan solution are fully mixed, and then the casting film forming method is adopted to form the composite film, and the prepared composite film has the characteristics of high strength, good heat resistance and the like.
Preferably, the wheat straw in the step (1) is sieved by a 40-50 mesh sieve.
Preferably, the volume ratio of benzene to alcohol in the benzene-alcohol mixed solution in the step (2) is 2: 1.
Preferably, the extraction time in the step (2) is 6 to 8 hours.
Preferably, the distance between the sample and the grinding disc in the step (4) is-9-0 mm.
Preferably, the disc mill is repeated 5 to 10 times in the step (4).
Preferably, the concentration of the hemicellulose solution in the step (5) is 1-2%.
Preferably, the concentration of the chitosan solution in the step (5) is 1-2%.
Preferably, in the step (5), the hemicellulose solution, the chitosan solution and the nano holocellulose solution are mixed and then formed into a film by adopting a casting film forming method.
The invention also provides a composite membrane prepared by the preparation method of the nano holocellulose reinforced composite membrane.
The invention has the beneficial effects that:
(1) according to the invention, the nano holocellulose solution, the hemicellulose solution and the chitosan solution are fully mixed, and then the casting film forming method is adopted to form the composite film, and the prepared composite film has the characteristics of high strength, good heat resistance and the like.
(2) The method has the characteristics of low cost, simple process, easy industrial production investment, simple operation, high efficiency and little pollution, and can become a way for preparing novel functional materials by efficiently utilizing biomass raw materials.
Drawings
FIG. 1 is an AFM image of nano-sized holocellulose prepared in example 2 of the present invention;
FIG. 2 is an infrared spectrum of the raw material and composite film of examples 1 to 4 of the present invention and comparative example 1;
FIG. 3 is an X-ray diffraction pattern of the raw materials and composite films of examples 1-4 of the present invention and comparative example 1;
FIG. 4 is a result of light transmittance of the composite films of examples 1 to 4 of the present invention and comparative example 1;
FIG. 5 is a stress-strain diagram of composite films of examples 1-4 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail below.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Comparative example 1
Mixing 5mL of 2% hemicellulose solution and 5mL of 2% chitosan solution, stirring for 1h to fully mix the two solutions, adding 0.5mL of epoxy chloropropane into the mixed solution, continuing stirring, reacting at 60 ℃ for 1h, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain a composite film sample which is marked as HC-1;
performance test: the composite film prepared by the comparative example has the tensile strength of 19.42MPa, the elongation at break of 8.51 percent and the Young modulus of 7.04 MPa.
Example 1
A preparation method of a nano holocellulose reinforced composite membrane comprises the following steps:
(1) crushing a wheat straw raw material, and sieving the crushed wheat straw raw material with a 40-mesh sieve to obtain wheat straw powder for later use;
(2) adding the wheat straw powder obtained in the step (1) into a benzene-alcohol mixed solution (the volume ratio of benzene to alcohol is 2:1) according to a bath ratio of w/v being 1:25, and heating and extracting for 8 hours in a constant-temperature water bath kettle at 90 ℃ to obtain an extract-free sample;
(3) adding the sample without the extract prepared in the step (2) and sodium chlorite into glacial acetic acid according to a bath ratio of w/w/v being 4:1.2:1, heating the mixture in a constant-temperature water bath kettle at 75 ℃ for 1h, filtering the mixture after the reaction is finished, washing the mixture to be neutral by distilled water, and drying the mixture at 105 ℃ for 6h to obtain the holocellulose;
(4) ball-milling the holocellulose prepared in the step (3), swelling the ball-milled holocellulose with deionized water, adjusting the swollen holocellulose to a suspension with the concentration of 0.5% of the holocellulose solution, treating the obtained suspension with an ultramicron disc mill (MKCA6-2, Japan Masuko), and circularly disc-milling at the interval of-9 at the rotating speed of 1500r/min for 15min for 6 times to obtain the nano holocellulose;
(5) mixing 5mL of 2% hemicellulose solution and 5mL of 2% chitosan solution, stirring for 1h to fully mix the solutions, adding 0.1mL of nano holocellulose and 0.5mL of epoxy chloropropane into the mixed solution respectively, continuing stirring, reacting for 1h at 60 ℃, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain a composite film sample which is marked as HC-2.
Performance test: the tensile strength of the composite film prepared in this example was 29.15MPa, the elongation at break was 22.23%, and the Young's modulus was 5.58 MPa.
Example 2
A preparation method of a nano holocellulose reinforced composite membrane comprises the following steps:
(1) crushing a wheat straw raw material, and sieving the crushed wheat straw raw material with a 40-mesh sieve to obtain wheat straw powder for later use;
(2) adding the wheat straw powder obtained in the step (1) into a benzene-alcohol mixed solution (the volume ratio of benzene to alcohol is 2:1) according to a bath ratio of w/v being 1:25, and heating and extracting for 8 hours in a constant-temperature water bath kettle at 90 ℃ to obtain an extract-free sample;
(3) adding the sample without the extract prepared in the step (2) and sodium chlorite into glacial acetic acid according to a bath ratio of w/w/v being 4:1.2:1, heating the mixture in a constant-temperature water bath kettle at 75 ℃ for 1h, filtering the mixture after the reaction is finished, washing the mixture to be neutral by distilled water, and drying the mixture at 105 ℃ for 6h to obtain the holocellulose;
(4) ball-milling the holocellulose prepared in the step (3), swelling the ball-milled holocellulose with deionized water, adjusting the swollen holocellulose to a suspension with the concentration of 0.5-2.0 of the holocellulose solution, treating the obtained suspension with an ultramicron disc mill (MKCA6-2, Japan Masuko), circularly disc-milling at the interval of-9 at the rotating speed of 1500r/min for 15min for 6 times to obtain nano holocellulose;
(5) mixing 5mL of 2% hemicellulose solution and 5mL of 2% chitosan solution, stirring for 1h to fully mix the solutions, adding 0.2mL of nano holocellulose and 0.5mL of epoxy chloropropane into the mixed solution respectively, continuing stirring, reacting for 1h at 60 ℃, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain a composite film sample which is marked as HC-3.
Performance test: the tensile strength of the composite film prepared in the example was 34.93MPa, the elongation at break was 27.91%, and the Young's modulus was 8.23 MPa.
As can be seen from figure 1, after mechanical treatment, the holocellulose still keeps a fibrous structure, and the fibers are intertwined with each other and have the length of between 300 and 1000 nm.
Example 3
A preparation method of a nano holocellulose reinforced composite membrane comprises the following steps:
(1) crushing a wheat straw raw material, and sieving the crushed wheat straw raw material with a 40-mesh sieve to obtain wheat straw powder for later use;
(2) adding the wheat straw powder obtained in the step (1) into a benzene-alcohol mixed solution (the volume ratio of benzene to alcohol is 2:1) according to a bath ratio of w/v being 1:25, and heating and extracting for 8 hours in a constant-temperature water bath kettle at 90 ℃ to obtain an extract-free sample;
(3) adding the sample without the extract prepared in the step (2) and sodium chlorite into glacial acetic acid according to a bath ratio of w/w/v being 4:1.2:1, heating the mixture in a constant-temperature water bath kettle at 75 ℃ for 1h, filtering the mixture after the reaction is finished, washing the mixture to be neutral by distilled water, and drying the mixture at 105 ℃ for 6h to obtain the holocellulose;
(4) ball-milling the holocellulose prepared in the step (3), swelling the ball-milled holocellulose with deionized water, adjusting the swollen holocellulose to a suspension with the concentration of 0.5-2.0 of the holocellulose solution, treating the obtained suspension with an ultramicron disc mill (MKCA6-2, Japan Masuko), circularly disc-milling at the interval of-9 at the rotating speed of 1500r/min for 15min for 6 times to obtain nano holocellulose;
(5) mixing 5mL of 2% hemicellulose solution and 5mL of 2% chitosan solution, stirring for 1h to fully mix the solutions, adding 0.4mL of nano holocellulose and 0.5mL of epoxy chloropropane into the mixed solution respectively, continuing stirring, reacting for 1h at 60 ℃, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain a composite film sample which is marked as HC-4.
Performance test: the tensile strength of the composite film prepared in the embodiment is 26.23MPa, the elongation at break is 26.22%, and the Young modulus is 6.76 MPa.
Example 4
A preparation method of a nano holocellulose reinforced composite membrane comprises the following steps:
(1) crushing a wheat straw raw material, and sieving the crushed wheat straw raw material with a 40-mesh sieve to obtain wheat straw powder for later use;
(2) adding the wheat straw powder obtained in the step (1) into a benzene-alcohol mixed solution (the volume ratio of benzene to alcohol is 2:1) according to a bath ratio of w/v being 1:25, and heating and extracting for 8 hours in a constant-temperature water bath kettle at 90 ℃ to obtain an extract-free sample;
(3) adding the sample without the extract prepared in the step (2) and sodium chlorite into glacial acetic acid according to a bath ratio of w/w/v being 4:1.2:1, heating the mixture in a constant-temperature water bath kettle at 75 ℃ for 1h, filtering the mixture after the reaction is finished, washing the mixture to be neutral by distilled water, and drying the mixture at 105 ℃ for 6h to obtain the holocellulose;
(4) ball-milling the holocellulose prepared in the step (3), swelling the ball-milled holocellulose with deionized water, adjusting the swollen holocellulose to a suspension with the concentration of 0.5-2.0 of the holocellulose solution, treating the obtained suspension with an ultramicron disc mill (MKCA6-2, Japan Masuko), circularly disc-milling at the interval of-9 at the rotating speed of 1500r/min for 15min for 6 times to obtain nano holocellulose;
(5) mixing 5mL of 2% hemicellulose solution and 5mL of 2% chitosan solution, stirring for 1h to fully mix the solutions, adding 0.6mL of nano holocellulose and 0.5mL of epoxy chloropropane into the mixed solution respectively, continuing stirring, reacting for 1h at 60 ℃, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain a composite film sample which is marked as HC-5.
Performance test: the tensile strength of the composite film prepared in the embodiment is 24.36MPa, the elongation at break is 12.87%, and the Young modulus is 9.98 MPa.
FIG. 2 is an infrared spectrum of the raw material and the composite film of examples 1 to 4 of the present invention and comparative example 1, and the results show that the addition of the nano holocellulose as a reinforcing phase to the hemicellulose/chitosan composite film is physically combined and does not cause a chemical reaction.
Fig. 3 is an X-ray diffraction spectrum of the raw materials and the composite films of examples 1 to 4 and comparative example 1, and the results show that characteristic peaks appear in five composite films at 2 θ of 21 to 24 °, and the crystal form change of the composite films is not changed by adding the nano holocellulose.
FIG. 4 is the results of transmittance of the composite films of examples 1 to 4 and comparative example 1, showing that the transmittance of 5 composite films is not changed with the addition of nano holocellulose, and is all above 80%, wherein the transmittance of the composite film sample prepared in example 2 is the highest, reaching 90%; meanwhile, the light transmittance of the composite film in an ultraviolet light wave band is close to 0, and the composite film has better ultraviolet resistance.
FIG. 5 is a stress-strain diagram of the composite films of examples 1 to 4 and comparative example 1, and the results show that the mechanical strength of the hemicellulose-based composite film can be significantly improved by adding nano holocellulose; according to the invention, after the nano holocellulose solution, the hemicellulose solution and the chitosan solution are fully mixed, the composite film is formed by adopting a tape casting film forming method, the prepared composite film has the characteristics of good mechanical property, high strength, good heat resistance and the like, and when 0.2mL of nano holocellulose with the concentration of 0.5% is added, the tensile strength of the prepared composite film is up to 34.93 MPa.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and various process schemes having no substantial difference from the concept of the present invention are within the protection scope of the present invention.
Claims (6)
1. A preparation method of a nano holocellulose reinforced composite membrane is characterized by comprising the following steps:
(1) crushing and sieving a wheat straw raw material to obtain wheat straw powder for later use;
(2) adding the wheat straw powder obtained in the step (1) into a benzene-alcohol mixed solution according to a bath ratio of w/v to 1:25, and heating and extracting in a constant-temperature water bath kettle at 90 ℃ to obtain an extract-free sample;
(3) adding the sample without the extract prepared in the step (2) and sodium chlorite into glacial acetic acid according to a bath ratio of w/w/v being 4:1.2:1, heating the mixture in a constant-temperature water bath kettle at 75 ℃ for 1h, filtering the mixture after the reaction is finished, washing the mixture to be neutral by distilled water, and drying the mixture at 105 ℃ for 6h to obtain the holocellulose;
(4) ball-milling the holocellulose prepared in the step (3), swelling the ball-milled holocellulose with deionized water, adjusting the swollen holocellulose to a suspension with the concentration of 0.5% of the holocellulose solution, treating the obtained suspension with an ultramicron disc mill, wherein the distance between a sample and a grinding disc is-9 mm, repeating disc milling for many times, the rotating speed of the disc mill is 1500r/min, and the disc milling time is 15min, thus preparing the nano holocellulose;
(5) according to the volume ratio of 50:50:1:5-50:50:4:5, mixing a hemicellulose solution with a chitosan solution, wherein the concentration of the hemicellulose solution is 2% and the concentration of the chitosan solution is 2%, stirring for 1-2h to fully mix, adding nano holocellulose and epoxy chloropropane into the mixed solution respectively, then continuing stirring, reacting for 1h at 60 ℃, casting the mixed solution into a film after the reaction is finished, and drying at room temperature to obtain the composite film sample.
2. The method for preparing a nano holocellulose reinforced composite membrane according to claim 1, which is characterized in that: the wheat straw in the step (1) is sieved by a 40-mesh sieve.
3. The method for preparing a nano holocellulose reinforced composite membrane according to claim 1, which is characterized in that: the volume ratio of benzene to alcohol in the benzene-alcohol mixed solution in the step (2) is 2: 1.
4. The method for preparing a nano holocellulose reinforced composite membrane according to claim 1, which is characterized in that: the extraction time in the step (2) is 8 h.
5. The method for preparing a nano holocellulose reinforced composite membrane according to claim 1, which is characterized in that: and (4) repeating the disc grinding for 6 times.
6. A composite membrane prepared by the method for preparing a nano holocellulose reinforced composite membrane according to any one of claims 1 to 5.
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