CN112694629A - Method for preparing biodegradable transparent film by using waste wood biomass - Google Patents
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Abstract
The invention discloses a method for preparing a biodegradable transparent film by using waste wood biomass. The method comprises the steps of cleaning, drying and crushing the waste woody biomass into powder, extracting and dewaxing by absolute ethyl alcohol, mixing with a methanesulfonic acid aqueous solution for prehydrolysis after drying, filtering, washing and drying, and then mixing with alkaline Na2SO3Mixing, reacting, filtering, washing and drying to obtain cellulose; adding a mixture of acetic acid and acetic anhydride, carrying out oil bath heating reaction by using sulfuric acid as a catalyst, centrifuging, adding water into supernate to separate out precipitate, filtering, washing and drying, and partially hydrolyzing to obtain cellulose acetate; mixing the solution with a plasticizer, an anti-reflection agent and a solvent, stirring, standing and defoaming to obtain a cellulose acetate transparent solution; forming a film by a dry phase inversion technology after coating the template; and (4) stripping the film from the template to obtain the cellulose acetate transparent film product. The invention advances the research process of high-value utilization of biomass resources, and the same as the research processIt opens up a new way for solving the problems of white pollution and the like.
Description
Technical Field
The invention relates to preparation of a film, in particular to a method for preparing a biodegradable transparent film by using waste wood biomass.
Background
The high molecular functional materials synthesized by using fossil resources (coal, petroleum and natural gas) as raw materials are generally difficult to degrade, and become white pollution after being discarded, thereby bringing great harm to the environment. With the development of environmental protection technology and the advocation of green environmental protection in society, the problem of white pollution has been more and more emphasized by people. In order to better solve a series of problems such as resource shortage and environmental pollution, people are seeking alternatives of fossil resources. The biomass material has the characteristics of abundant resources, wide sources, renewability, biodegradation and the like, and is considered as a potential fossil alternative resource. Cellulose acetate is a thermoplastic resin obtained by esterifying cellulose raw material derived from woody biomass with anhydride, is the most widely used film-making raw material at present, and has the characteristics of low cost, stable property, excellent strength, good heat resistance, simple preparation process, wide raw material source, biodegradability and the like, so that the cellulose acetate is widely applied to the research fields of materials such as plastics, textiles, films, cigarette filters, packages, reverse osmosis membranes and the like. However, few reports of the invention technology for preparing the biodegradable transparent cellulose acetate film by directly utilizing the waste woody biomass are reported at present. Therefore, aiming at the defect that petroleum-based high polymer materials are difficult to degrade, the invention takes the woody biomass as the raw material to prepare the biodegradable transparent film which is environment-friendly, excellent in performance and excellent in strength.
Disclosure of Invention
In order to overcome the defect that the existing petroleum-based high polymer material is difficult to degrade and better solve a series of problems of energy shortage, environmental pollution and the like, the invention discloses a method for preparing a biodegradable transparent film by utilizing waste woody biomass, which has the advantages of simple process, environmental friendliness and excellent performance.
The invention aims to provide a method for preparing a biodegradable transparent film by using waste woody biomass, which comprises the following steps:
(1) adding waste wood biomass powder into a reaction container, mixing with a methanesulfonic acid aqueous solution, carrying out prehydrolysis for 2-4 hours at 80-120 ℃, filtering, washing and drying, wherein the mass fraction of the methanesulfonic acid aqueous solution is 4-10%, and the mass-volume ratio of the waste wood biomass powder to the methanesulfonic acid aqueous solution is 1:15-30 g/mL;
(2) adding the dried powder obtained in the step (1) into another reaction container, and adding Na2SO3And a water-mixed solution, wherein in the mixed solution, Na2SO3The mass volume ratio of the powder to water is 1:50-100g/mL, the powder is dried, and Na is added2SO3The mass volume ratio of the mixed solution to the water is 1:10-20g/mL, the mixed solution is uniformly mixed, and then NaOH solution is added, wherein the mass fraction of the NaOH solution is 20% -40%, and the mass of the NaOH solution is 0.4% -0.8% of the mass of the solvent system;
(3) heating the reaction substance obtained in the step (2) in an oil bath for reaction for 1-3 hours under the conditions of stirring and 80-120 ℃, filtering the mixture after reaction, washing the filter residue to be neutral, and drying to obtain cellulose;
(4) grinding the cellulose obtained in the step (3) into powder, pouring the powder into another reactor, adding glacial acetic acid, wherein the mass volume ratio of the powder to the glacial acetic acid is 1:7-15g/mL, carrying out oil bath at 50-80 ℃ for 1-3 hours, then adding acetic anhydride and a sulfuric acid catalyst, wherein the mass ratio of the acetic anhydride to the glacial acetic acid is 1:1-5, the sulfuric acid catalyst is a sulfuric acid solution with the mass fraction of not less than 98%, and the mass of the catalyst is 0.5-2.5% of the mass of the cellulose powder raw material;
(5) heating the reaction substance obtained in the step (4) in oil bath for 1-3 hours under the conditions of stirring and 60-100 ℃;
(6) centrifuging the reaction mixture obtained in the step (5), adding distilled water into supernate to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate I;
(7) putting the cellulose acetate I in the step (6) into a 0.1-0.5mol/L sodium hydroxide aqueous solution, and adding the cellulose acetate I and the sodium hydroxide aqueous solution according to the mass-volume ratio of 1:50-100g/mL, soaking at normal temperature for 1-3 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II;
(8) adding the cellulose acetate II powder obtained in the step (7) into another reactor, adding a polar aprotic solvent, wherein the mass volume ratio of the cellulose acetate powder to the polar aprotic solvent is 1:4-12g/mL, adding a plasticizer, wherein the mass of the plasticizer is 10.0-20.0% of that of the cellulose acetate II, and adding an anti-reflection agent, wherein the volume of the anti-reflection agent is 10.0-20.0% of that of the solvent;
(9) stirring the mixture obtained in the step (8) to react for 2-4 hours in a normal-temperature closed environment, and standing for 2-3 hours to completely dissolve cellulose acetate in the solvent to obtain a uniform and transparent cellulose acetate solution;
(10) coating the cellulose acetate solution obtained in the step (9) on a template by adopting a flow extension method, and forming a film by using a dry phase inversion technology;
(11) and (3) stripping the film from the template, and cutting the film product into a proper size according to actual requirements to obtain the cellulose acetate transparent film product.
Further, in the step (1), the waste wood biomass powder is obtained by washing, drying and crushing waste wood biomass to obtain powder, then extracting the powder with absolute ethyl alcohol for 4-8 hours, dewaxing the powder and then drying the powder.
Further, the waste wood biomass is any one or a combination of more than two of corn stalks, straws, bamboos, reeds, bagasse, pennisetum and wood powder.
Further, in the step (7), the cellulose acetate II is cellulose diacetate.
Further, in the step (8), the polar aprotic solvent is at least one of tetrahydrofuran, chloroform, and acetone.
Further, in the step (8), the plasticizer is at least one of glycerol and polyethylene glycol.
Further, in the step (8), the anti-reflection agent is at least one of ethanol, propanol, butanol and pentanol.
Further, in the step (9), the reaction process is carried out in a closed environment, and the atmosphere is air atmosphere or nitrogen atmosphere.
Further, in the step (10), the solution is coated to a thickness of 100 to 500. mu.m.
Further, in the step (10), the dry phase inversion condition is an air atmosphere or a nitrogen atmosphere, and the relative humidity of air is less than 50%.
Further, in the step (10), the total thickness of the film is controlled to be 20 to 80 μm by adjusting the thickness of the cellulose acetate solution coated on the template.
The film light transmittance of the biodegradable transparent film product is more than or equal to 93 percent, the haze is 0-0.5 percent, the tensile strength is 60-120MPa, and the elongation is 2-10 percent.
Compared with the prior art for preparing petroleum-based packaging films, the invention has the following advantages and effects:
(1) the raw material used by the invention is wood biomass, the source of the raw material is wide, and the cost is low;
(2) the method can purify the main component cellulose in the natural waste woody biomass, prepares the cellulose acetate through acetylation, and prepares the transparent film by dissolving the cellulose acetate and adopting a dry phase inversion technology. The invention not only can generate considerable ecological and economic benefits by fully utilizing the cellulose in the biomass to prepare the biodegradable transparent film material, but also can better solve a series of problems of energy shortage, environmental pollution and the like.
The invention opens up a new way for developing and utilizing the green biodegradable biomass-based transparent film instead of fossil-based plastics.
Drawings
FIG. 1 shows a photograph (left) of the appearance of the product obtained in example 1 and an electron microscope scan (right).
FIG. 2 shows a photograph (left) of the appearance of the product obtained in example 2 and an electron microscope scan (right).
FIG. 3 shows a photograph (left) of the appearance of the product obtained in example 3 and an electron microscope scan (right).
FIG. 4 shows a photograph (left) and an electron microscope scan (right) of the appearance of the product obtained in example 4.
FIG. 5 shows a photograph (left) and an electron microscope scan (right) of the appearance of the product obtained in example 5.
FIG. 6 shows a photograph (left) and an electron microscope scan (right) of the appearance of the product obtained in example 6.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Washing the waste corn stalks with distilled water, drying and crushing into powder; weighing 20g of corn straw powder, adding the corn straw powder into a Soxhlet extractor, extracting the powder for 6 hours by using absolute ethyl alcohol, dewaxing the powder, and drying the powder in a 60 ℃ drying oven; adding the dried corn straw powder into a reactor, mixing with 600mL of 8% by mass methanesulfonic acid aqueous solution, carrying out prehydrolysis for 4 hours under the heating condition of 80 ℃, filtering, washing, drying, adding into another reaction vessel, adding 240mL of 2.0% by mass Na2SO3And adding 10mL of NaOH solution with the mass fraction of 20% into the aqueous solution, carrying out oil bath stirring and heating at 100 ℃ for reaction for 1 hour, filtering the mixture after the reaction, washing the filter residue to be neutral, and drying to obtain the cellulose. Grinding the dried cellulose into powder, weighing 5g, pouring the powder into another reactor, adding 35mL of glacial acetic acid, carrying out oil bath at 50 ℃ for 3 hours, adding 35mL of acetic anhydride and 0.05g of sulfuric acid catalyst with the mass fraction of 98%, carrying out oil bath stirring and heating at 80 ℃ for 2 hours, centrifuging the reaction mixture, adding distilled water into the supernatant to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain the cellulose acetate I. Soaking 5g of cellulose acetate I in 250ml of 0.1mol/L sodium hydroxide aqueous solution at normal temperature for 3 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and adding the solid filter residue into the mixtureFreezing and drying to obtain cellulose acetate II; weighing 3g of cellulose acetate II, 0.3g of glycerol, 2mL of ethanol and 20mL of tetrahydrofuran solvent, placing the mixture in a sealed container, stirring the mixture for 2 hours at normal temperature and normal pressure, standing the mixture for 2 hours to completely dissolve cellulose acetate powder in tetrahydrofuran, coating the obtained transparent solution on a glass template by a flow-extension method, and performing phase inversion to form a film in an air atmosphere at normal temperature and normal pressure and at a relative humidity of 50%; stripping the film from the template, and controlling the total thickness of the film to be 0.06mm by adjusting the thickness of the cellulose acetate solution coated on the template; and cutting the film product into a proper size according to the requirement to obtain the biomass-based transparent film product.
Example 2
Washing the waste straw with distilled water, drying, and pulverizing into powder; weighing 30g of straw powder, adding the straw powder into a Soxhlet extractor, extracting the straw powder with absolute ethyl alcohol for 6 hours, dewaxing the powder, and drying the powder in a 60 ℃ drying oven; adding the above dried straw powder into a reactor, mixing with 450mL of 4% methanesulfonic acid aqueous solution, prehydrolyzing at 120 deg.C for 2 hr, filtering, washing, drying, adding into another reaction vessel, adding 290mL of 1.0% Na2SO3And adding 10mL of NaOH solution with the mass fraction of 20% into the aqueous solution, carrying out oil bath stirring and heating at the temperature of 120 ℃ for reaction for 1 hour, filtering the mixture after the reaction, washing the filter residue to be neutral, and drying to obtain the cellulose. Grinding the dried cellulose into powder, weighing 10g, pouring into another reactor, adding 100mL of glacial acetic acid, carrying out oil bath at 60 ℃ for 2 hours, adding 50mL of acetic anhydride and 0.05g of sulfuric acid catalyst with the mass fraction of 98%, carrying out oil bath stirring and heating at 80 ℃ for 2 hours, centrifuging the reaction mixture, adding distilled water into the supernatant to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain the cellulose acetate I. Soaking 5g of cellulose acetate I in 250mL of 0.5mol/L sodium hydroxide aqueous solution at normal temperature for 1 hour, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II; weighingPlacing 5g of cellulose acetate powder, 1.0g of glycerol, 5mL of propanol and 25mL of tetrahydrofuran solvent in a sealed container, stirring for 3 hours at normal temperature and normal pressure, standing for 2 hours to completely dissolve the cellulose acetate powder in the tetrahydrofuran, coating the obtained transparent solution on a glass template by a flow extension method, and performing dry phase inversion to form a film in an air atmosphere at normal temperature and normal pressure and under the environment with the relative humidity of 50%; stripping the film from the template, and controlling the total thickness of the film to be 0.06mm by adjusting the thickness of the cellulose acetate solution coated on the template; and cutting the film product into a proper size according to the requirement to obtain the biomass-based transparent film product.
Example 3
Washing the waste bamboo with distilled water, drying, and pulverizing into powder; weighing 30g of bamboo powder, adding the bamboo powder into a Soxhlet extractor, extracting the bamboo powder for 6 hours by using absolute ethyl alcohol, dewaxing the powder, and drying the powder in a 60 ℃ drying oven; adding the dried bamboo powder into a reactor, mixing with 500mL of 4% methanesulfonic acid aqueous solution, performing prehydrolysis for 3 hours under the heating condition of 100 ℃, filtering, washing, drying, adding into another reaction vessel, adding 290mL of 1.5% Na2SO3And adding 10mL of NaOH solution with the mass fraction of 20% into the aqueous solution, carrying out oil bath stirring and heating at 100 ℃ for reaction for 1 hour, filtering the mixture after the reaction, washing the filter residue to be neutral, and drying to obtain the cellulose. Grinding the dried cellulose into powder, weighing 10g, pouring into another reactor, adding 120mL of glacial acetic acid, carrying out oil bath at 50 ℃ for 3 hours, adding 40mL of acetic anhydride and 0.2g of sulfuric acid catalyst with the mass fraction of 98%, carrying out oil bath stirring and heating at 100 ℃ for 1 hour, centrifuging the reaction mixture, adding distilled water into the supernatant to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain the cellulose acetate I. Soaking 5g of cellulose acetate I in 500mL of 0.1mol/L sodium hydroxide aqueous solution at normal temperature for 2 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II; weighing 5g of cellulose acetate II powder, 0.6g of polyethylene glycol, 5mL of butanol and 25mL of tetraPutting a hydrogen furan solvent into a sealed container, stirring for 3 hours at normal temperature and normal pressure, standing for 2 hours to completely dissolve cellulose acetate powder in tetrahydrofuran, coating the obtained transparent solution on a glass template by a flow-extension method, and performing dry phase inversion to form a film in an air atmosphere at normal temperature and normal pressure and under the environment of 50% of relative humidity; stripping the film from the template, and controlling the total thickness of the film to be 0.06mm by adjusting the thickness of the cellulose acetate solution coated on the template; and cutting the film product into a proper size according to the requirement to obtain the biomass-based transparent film product.
Example 4
Washing the waste reed with distilled water, drying and crushing into powder; weighing 30g of reed powder, adding the reed powder into a Soxhlet extractor, extracting the reed powder with absolute ethyl alcohol for 6 hours, dewaxing the reed powder, and drying the reed powder in a 60 ℃ drying oven; adding the above dried reed powder into a reactor, mixing with 500mL of 4% methanesulfonic acid aqueous solution, performing prehydrolysis for 2 hours under heating at 120 deg.C, filtering, washing, drying, adding into another reaction vessel, adding 240mL of 1.0% Na2SO3And adding 10mL of NaOH solution with the mass fraction of 20% into the aqueous solution, carrying out oil bath stirring and heating at the temperature of 120 ℃ for reaction for 1 hour, filtering the mixture after the reaction, washing the filter residue to be neutral, and drying to obtain the cellulose. Grinding the dried cellulose into powder, weighing 10g, pouring into another reactor, adding 100mL of glacial acetic acid, carrying out oil bath at 80 ℃ for 1 hour, adding 50mL of acetic anhydride and 0.25g of sulfuric acid catalyst with the mass fraction of 98%, carrying out oil bath stirring and heating at 80 ℃ for 1.5 hours, centrifuging the reaction mixture, adding distilled water into the supernatant to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and carrying out freeze drying on the solid filter residue to obtain the cellulose acetate I. Soaking 5g of cellulose acetate I in 400mL of 0.2mol/L sodium hydroxide aqueous solution at normal temperature for 2 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II; weighing 5g of cellulose acetate powder, 0.5g of glycerol, 3mL of amyl alcohol and 30mL of trichloromethane solvent, placing in a sealed container, and keeping at normal temperature and normal pressureStirring for 2 hours, standing for 2 hours to completely dissolve the cellulose acetate powder in the chloroform, coating the obtained transparent solution on a glass template by a flow extension method, and forming a film by dry phase inversion in an air atmosphere at normal temperature and normal pressure and with relative humidity of 50%; stripping the film from the template, and controlling the total thickness of the film to be 0.04mm by adjusting the thickness of the cellulose acetate solution coated on the template; and cutting the film product into a proper size according to the requirement to obtain the biomass-based transparent film product.
Example 5
Washing waste bagasse with distilled water, drying, and pulverizing into powder; weighing 30g of bagasse powder, adding the bagasse powder into a Soxhlet extractor, extracting the powder for 6 hours by using absolute ethyl alcohol, dewaxing the powder, and drying the powder in a 60 ℃ drying oven; adding the above dried bagasse powder into a reactor, mixing with 500mL of 4% by weight methanesulfonic acid aqueous solution, prehydrolyzing at 120 deg.C for 2 hr, filtering, washing, drying, adding into another reaction vessel, adding 240mL of 1.0% by weight Na2SO3And adding 10mL of NaOH solution with the mass fraction of 20% into the aqueous solution, carrying out oil bath stirring and heating at the temperature of 120 ℃ for reaction for 1 hour, filtering the mixture after the reaction, washing the filter residue to be neutral, and drying to obtain the cellulose. Grinding the dried cellulose into powder, weighing 10g, pouring into another reactor, adding 100mL of glacial acetic acid, carrying out oil bath at 60 ℃ for 2 hours, adding 50mL of acetic anhydride and 0.2g of sulfuric acid catalyst with the mass fraction of 98%, carrying out oil bath stirring and heating at 80 ℃ for 2 hours, centrifuging the reaction mixture, adding distilled water into the supernatant to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain the cellulose acetate I. Soaking 5g of cellulose acetate I in 300mL of 0.3mol/L sodium hydroxide aqueous solution at normal temperature for 2 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II; weighing 5g of cellulose acetate powder, 0.6g of glycerol, 3mL of propanol and 50mL of acetone solvent, placing the mixture in a sealed container, stirring the mixture for 2 hours at normal temperature and normal pressure, and standing the mixture for 2 hours to ensure that the cellulose acetate powderCompletely dissolving the element powder in acetone, coating the obtained transparent solution on a glass template by a flow extension method, and forming a film by dry phase inversion in an air atmosphere at normal temperature and normal pressure and under the environment of 50% relative humidity; stripping the film from the template, and controlling the total thickness of the film to be 0.04mm by adjusting the thickness of the cellulose acetate solution coated on the template; and cutting the film product into a proper size according to the requirement to obtain the biomass-based transparent film product.
Example 6
Washing the waste wood with distilled water, drying, and pulverizing into powder; weighing 30g of wood powder, adding the wood powder into a Soxhlet extractor, extracting the powder for 6 hours by using absolute ethyl alcohol, and then drying the powder in a drying oven at the temperature of 60 ℃; adding the dried wood powder into a reactor, mixing with 500mL of 4% methanesulfonic acid aqueous solution, performing prehydrolysis at 120 deg.C for 2 hr, filtering, washing, drying, adding into another reaction vessel, adding 240mL of 1.0% Na2SO3And adding 10mL of NaOH solution with the mass fraction of 20% into the aqueous solution, carrying out oil bath stirring and heating at the temperature of 120 ℃ for reaction for 1 hour, filtering the mixture after the reaction, washing the filter residue to be neutral, and drying to obtain the cellulose. Grinding the dried cellulose into powder, weighing 10g, pouring into another reactor, adding 100mL of glacial acetic acid, carrying out oil bath at 60 ℃ for 3 hours, adding 50mL of acetic anhydride and 0.25g of sulfuric acid catalyst with the mass fraction of 98%, carrying out oil bath stirring and heating at 80 ℃ for 3 hours, centrifuging the reaction mixture, adding distilled water into the supernatant to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain the cellulose acetate I. Soaking 5g of cellulose acetate I in 200mL of 0.2mol/L sodium hydroxide aqueous solution at normal temperature for 3 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II; weighing 5g of cellulose acetate II powder, 0.5g of polyethylene glycol and 50mL of chloroform solvent, placing the mixture in a sealed container, stirring the mixture for 4 hours at normal temperature and normal pressure, standing the mixture for 3 hours to completely dissolve the cellulose acetate powder in the chloroform, and carrying out continuous casting on the obtained transparent solutionCoating the glass template with a flow method, and forming a film by dry phase inversion in an air atmosphere at normal temperature and normal pressure and under the environment with the relative humidity of 50%; stripping the film from the template, and controlling the total thickness of the film to be 0.02mm by adjusting the thickness of the cellulose acetate solution coated on the template; and cutting the film product into a proper size according to the requirement to obtain the biomass-based transparent film product.
The films prepared in examples 1 to 6 were subjected to electron microscope scanning using a Zeiss Sigma 300 instrument and to performance testing as follows:
determination of tensile Strength and elongation at Break:
according to GB/T13022-1991, the film is cut into dumbbell-shaped strips with a knife, the width and thickness of the film are measured with a vernier caliper, the film is stretched at a speed of 300mm/min with a tensile tester, the tensile strength at break and the elongation at break of the film are recorded, and the test results are shown in Table 1.
Determination of transparency and haze:
the light transmittance and haze were measured at 650nm wavelength according to GB/T2410-2008 with a 721 spectrophotometer, the results of which are shown in Table 1.
Table 1:
| case(s) | Tensile Strength (MPa) | Elongation at Break (%) | Light transmittance (%) | Haze (%) |
| Example 1 | 81.16 | 5.8 | 93.2 | 0.85 |
| Example 2 | 84.83 | 6.3 | 93.2 | 0.86 |
| Example 3 | 89.3 | 7.6 | 93.3 | 0.71 |
| Example 4 | 84.02 | 8.5 | 93.3 | 0.33 |
| Example 5 | 71.27 | 3.9 | 93.4 | 0.08 |
| Example 6 | 68.36 | 3.3 | 93.5 | 0.10 |
Claims (10)
1. A method for preparing a biodegradable transparent film by using waste woody biomass is characterized by comprising the following steps:
(1) adding waste wood biomass powder into a reaction container, mixing with a methanesulfonic acid aqueous solution, carrying out prehydrolysis for 2-4 hours at 80-120 ℃, filtering, washing and drying, wherein the mass fraction of the methanesulfonic acid aqueous solution is 4-10%, and the mass-volume ratio of the waste wood biomass powder to the methanesulfonic acid aqueous solution is 1:15-30 g/mL;
(2) adding the dried powder obtained in the step (1) into another reaction container, and adding Na2SO3And a water-mixed solution, wherein in the mixed solution, Na2SO3The mass volume ratio of the powder to water is 1:50-100g/mL, the powder is dried, and Na is added2SO3The mass volume ratio of the mixed solution to the water is 1:10-20g/mL, the mixed solution is uniformly mixed, and then NaOH solution is added, wherein the mass fraction of the NaOH solution is 20% -40%, and the mass of the NaOH solution is 0.4% -0.8% of the mass of the solvent system;
(3) heating the reaction substance obtained in the step (2) in an oil bath for reaction for 1-3 hours under the conditions of stirring and 80-120 ℃, filtering the mixture after reaction, washing the filter residue to be neutral, and drying to obtain cellulose;
(4) grinding the cellulose obtained in the step (3) into powder, pouring the powder into another reactor, adding glacial acetic acid, wherein the mass volume ratio of the powder to the glacial acetic acid is 1:7-15g/mL, carrying out oil bath at 50-80 ℃ for 1-3 hours, then adding acetic anhydride and a sulfuric acid catalyst, wherein the mass ratio of the acetic anhydride to the glacial acetic acid is 1:1-5, the sulfuric acid catalyst is a sulfuric acid solution with the mass fraction of not less than 98%, and the mass of the catalyst is 0.5-2.5% of the mass of the cellulose powder raw material;
(5) heating the reaction substance obtained in the step (4) in oil bath for 1-3 hours under the conditions of stirring and 60-100 ℃;
(6) centrifuging the reaction mixture obtained in the step (5), adding distilled water into supernate to separate out white flocculent precipitate, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate I;
(7) and (3) adding 0.1-0.5mol/L sodium hydroxide aqueous solution into the cellulose acetate I obtained in the step (6), wherein the mass-volume ratio of the cellulose acetate I to the sodium hydroxide aqueous solution is 1:50-100g/mL, soaking at normal temperature for 1-3 hours, filtering the solid-liquid mixture, washing the filter residue to be neutral, and freeze-drying the solid filter residue to obtain cellulose acetate II;
(8) adding the cellulose acetate II powder obtained in the step (7) into another reactor, adding a polar aprotic solvent, wherein the mass volume ratio of the cellulose acetate II powder to the polar aprotic solvent is 1:4-12g/mL, adding a plasticizer, wherein the mass of the plasticizer is 10.0-20.0% of that of the cellulose acetate II, and adding an anti-reflection agent, wherein the volume of the anti-reflection agent is 10.0-20.0% of that of the solvent;
(9) stirring the mixture obtained in the step (8) to react for 2-4 hours in a normal-temperature closed environment, and standing for 2-3 hours to completely dissolve cellulose acetate in the solvent to obtain a uniform and transparent cellulose acetate solution;
(10) coating the cellulose acetate solution obtained in the step (9) on a template by adopting a flow extension method, and forming a film by using a dry phase inversion technology;
(11) and (3) stripping the film from the template, and cutting the film product into a proper size according to actual requirements to obtain the cellulose acetate transparent film product.
2. The method for preparing the biodegradable transparent film by using the waste woody biomass as claimed in claim 1, wherein in the step (1), the waste woody biomass powder is obtained by washing, drying and crushing the waste woody biomass to obtain powder, then extracting the powder with absolute ethyl alcohol for 4 to 8 hours, dewaxing the powder and then drying the powder.
3. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 2, wherein the waste woody biomass is any one or a combination of two or more of corn stover, straw, bamboo, reed, bagasse, pennisetum, and wood flour.
4. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the cellulose acetate II is cellulose diacetate in the step (7).
5. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the polar aprotic solvent is at least one of tetrahydrofuran, chloroform and acetone in the step (8).
6. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the plasticizer is at least one of glycerol and polyethylene glycol in the step (8).
7. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the anti-reflection agent is at least one of ethanol, propanol, butanol and pentanol in the step (8).
8. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the solution is coated to a thickness of 100 to 500 μm in the step (10).
9. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the dry phase inversion technique is performed under the condition of an air atmosphere or a nitrogen atmosphere and the relative humidity of air is less than 50% in the step (10).
10. The method for preparing a biodegradable transparent film using the waste woody biomass according to claim 1, wherein the total thickness of the film is controlled to be 20 to 80 μm by adjusting the thickness of the cellulose acetate solution coated on the template in the step (10).
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| CN114805878A (en) * | 2022-05-25 | 2022-07-29 | 华南农业大学 | Method for preparing degradable biological film by using agricultural and forestry waste and application thereof |
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| CN114805878A (en) * | 2022-05-25 | 2022-07-29 | 华南农业大学 | Method for preparing degradable biological film by using agricultural and forestry waste and application thereof |
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