CN108221063B - Preparation method for preparing film material by using banana nanofibers - Google Patents

Preparation method for preparing film material by using banana nanofibers Download PDF

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CN108221063B
CN108221063B CN201810069485.8A CN201810069485A CN108221063B CN 108221063 B CN108221063 B CN 108221063B CN 201810069485 A CN201810069485 A CN 201810069485A CN 108221063 B CN108221063 B CN 108221063B
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treatment
temperature
crude
ramie
banana
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CN108221063A (en
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辛明
孙健
零东宁
李昌宝
李丽
周主贵
何雪梅
郑凤锦
李志春
唐雅园
盛金凤
李杰民
刘国明
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Guangxi Zhuang Nationality Autonomous Region Academy of Agricultural Sciences
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01CCHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C1/00Treatment of vegetable material
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425Cellulose series
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4266Natural fibres not provided for in group D04H1/425
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326Condensation or reaction polymers
    • D04H1/435Polyesters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning

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  • Engineering & Computer Science (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Molecular Biology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to the technical field of film processing, in particular to a preparation method for preparing a film material by using banana nanofibers, which comprises two steps of preparing banana fibers and preparing a nanofiber film material; according to the invention, besides the banana fiber, the cedar wood dust, chitosan and polylactic acid are added for chelation, so that the corrosion resistance and the compression resistance of the nanofiber film material can be improved, and meanwhile, the banana fiber and the polylactic acid used in the method are degradable substances and are used for producing the nanofiber film to enable the film to be degradable, so that the problem of environmental pollution is solved.

Description

Preparation method for preparing film material by using banana nanofibers
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of film processing, in particular to a preparation method for preparing a film material by using banana nanofibers.
[ background of the invention ]
The film material has the characteristics of high strength, light weight, corrosion resistance, low price and the like, and is widely applied to production and life of people. The application of the film material brings great convenience to people and brings serious negative effects, most of the waste film materials can be degraded under special conditions, the light and biological degradation speed of the waste film materials in the natural environment is very slow, the waste film materials can completely disappear after about hundreds of years, and the waste film materials can be treated by burying, burning and other methods, but the methods have great defects. The waste plastics after being used in large quantity can not be automatically degraded, and can cause serious environmental pollution after being remained in the natural environment for a long time, thereby not only influencing the ecological balance, but also threatening the health of human beings. According to incomplete statistics, the film materials produced in the world per year exceed billion tons, while the film materials in China account for a considerable proportion, and the disposable film materials are more. The used waste film material has the characteristics of large quantity, wide distribution, difficult recovery and the like, and forms white garbage to cause serious environmental pollution. In order to solve the problem, research and development of degradable plastics become an ideal way for solving white pollution, the degradable plastics can be automatically and completely decomposed under natural conditions after being discarded, and the pollution to the environment is very small. The degradation process of plastics refers to a process in which macromolecular chains constituting the plastics are cut into small molecules by the action of light and microorganisms, and the large molecules are decomposed into CO2And H2O, eventually disappears in nature.
At present, a precedent of producing a degradable film material by using degradable organic matters such as cellulose and starch is provided, but the technical defects of low toughness, low pressure resistance, low light transmittance and low water permeability still exist; china now becomes a large banana production country, banana can produce stalks which are approximately equal to fruits after being harvested, most of the banana is directly discarded in each production area of China, the environment pollution of banana plantations is caused, and a large amount of plant resources are wasted. The banana fiber widely exists in pseudostem bast, leaf and fruit shaft, belongs to natural cellulose fiber and has the advantages of natural hemp fiber. If the cellulose can be effectively utilized to prepare the nano-fiber film material, the utilization value of the banana waste can be effectively improved, and the added value of the banana waste can be improved.
Because the banana waste contains more lignin and colloid, the impurities can greatly influence the purity of fiber extraction, and if the banana waste cannot be degummed and pretreated well, the banana fiber film product has poor light transmittance, poor water permeability, poor oxygen permeability and poor quality, and has technical defects.
[ summary of the invention ]
In view of the above, there is a need to produce a banana nanofiber film with high strength, good thinness, good light transmittance, good water permeability and good oxygen permeability, so as to further improve the utilization field and the utilization value of banana waste and improve the added value of banana waste products.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method for preparing a film material by using banana nanofibers comprises the following steps:
preparing banana fiber:
(1) pretreatment of raw materials: cutting banana peel, leaf or stem into sections, then breaking and tearing into slices with the thickness of 0.5-2 mm, squeezing, scraping impurities and drying to obtain rough ramie;
(2) degumming treatment: sequentially carrying out puffing treatment, oxidation treatment, acid treatment, biological enzyme treatment, enzyme inactivation treatment, dehydration, oil feeding and drying on the coarse ramie obtained in the step (1) to obtain coarse fibers;
the processing method of the puffing treatment comprises the following steps: mixing crude hemp with a sodium hydroxide solution with the mass concentration of 2g/L-4g/L according to the solid-liquid mass ratio of 1:17-22, quickly heating to 95-100 ℃, decocting at constant temperature for 20min-30min, draining the sodium hydroxide solution, fishing out the crude hemp, putting the crude hemp into hot water with the pressure condition of 7MPa-8MPa and the temperature of 90-95 ℃ for 10min-15min, draining the hot water, putting the crude hemp into cold water with the pressure condition of 2MPa-3MPa and the temperature of 0-5 ℃ for 10min-15min, filtering and airing to finish the bulking treatment process;
the treatment method of the oxidation treatment comprises the following steps: mixing the bulked crude ramie with an oxidant solution according to a solid-liquid mass ratio of 1:20-25, then rapidly heating to 95-100 ℃, decocting at a constant temperature for 15-20 min, draining the oxidant solution, putting the crude ramie into hot water at a temperature of 90-95 ℃, keeping the constant temperature for 5-10 min, then putting the crude ramie into cold water at a temperature of 0-5 ℃, keeping the constant temperature for 5-10 min, filtering, and airing to finish the oxidation treatment process;
the acid treatment method comprises the following steps: mixing the oxidized crude ramie with a sulfuric acid solution with the mass concentration of 1g/L-3g/L according to the solid-liquid mass ratio of 1:15-20, then rapidly heating to 95-100 ℃, decocting at constant temperature for 15min-20min, taking out the crude ramie, putting the crude ramie into hot water with the temperature of 90-95 ℃ for washing for 5min, then putting the crude ramie into cold water with the temperature of 0-5 ℃ for washing for 10min, and then airing to finish the acid treatment process;
the treatment method of the biological enzyme treatment comprises the following steps: mixing the acid-treated crude ramie with a biological enzyme solution according to a solid-liquid mass ratio of 1:18-23, keeping the temperature at 30-40 ℃ for 20-25 min, taking out the crude ramie, and putting the crude ramie into cold water at 0-5 ℃ for washing for 10 min; finishing the biological enzyme treatment process;
the treatment method of the enzyme inactivation treatment comprises the following steps: putting the crude ramie treated by the biological enzyme into hot water with the temperature of 85-90 ℃, and decocting for 30-35 min at constant temperature; completing the enzyme inactivation treatment process;
the dehydration treatment method comprises the following steps: putting the enzyme-inactivated crude ramie into a vacuum diatomite filter press with the vacuum degree of 0.01MPa-0.1MPa for vacuum filter pressing to complete the dehydration treatment process;
the oil feeding treatment method comprises the following steps: uniformly spraying a layer of tea seed oil on the dehydrated rough ramie to finish the oil feeding treatment process;
the drying treatment method comprises the following steps: placing the oiled crude ramie into a hot air dryer at the temperature of 50-60 ℃ until the water content of the crude ramie is 3-5% to obtain banana fiber;
(II) preparing a nanofiber film:
(3) preparing a precursor solution: mixing the banana fiber, the cedar chips, the polylactic acid, the chitosan and the cellulose binary system fiber solution obtained in the step (2) according to the mass ratio of 10-13:1:4-7:1-2:10-15 to obtain banana fiber-based plastic; stirring and mixing tin chloride and ethylene glycol according to the mass ratio of 1:3-8 to obtain a tin precursor solution;
(4) preparing a spinning solution: dropwise adding the tin precursor solution obtained in the step (3) into the banana fiber-based plastic, continuously stirring, then adding solid phosphorus pentoxide and boric acid into the mixed solution of the tin precursor and the banana fiber precursor, and fully stirring to obtain a spinning solution; the mass ratio of the tin precursor to the banana fiber-based plastic is 1: 6-9;
(5) preparing a nanofiber film: and (3) mixing the spinning solution obtained in the step (4), the aloe extract, the chitosan and the spinning solution according to the mass ratio of 4-7:1-3:1, removing bubbles by using ultrasound, processing the mixture into a fiber membrane by using a high-voltage electrostatic spinning machine, and pre-oxidizing and carbonizing the fiber membrane to obtain the banana nanofiber membrane.
Further, the oxidant solution in the step (2) is prepared by mixing hydrogen peroxide, methyl orange, a salix populi extract and water according to the mass ratio of 3-5:1-3:6-9: 30-35.
Further, the biological enzyme solution in the step (2) is prepared by mixing pectinase, hemicellulase, lignin degrading enzyme, barbaloin and water according to the mass ratio of 2-4:2-4:1-3:5-9: 30-35.
Further, the cellulose binary system in the step (3) comprises a lithium chloride/dimethylacetamide system or an ammonia/ammonium thiocyanate system.
Further, the lithium chloride/dimethylacetamide system is prepared by mixing lithium chloride, dimethylacetamide and water according to a mass ratio of 4-6:1: 10-15.
Further, the ammonia/ammonium thiocyanate system is prepared by mixing ammonium thiocyanate, ammonia and water according to the mass ratio of 65-75:25-30: 1.
Further, the addition amount of the phosphorus pentoxide in the step (4) is 1g/L-3 g/L; the addition amount of boric acid is 0.5g/L-2 g/L.
Further, the process conditions of the high-voltage electrostatic spinning machine are as follows: the spinning voltage is 15kV-25kV, the flow rate of the spinning solution is 0.5-1mL/h, the rotating speed is 4000r/min-5000r/min, the relative humidity is 30% -40%, the spinning time is 4h-6h, and the spinning solution is received by a roller.
Further, the pre-oxidation method comprises the following steps: placing the fiber membrane in hot air with the pre-oxidation temperature of 250-300 ℃, and preserving heat for 3-5 h to complete the pre-oxidation process; the carbonization method comprises the following steps: and (3) placing the pre-oxidized fiber membrane in a carbonization furnace, heating at the speed of 4-6 ℃/min until the temperature is raised to 700-750 ℃, preserving the heat for 2-3 h at the temperature, then cooling at the speed of 4-6 ℃/min, and finishing the carbonization process when the temperature is reduced to room temperature.
The invention has the following beneficial effects:
1. the banana nanofiber processing method comprises the steps of carrying out puffing treatment, oxidation treatment, acid treatment, biological enzyme treatment, enzyme inactivation treatment, dehydration, oil supply and drying on banana hemp, wherein the pretreatment is carried out on the banana hemp by combining the steps of the puffing treatment, the oxidation treatment, the acid treatment, the biological enzyme treatment, the enzyme inactivation treatment, the dehydration, the oil supply and the drying, the colloid and the impurity removal in the banana hemp can be effectively removed, so that the fiber content is increased, the puffing treatment is carried out on the hemp by soaking the hemp in high-temperature alkali liquor, the acting force among the colloids can be effectively weakened, the lignin is dissolved, then the puffing is carried out on the hemp by firstly heating and pressurizing and then quickly reducing the pressure, the hydrogen bond breakage among the colloids is accelerated, the colloid macromolecules are scattered, the; although the rough ramie is subjected to the swelling treatment, the colloid and lignin components in the rough ramie cannot be dissolved and separated, and further treatment is needed, the swelling treatment is carried out on the rough ramie and an oxidant (prepared by hydrogen peroxide, methyl orange, a salix populi extract and water) to effectively remove the induction force among the colloids, the colloid and the lignin are more effectively dissolved, the hydrogen peroxide has strong oxidizing property, but the structure of cellulose can be damaged by using excessive hydrogen peroxide, and the inventor researches and discovers that when the hydrogen peroxide is matched with the methyl orange and the salix populi extract according to a certain amount, the decomposition capability of the colloid and the lignin can be effectively improved, and the strength of the cellulose can be effectively maintained; after the swelling and oxidation treatment, the fiber can not meet the requirement of producing the nanofiber, the acid treatment is carried out by a sulfuric acid solution, the fiber is rapidly cooled after being heated by the acid treatment, the toughness of the fiber can be effectively improved, and the fineness of the nanofiber can be conveniently improved in the later-stage production of the nanofiber; however, although the banana fiber is subjected to puffing, oxidation and acid treatment, part of the pectin, lignin and hemicellulose decomposed into small molecules after puffing are still attached to the cellulose, and in order to further purify the fiber content of the banana fiber, a corresponding biological enzyme solution (pectinase, hemicellulase, lignin degrading enzyme, barbaloin and water) is prepared according to the characteristics of the components of the pectin to specifically decompose the pectin, lignin and hemicellulose, so that impurities are effectively removed, the fiber content is improved, and preparation is made for next-step production of the nanofiber; after the pretreatment of puffing, oxidation, acidification and biological enzyme, the cellulose content of the banana fiber is relatively pure, and the banana fiber is sprayed by using tea seed oil at the moment, so that the fiber components can be effectively protected, the unsaturated acid content of the fiber can be improved, the electrolytic capacity of the banana fiber spinning solution is improved, and the extremely thin nanofiber film can be produced.
2. The nanofiber film of this application has added the cedar wood bits except using the banana fiber, chitosan and polylactic acid chelate, cedar wood bits and chitosan have stronger hardness, can improve the toughness and the compressive capacity of nanofiber film material, and simultaneously, the banana fiber that this application used, polylactic acid all is degradable material, it makes the film degradable to be used for producing the nanofiber film, environmental pollution's problem has been solved, this application still uses high-pressure electrostatic spinning technology to prepare the nanofiber film, this technology can effectively improve the purity of nanofiber film, effectively get rid of impurity, produce out thin nanofiber film, improve the quality of nanofiber film.
[ detailed description ] embodiments
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification (including any accompanying claims, abstract) is merely an example of a generic series of equivalent or similar features, unless explicitly described as such.
Example 1:
the embodiment provides a preparation method for preparing a film material by using banana nanofibers, which comprises the following steps of preparing the banana fibers and preparing the nanofiber film material:
preparing banana fiber:
(1) pretreatment of raw materials: cutting banana peel, leaf or stem into sections, then breaking and tearing into slices with the thickness of 0.5mm, squeezing, scraping impurities and drying to obtain rough ramie;
(2) degumming treatment: sequentially carrying out puffing treatment, oxidation treatment, acid treatment, biological enzyme treatment, enzyme inactivation treatment, dehydration, oil feeding and drying on the coarse ramie obtained in the step (1) to obtain coarse fibers;
the processing method of the puffing treatment comprises the following steps: mixing crude hemp with a sodium hydroxide solution with the mass concentration of 2g/L according to the solid-liquid mass ratio of 1:17, then rapidly heating to 95 ℃, boiling at constant temperature for 20min, draining the sodium hydroxide solution, fishing out the crude hemp, putting the crude hemp into hot water with the pressure condition of 7MPa and the temperature of 90 ℃ for constant temperature keeping for 10min, then draining the hot water, putting the crude hemp into cold water with the pressure condition of 2MPa and the temperature of 0 ℃ for constant temperature keeping for 10min, filtering and airing to finish the swelling treatment process;
the treatment method of the oxidation treatment comprises the following steps: mixing the bulked crude ramie with an oxidant solution according to a solid-liquid mass ratio of 1:20, rapidly heating to 95 ℃, decocting at a constant temperature for 15min, draining the oxidant solution, putting the crude ramie into hot water at a temperature of 90 ℃, keeping the constant temperature for 5min, putting the crude ramie into cold water at a temperature of 0 ℃, keeping the constant temperature for 5min, filtering, and airing to finish an oxidation treatment process;
the acid treatment method comprises the following steps: mixing the oxidized crude ramie with a sulfuric acid solution with the mass concentration of 1g/L according to the solid-liquid mass ratio of 1:15, then rapidly heating to 95 ℃, decocting at constant temperature for 15min, taking out the crude ramie, putting the crude ramie into hot water with the temperature of 90 ℃ for washing for 5min, then putting the crude ramie into cold water with the temperature of 0 ℃ for washing for 10min, and then airing to finish the acid treatment process;
the treatment method of the biological enzyme treatment comprises the following steps: mixing the acid-treated crude hemp with a biological enzyme solution according to a solid-liquid mass ratio of 1:18-23, keeping the temperature at 30 ℃ for 20min, taking out the crude hemp, and washing the crude hemp in cold water at 0 ℃ for 10 min; finishing the biological enzyme treatment process;
the treatment method of the enzyme inactivation treatment comprises the following steps: putting the crude hemp after the biological enzyme treatment into hot water of 85 ℃, and decocting for 30min at constant temperature; completing the enzyme inactivation treatment process;
the dehydration treatment method comprises the following steps: putting the enzyme-inactivated crude ramie into a vacuum diatomite filter press with the vacuum degree of 0.01MPa for vacuum filter pressing to complete the dehydration treatment process;
the oil feeding treatment method comprises the following steps: uniformly spraying a layer of tea seed oil on the dehydrated rough ramie to finish the oil feeding treatment process;
the drying treatment method comprises the following steps: placing the oiled rough ramie into a hot air dryer at 50 ℃ until the moisture content of the rough ramie is 3% to obtain banana fiber;
(II) preparing a nanofiber film:
(3) preparing a precursor solution: mixing the banana fiber obtained in the step (2), the cedar chips, the polylactic acid, the chitosan and the cellulose binary system fiber dissolving solution according to the mass ratio of 10:1:4:1:10 to obtain banana fiber-based plastic; stirring and mixing tin chloride and ethylene glycol according to the mass ratio of 1:3 to obtain a tin precursor solution;
(4) preparing a spinning solution: dropwise adding the tin precursor solution obtained in the step (3) into banana fiber-based plastic, continuously stirring, then adding solid phosphorus pentoxide and boric acid (wherein the addition amount of the phosphorus pentoxide is 1g/L and the addition amount of the boric acid is 0.5g/L) into the mixed solution of the tin precursor and the banana fiber precursor, and fully stirring to obtain a spinning solution; the mass ratio of the tin precursor to the banana fiber-based plastic is 1: 6;
(5) preparing a nanofiber film: mixing the spinning solution, the aloe extract, the chitosan and the spinning solution obtained in the step (4) according to a mass ratio of 4:1:1:1, removing bubbles by using ultrasound, treating the mixture by using a high-voltage electrostatic spinning machine under the conditions that the spinning voltage is 15kV, the flow rate of the spinning solution is 0.5mL/h, the rotating speed is 4000r/min, the relative humidity is 30 percent and the spinning time is 4h, and receiving the mixture by using a roller to obtain a fiber membrane; and (2) placing the fiber membrane in hot air at the temperature of 250 ℃, preserving heat for 3h for pre-oxidation, placing the fiber membrane in a carbonization furnace after pre-oxidation, heating at the speed of 4 ℃/min until the temperature is raised to 700 ℃, preserving heat for 2h at the temperature, and then cooling to room temperature at the speed of 4 ℃/min to obtain the nanofiber membrane.
Wherein the oxidant solution is prepared by mixing hydrogen peroxide, methyl orange, salix populi extract and water according to the mass ratio of 3:1:6: 30.
In the oxidant solution, the extraction method of the salix populi extract comprises the following steps: drying poplar bark and then crushing the dried poplar bark into 300 meshes, mixing the powder with 75% ethanol solution by volume according to a solid-to-liquid ratio of 1:5, putting the mixture into an ultrasonic extractor, and performing intermittent ultrasonic extraction at a power of 400w, wherein the total extraction time of the intermittent extraction is 2 hours, namely ultrasonic extraction for 2min, stopping the ultrasonic extraction for 10s and ultrasonic extraction for 2 min; performing ultrasonic extraction, placing the mixture into a reflux extractor, performing constant temperature extraction at 150 deg.C for 12h, and performing rotary evaporation and concentration on the extractive solution until the water content is 5% to obtain Salix babylonica extract with Salix babylonica glycoside content of 98.09 mg/g; the content of sodium salicylate is 146.09 mg/g.
Wherein the biological enzyme solution is prepared by mixing pectinase, hemicellulase, lignin degrading enzyme, barbaloin and water according to the mass ratio of 2:2:1:5: 30.
In the biological enzyme solution, the enzyme activity of the pectinase is 1000U/g: the enzyme activity of the hemicellulase is 800U/g, and the enzyme activity of the lignin degrading enzyme is 1200U/g.
Wherein the cellulose binary system is a lithium chloride/dimethylacetamide system.
The lithium chloride/dimethylacetamide system is prepared by mixing lithium chloride, dimethylacetamide and water according to a mass ratio of 4:1: 10.
Wherein the above-mentioned cedar wood chips are taken from the trunk of cedar (Cunninghamialanceolata (Lamb.) Hook.).
Example 2:
the embodiment provides a preparation method for preparing a film material by using banana nanofibers, which comprises the following steps of preparing the banana fibers and preparing the nanofiber film material:
preparing banana fiber:
(1) pretreatment of raw materials: cutting banana peel, leaf or stem into sections, then breaking and tearing into slices with the thickness of 2mm, squeezing, scraping impurities and drying to obtain rough ramie;
(2) degumming treatment: sequentially carrying out puffing treatment, oxidation treatment, acid treatment, biological enzyme treatment, enzyme inactivation treatment, dehydration, oil feeding and drying on the coarse ramie obtained in the step (1) to obtain coarse fibers;
the processing method of the puffing treatment comprises the following steps: mixing the crude ramie with a sodium hydroxide solution with the mass concentration of 4g/L according to the solid-liquid mass ratio of 1:22, then rapidly heating to 100 ℃, decocting at constant temperature for 30min, draining the sodium hydroxide solution, fishing out the crude ramie, putting the crude ramie into hot water with the pressure condition of 8MPa and the temperature of 95 ℃ for constant temperature for 15min, draining the hot water, putting the crude ramie into cold water with the pressure condition of 3MPa and the temperature of 5 ℃ for constant temperature for 15min, filtering and airing to finish the puffing treatment process;
the treatment method of the oxidation treatment comprises the following steps: mixing the bulked crude ramie with an oxidant solution according to a solid-liquid mass ratio of 1:25, quickly heating to 100 ℃, decocting at a constant temperature for 20min, draining the oxidant solution, putting the crude ramie into hot water at a temperature of 95 ℃, keeping the constant temperature for 10min, putting the crude ramie into cold water at a temperature of 5 ℃, keeping the constant temperature for 10min, filtering, and airing to finish an oxidation treatment process;
the acid treatment method comprises the following steps: mixing the oxidized crude ramie with a sulfuric acid solution with the mass concentration of 3g/L according to the solid-liquid mass ratio of 1:20, then rapidly heating to 100 ℃, decocting at constant temperature for 20min, taking out the crude ramie, washing in hot water with the temperature of 95 ℃ for 5min, washing in cold water with the temperature of 5 ℃ for 10min, and then drying in the air to finish the acid treatment process;
the treatment method of the biological enzyme treatment comprises the following steps: mixing the acid-treated crude hemp with a biological enzyme solution according to a solid-liquid mass ratio of 1:23, keeping the temperature at 40 ℃ for 25min, taking out the crude hemp, and putting the crude hemp into cold water at 5 ℃ for washing for 10 min; finishing the biological enzyme treatment process;
the treatment method of the enzyme inactivation treatment comprises the following steps: putting the crude hemp after the biological enzyme treatment into hot water of 90 ℃, and decocting for 35min at constant temperature; completing the enzyme inactivation treatment process;
the dehydration treatment method comprises the following steps: putting the enzyme-inactivated crude ramie into a vacuum diatomite filter press with the vacuum degree of 0.1MPa for vacuum filter pressing to complete the dehydration treatment process;
the oil feeding treatment method comprises the following steps: uniformly spraying a layer of tea seed oil on the dehydrated rough ramie to finish the oil feeding treatment process;
the drying treatment method comprises the following steps: placing the oiled rough ramie into a hot air dryer at the temperature of 60 ℃ until the moisture content of the rough ramie is 5% to obtain banana fiber;
(II) preparing a nanofiber film:
(3) preparing a precursor solution: mixing the banana fiber obtained in the step (2), the cedar chips, the polylactic acid, the chitosan and the cellulose binary system fiber dissolving solution according to the mass ratio of 13:1:7:2:15 to obtain banana fiber-based plastic; stirring and mixing tin chloride and ethylene glycol according to the mass ratio of 1:8 to obtain a tin precursor solution;
(4) preparing a spinning solution: dropwise adding the tin precursor solution obtained in the step (3) into banana fiber-based plastic, continuously stirring, then adding solid phosphorus pentoxide and boric acid (wherein the addition amount of the phosphorus pentoxide is 3g/L and the addition amount of the boric acid is 2g/L) into the mixed solution of the tin precursor and the banana fiber precursor, and fully stirring to obtain a spinning solution; the mass ratio of the tin precursor to the banana fiber-based plastic is 1: 9;
(5) preparing a nanofiber film: mixing the spinning solution, the aloe extract, the chitosan and the spinning solution obtained in the step (4) according to the mass ratio of 7:3:3:1, removing bubbles by using ultrasound, treating the mixture by using a high-voltage electrostatic spinning machine under the conditions that the spinning voltage is 25kV, the flow rate of the spinning solution is 1mL/h, the rotating speed is 5000r/min, the relative humidity is 40 percent, and the spinning time is 6h, and receiving the mixture by using a roller to obtain a fiber membrane; and (2) placing the fiber membrane in hot air at the temperature of 300 ℃, preserving heat for 5h for pre-oxidation, placing the fiber membrane in a carbonization furnace after pre-oxidation, heating at the speed of 6 ℃/min until the temperature is raised to 750 ℃, preserving heat for 3h at the temperature, and then cooling to room temperature at the speed of 6 ℃/min to obtain the nanofiber membrane.
Wherein the oxidant solution is prepared by mixing hydrogen peroxide, methyl orange, salix populi extract and water according to the mass ratio of 5:3:9: 35.
In the oxidant solution, the extraction method of the salix populi extract is completely consistent with that of example 1.
Wherein the biological enzyme solution is prepared by mixing pectinase, hemicellulase, lignin degrading enzyme, barbaloin and water according to the mass ratio of 4:4:3:9: 35.
In the biological enzyme solution, the enzyme activity of the pectinase is 1500U/g: the enzyme activity of the hemicellulase is 1200U/g, and the enzyme activity of the lignin degrading enzyme is 1000U/g.
Among these, the cellulose binary system uses a lithium chloride/dimethylacetamide system.
The lithium chloride/dimethylacetamide system is prepared by mixing lithium chloride, dimethylacetamide and water according to the mass ratio of 6:1: 15.
Wherein the above-mentioned cedar wood chips are taken from the trunk of cedar (Cunninghamialanceolata (Lamb.) Hook.).
Example 3:
the embodiment provides a preparation method for preparing a film material by using banana nanofibers, which comprises the following steps of preparing the banana fibers and preparing the nanofiber film material:
preparing banana fiber:
(1) pretreatment of raw materials: cutting banana peel, leaf or stem into sections, then breaking and tearing into slices with the thickness of 1mm, squeezing, scraping impurities and drying to obtain rough ramie;
(2) degumming treatment: sequentially carrying out puffing treatment, oxidation treatment, acid treatment, biological enzyme treatment, enzyme inactivation treatment, dehydration, oil feeding and drying on the coarse ramie obtained in the step (1) to obtain coarse fibers;
the processing method of the puffing treatment comprises the following steps: mixing crude hemp with a sodium hydroxide solution with the mass concentration of 3g/L according to the solid-liquid mass ratio of 1:20, then rapidly heating to 98 ℃, decocting at constant temperature for 25min, draining the sodium hydroxide solution, fishing out the crude hemp, putting the crude hemp into hot water with the pressure condition of 7.5MPa and the temperature of 92 ℃ for constant temperature maintenance for 12min, then draining the hot water, putting the crude hemp into cold water with the pressure condition of 2.5MPa and the temperature of 2 ℃ for constant temperature maintenance for 12min, filtering and airing to finish the bulking treatment process;
the treatment method of the oxidation treatment comprises the following steps: mixing the bulked crude ramie with an oxidant solution according to a solid-liquid mass ratio of 1:22, quickly heating to 98 ℃, decocting at a constant temperature for 17min, draining the oxidant solution, putting the crude ramie into hot water at a temperature of 92 ℃, keeping the constant temperature for 7min, putting the crude ramie into cold water at a temperature of 2 ℃, keeping the constant temperature for 7min, filtering, and airing to finish an oxidation treatment process;
the acid treatment method comprises the following steps: mixing the oxidized crude ramie with a sulfuric acid solution with the mass concentration of 2g/L according to the solid-liquid mass ratio of 1:17, then rapidly heating to 98 ℃, decocting at constant temperature for 18min, taking out the crude ramie, washing in hot water with the temperature of 92 ℃ for 5min, washing in cold water with the temperature of 2 ℃ for 10min, and drying in the air to finish the acid treatment process;
the treatment method of the biological enzyme treatment comprises the following steps: mixing the acid-treated crude hemp with a biological enzyme solution according to a solid-liquid mass ratio of 1:20, keeping the temperature at 35 ℃ for 22min, taking out the crude hemp, and putting the crude hemp into cold water at 3 ℃ for washing for 10 min; finishing the biological enzyme treatment process;
the treatment method of the enzyme inactivation treatment comprises the following steps: putting the crude hemp after the biological enzyme treatment into hot water of 87 ℃, and decocting for 32min at constant temperature; completing the enzyme inactivation treatment process;
the dehydration treatment method comprises the following steps: putting the enzyme-inactivated crude ramie into a vacuum diatomite filter press with the vacuum degree of 0.08MPa for vacuum filter pressing to complete the dehydration treatment process;
the oil feeding treatment method comprises the following steps: uniformly spraying a layer of tea seed oil on the dehydrated rough ramie to finish the oil feeding treatment process;
the drying treatment method comprises the following steps: putting the oiled rough ramie into a hot air dryer at the temperature of 55 ℃ until the moisture content of the rough ramie is 4% to obtain banana fiber;
(II) preparing a nanofiber film:
(3) preparing a precursor solution: mixing the banana fiber obtained in the step (2), the cedar chips, the polylactic acid, the chitosan and the cellulose binary system fiber dissolving solution according to the mass ratio of 11:1:6:1.5:12 to obtain banana fiber-based plastic; stirring and mixing tin chloride and ethylene glycol according to the mass ratio of 1:5 to obtain a tin precursor solution;
(4) preparing a spinning solution: dropwise adding the tin precursor solution obtained in the step (3) into banana fiber-based plastic, continuously stirring, then adding solid phosphorus pentoxide and boric acid (wherein the addition amount of the phosphorus pentoxide is 2g/L and the addition amount of the boric acid is 1g/L) into the mixed solution of the tin precursor and the banana fiber precursor, and fully stirring to obtain a spinning solution; the mass ratio of the tin precursor to the banana fiber-based plastic is 1: 8;
(5) preparing a nanofiber film: mixing the spinning solution, the aloe extract, the chitosan and the spinning solution obtained in the step (4) according to the mass ratio of 5:2:2:1, removing bubbles by using ultrasound, treating the mixture by using a high-voltage electrostatic spinning machine under the conditions that the spinning voltage is 20kV, the flow rate of the spinning solution is 0.8mL/h, the rotating speed is 4500r/min, the relative humidity is 35 percent and the spinning time is 5h, and receiving the mixture by using a roller to obtain a fiber membrane; and (2) placing the fiber membrane in hot air at the temperature of 280 ℃, preserving heat for 4h for pre-oxidation, placing the fiber membrane in a carbonization furnace after pre-oxidation, heating at the speed of 5 ℃/min until the temperature is raised to 720 ℃, preserving heat at the temperature for 2.5h, and then cooling to room temperature at the speed of 5 ℃/min to obtain the nanofiber membrane.
Wherein the oxidant solution is prepared by mixing hydrogen peroxide, methyl orange, salix populi extract and water according to the mass ratio of 4:2:7: 33.
In the oxidant solution, the extraction method of the salix populi extract is completely consistent with that of example 1.
Wherein the biological enzyme solution is prepared by mixing pectinase, hemicellulase, lignin degrading enzyme, barbaloin and water according to the mass ratio of 3:3:2:7: 32.
In the biological enzyme solution, the enzyme activity of the pectinase is 1200U/g: the enzyme activity of the hemicellulase is 900U/g, and the enzyme activity of the lignin degrading enzyme is 1300U/g.
Among these, the cellulose binary system uses a lithium chloride/dimethylacetamide system.
The lithium chloride/dimethylacetamide system is prepared by mixing lithium chloride, dimethylacetamide and water according to a mass ratio of 5:1: 13.
Wherein the above-mentioned cedar wood chips are taken from the trunk of cedar (Cunninghamialanceolata (Lamb.) Hook.).
Example 4:
the other preparation method of this example is exactly the same as example 1, but the cellulose binary system uses an ammonia/ammonium thiocyanate system. Wherein the ammonia/ammonium thiocyanate system is prepared by mixing ammonium thiocyanate, ammonia and water according to the mass ratio of 65:25: 1.
Example 5:
the other preparation method of this example is exactly the same as example 2, but the cellulose binary system uses an ammonia/ammonium thiocyanate system. Wherein the ammonia/ammonium thiocyanate system is prepared by mixing ammonium thiocyanate, ammonia and water according to the mass ratio of 75:30: 1.
Example 6:
the other preparation method of this example is exactly the same as example 3, but the cellulose binary system uses an ammonia/ammonium thiocyanate system. Wherein the ammonia/ammonium thiocyanate system is prepared by mixing ammonium thiocyanate, ammonia and water according to the mass ratio of 70:28: 1.
Control group 1:
in the comparison group, the banana hemp is pretreated without using puffing treatment in the process of preparing the banana fiber, and other parameters and methods are completely consistent with those of the embodiment 1.
Control group 2:
in the comparison group, the banana hemp is pretreated without oxidation treatment in the process of preparing the banana fiber, and other parameters and methods are completely consistent with those of the embodiment 1.
Control group 3:
the control group does not use acid treatment to pretreat the banana hemp during the preparation of the banana fiber, and other parameters and methods are completely consistent with those of the example 1.
Control group 4:
in the control group, the banana hemp is pretreated without using biological enzyme treatment in the process of preparing the banana fiber, and other parameters and methods are completely consistent with those of the embodiment 1.
Control group 5:
the control group does not use tea seed oil to pretreat the banana fiber in the process of preparing the banana fiber, and other parameters and methods are completely consistent with those of the embodiment 1.
Control group 6:
other parameters and methods of the control group are completely consistent with those of example 1, but only the banana fiber, polylactic acid and cellulose binary system fiber dissolving solution is used for preparing the banana fiber-based plastic to prepare the nanofiber film.
Control group 7:
other parameters and methods of the control group are completely consistent with those of example 1, but only banana fiber, cedar wood chips, polylactic acid and cellulose binary system fiber solution is used for preparing banana fiber-based plastic to prepare the nanofiber film.
Control group 8:
other parameters and methods of the control group are completely consistent with those of example 1, but only the banana fiber, chitosan, polylactic acid and cellulose binary system fiber dissolving solution is used for preparing the banana fiber-based plastic for preparing the nanofiber film.
Control group 9:
the control group only uses the cedar chips, the chitosan, the polylactic acid and the cellulose binary system fiber solution to prepare the fiber-based plastic to prepare the nanofiber film, does not use the banana fiber, does not need the step of preparing the banana fiber, and has other parameters and methods completely consistent with those of the embodiment 1.
Test run 1:
the content of each component of the hemp crude after pretreatment in all the examples 1 to 6 and the comparative groups 1 to 9 of the present application is shown in table 1:
table 1 units: is based on
Group of Grease wax Hemicellulose Pectin Water soluble substance Lignin Cellulose, process for producing the same, and process for producing the same Gel content
Example 1 1.55 24.36 1.23 5.46 15.26 53.26 38.06
Example 2 1.64 26.31 1.3 5.61 15.36 53.47 37.58
Example 3 1.68 25.75 1.25 5.58 15.67 54.69 37.69
Example 4 1.61 24.42 1.29 5.52 15.32 53.32 38.12
Example 5 1.66 26.33 1.32 5.63 15.38 53.49 37.60
Example 6 1.62 25.69 1.19 5.52 15.61 54.63 37.63
Control group 1 1.56 25.69 1.26 5.59 15.78 55.16 37.94
Control group 2 1.57 25.46 1.06 6.03 15.69 52.03 37.49
Control group 3 1.61 25.77 1.09 5.74 15.83 51.26 37.92
Control group 4 1.63 24.87 1.15 5.84 15.67 53.26 36.97
Control group 5 1.59 25.97 1.16 5.86 15.09 51.36 36.89
Control group 6 1.62 25.75 1.20 5.65 15.84 55.22 37.88
Control group 7 1.51 25.4 1.05 5.97 15.63 51.97 37.43
Control group 8 1.67 25.83 1.15 5.80 15.89 51.32 37.98
Control group 9 1.58 24.82 1.10 5.79 15.62 53.21 36.92
As can be seen from the above table, after pretreatment of the stems, stalks and leaves of bananas in examples 1 to 6 and control groups 1 to 5, the contents of lipo-waxes, hemicellulose, pectin, water-soluble substances, lignin, cellulose and gum content of examples 1 to 6 and control groups 1 to 5 are substantially the same.
Test run 2:
the single films of examples 1 to 6 and control groups 1 to 5 were tested for residual gum rate, residual lignin; the average fiber thickness of the nanofiber film was observed and calculated under an electron microscope, and the test results for determining the strength of the nanofiber film are shown in table 2:
TABLE 2
Figure GDA0002736500390000131
Figure GDA0002736500390000141
As can be seen from the above table, the residual gum rate and the residual lignin content of examples 1 to 6 are lower than those of control groups 1 to 4, and are equivalent to those of control groups 5 to 9; the degumming treatment is carried out by the steps of puffing treatment, oxidation treatment, acid treatment and biological enzyme, the residual gum rate and the residual lignin content of the fiber can be effectively reduced, and the residual gum rate and the residual lignin content of the banana fiber cannot be influenced by the oil feeding treatment of the tea seed oil; the average thickness of the examples 1-6 is smaller than that of the control group 1-4, and is even smaller than that of the control group 5, which shows that the degumming treatment of the steps of the expanding treatment, the oxidation treatment, the acid treatment and the biological enzyme in the pretreatment process can effectively reduce the thickness of the nanofiber membrane, and the oil supply of the tea seed oil is more beneficial to producing thinner nanofiber membrane materials; the average thickness of examples 1-6 is substantially the same as that of control 6-8, and is smaller than that of control 9, which shows that the processing of nanofiber films using the banana fiber of the present application is more beneficial to producing thinner nanofibers, and the nanofiber films with improved fineness can be smoother; the film strength of the examples 1-6 is higher than that of the control group 1-4, the film strength of the control group 1-4 is higher than that of the control group 5-8, and the film strength of the control group 5-8 is higher than that of the control group 9, which shows that the degumming treatment of the banana fiber by the steps of the puffing treatment, the oxidation treatment, the acid treatment, the biological enzyme and the tea seed oil oiling can improve the strength of the banana fiber, and the strength of the nanofiber film can be effectively improved by adding the banana fiber when the nanofiber film is prepared.
Test run 3:
the films of example 1 and the control groups 6-9 are subjected to multilayer superposition, polylactic acid smearing and compaction to prepare the preservative film with the thickness of 0.01mm, the control group adopts a commercial PVC preservative film, and the O permeability of the preservative film is tested2Rate, permeability to CO2The rate, the elongation at break, the tensile strength and the anthracnose pathogen inhibition rate are tested, and the degradation capability and the degradation energy of the preservative film are testedThe force was measured by taking 100cm2The plastic wrap bury in the soil horizon that soil horizon thickness is 10cm, observe the decomposition condition of plastic wrap every day, all test the effective viable count content in soil horizon after the complete decomposition, the decomposition time behind the plastic wrap landfill soil, the concrete conditions see table 4:
TABLE 4
Figure GDA0002736500390000151
As can be seen from the above table, the Per-O in example 12Rate, permeability to CO2The rate is higher than that of the control group 9, which shows that the banana fiber of the application can improve the O penetration of the film2Rate and CO Permeability2Rate, Per O of example 12Rate, permeability to CO2The rate is higher than that of a control group, which shows that the nanofiber film of the application is more permeable to O than the conventional PVC preservative film2Rate, permeability to CO2The rate is higher; the elongation at break and the tensile strength of the preservative film produced by the production method are not greatly different from those of a contrast group, which shows that the difference between the film strength and the elongation of the preservative film produced by the production method is not large as that of a commercial PVC preservative film; the elongation at break and the tensile strength of the film in example 1 are obviously higher than those of the control groups 6-9, which shows that the elongation at break and the tensile strength of the film can be improved by preparing fiber-based plastics from banana fibers, China fir chips, polylactic acid, chitosan and binary system fibers; example 1 shows that the decomposition time of the preservative film is equivalent to that of the preservative films of the comparison groups 6-9, but the preservative films of the comparison groups are not decomposed, which shows that the preservative films produced by the method can be effectively decomposed, and the method is used for preparing fiber-based plastic raw materials: the banana fiber, the cedar wood chips, the polylactic acid and the chitosan all have soil decomposition capacity, the effective viable count of the soil is increased after the preservative films of the embodiment 1 and the comparison groups 6-9 are decomposed, and the effective viable count of the soil of the comparison group is not increased or decreased, which shows that the preservative film produced by the application can be effectively decomposed by microorganisms in the soil, and the soil microorganisms can not decompose the preservative film made of PVC materials.
Test run 4:
the films of example 1 and control 6-9 were laminated, polylactic acid coated, and compactedPreparing a mulching film with the thickness of 0.05mm, adopting a commercial PVC mulching film as a control group, and testing the light transmittance, the water absorption and the O permeability of the mulching film2Rate, permeability to CO2The rate, the elongation at break and the tensile strength are measured, the degradation capability of the preservative film is measured, and the degradation capability measuring method is that 100cm is taken2The plastic film bury in the soil horizon thickness is 10 cm's soil horizon, observe the decomposition condition of plastic film daily, all test the effective viable count content in soil horizon after decomposing completely, the plastic film buries the decomposition time behind the soil, and the concrete conditions see table 5:
TABLE 5
Figure GDA0002736500390000161
As can be seen from the table, the light transmittance and the water absorption of example 1 are greater than those of the control group, which indicates that the light transmittance and the water absorption of the mulching film produced by using the film of the present application can be effectively improved; permeability of example 12Rate, permeability to CO2The rate is higher than that of the control group 9, which shows that the banana fiber of the application can improve the O penetration of the film2Rate and CO Permeability2Rate, Per O of example 12Rate, permeability to CO2The rate is higher than that of a control group, which shows that the nanofiber membrane of the application has O permeation compared with the conventional PVC membrane2Rate, permeability to CO2The rate is higher; the elongation at break and tensile strength of the film produced in the embodiment 1 are not greatly different from those of the control group, which shows that the film produced by the production method of the application has the film strength and elongation which are not greatly different from those of the commercial PVC film; the elongation at break and the tensile strength of the film in example 1 are obviously higher than those of the control groups 6-9, which shows that the elongation at break and the tensile strength of the film can be improved by preparing fiber-based plastics from banana fibers, China fir chips, polylactic acid, chitosan and binary system fibers; example 1 shows that the decomposition time of the mulching films of the comparison groups 6-9 is equivalent, but the mulching films of the comparison groups are not decomposed, which shows that the mulching films produced by the method can be effectively decomposed, and the fiber-based plastic raw materials used by the application are prepared as follows: the banana fiber, the cedar wood chips, the polylactic acid and the chitosan all have soil decomposition capability, and the effective viable count of the soil is increased after the mulching films of the example 1 and the control groups 6-9 are decomposed, namelyObviously, the mulching film produced by the method can be effectively decomposed by microorganisms in soil, and the soil microorganisms cannot decompose the mulching film made of the PVC material.
In conclusion, the banana nanofiber film provided by the invention has the advantages that impurities such as pectin and lignin are effectively removed according to the characteristic of abundant pectin and lignin in banana waste, the fiber content of the nanofiber film is increased, and the toughness of the nanofiber film is improved2High efficiency and CO permeability2The nano-fiber film has high rate, strong toughness and high film strength, can be decomposed by soil, and has wider application field.
The above examples are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.

Claims (6)

1. A preparation method for preparing a film material by using banana nanofibers is characterized by comprising the following steps of:
preparing banana fiber:
(1) pretreatment of raw materials: cutting banana peel, leaf or stem into sections, then breaking and tearing into slices with the thickness of 0.5-2 mm, squeezing, scraping impurities and drying to obtain rough ramie;
(2) degumming treatment: sequentially carrying out puffing treatment, oxidation treatment, acid treatment, biological enzyme treatment, enzyme inactivation treatment, dehydration, oil feeding and drying on the coarse ramie obtained in the step (1) to obtain coarse fibers;
the processing method of the puffing treatment comprises the following steps: mixing crude hemp with a sodium hydroxide solution with the mass concentration of 2g/L-4g/L according to the solid-liquid mass ratio of 1:17-22, quickly heating to 95-100 ℃, decocting at constant temperature for 20min-30min, draining the sodium hydroxide solution, fishing out the crude hemp, putting the crude hemp into hot water with the pressure condition of 7MPa-8MPa and the temperature of 90-95 ℃ for 10min-15min, draining the hot water, putting the crude hemp into cold water with the pressure condition of 2MPa-3MPa and the temperature of 0-5 ℃ for 10min-15min, filtering and airing to finish the bulking treatment process;
the treatment method of the oxidation treatment comprises the following steps: mixing the bulked crude ramie with an oxidant solution according to a solid-liquid mass ratio of 1:20-25, then rapidly heating to 95-100 ℃, decocting at a constant temperature for 15-20 min, draining the oxidant solution, putting the crude ramie into hot water at a temperature of 90-95 ℃, keeping the constant temperature for 5-10 min, then putting the crude ramie into cold water at a temperature of 0-5 ℃, keeping the constant temperature for 5-10 min, filtering, and airing to finish the oxidation treatment process;
the acid treatment method comprises the following steps: mixing the oxidized crude ramie with a sulfuric acid solution with the mass concentration of 1g/L-3g/L according to the solid-liquid mass ratio of 1:15-20, then rapidly heating to 95-100 ℃, decocting at constant temperature for 15min-20min, taking out the crude ramie, putting the crude ramie into hot water with the temperature of 90-95 ℃ for washing for 5min, then putting the crude ramie into cold water with the temperature of 0-5 ℃ for washing for 10min, and then airing to finish the acid treatment process;
the treatment method of the biological enzyme treatment comprises the following steps: mixing the acid-treated crude ramie with a biological enzyme solution according to a solid-liquid mass ratio of 1:18-23, keeping the temperature at 30-40 ℃ for 20-25 min, taking out the crude ramie, and putting the crude ramie into cold water at 0-5 ℃ for washing for 10 min; finishing the biological enzyme treatment process;
the treatment method of the enzyme inactivation treatment comprises the following steps: putting the crude ramie treated by the biological enzyme into hot water with the temperature of 85-90 ℃, and decocting for 30-35 min at constant temperature; completing the enzyme inactivation treatment process;
the dehydration treatment method comprises the following steps: putting the enzyme-inactivated crude ramie into a vacuum diatomite filter press with the vacuum degree of 0.01MPa-0.1MPa for vacuum filter pressing to complete the dehydration treatment process;
the oil feeding treatment method comprises the following steps: uniformly spraying a layer of tea seed oil on the dehydrated rough ramie to finish the oil feeding treatment process;
the drying treatment method comprises the following steps: placing the oiled crude ramie into a hot air dryer at the temperature of 50-60 ℃ to dry the crude ramie until the water content of the crude ramie is 3-5% to obtain banana fiber;
(II) preparing a nanofiber film:
(3) preparing a precursor solution: mixing the banana fiber, the cedar chips, the polylactic acid, the chitosan and the cellulose binary system fiber solution obtained in the step (2) according to the mass ratio of 10-13:1:4-7:1-2:10-15 to obtain banana fiber-based plastic; stirring and mixing tin chloride and ethylene glycol according to the mass ratio of 1:3-8 to obtain a tin precursor solution;
(4) preparing a spinning solution: dropwise adding the tin precursor solution obtained in the step (3) into the banana fiber-based plastic, continuously stirring, then adding solid phosphorus pentoxide and boric acid into the mixed solution of the tin precursor and the banana fiber-based plastic, and fully stirring to obtain a spinning solution; the mass ratio of the tin precursor to the banana fiber-based plastic is 1: 6-9;
(5) preparing a nanofiber film: and (3) mixing the spinning solution obtained in the step (4), the aloe extract, the chitosan and the spinning solution according to the mass ratio of 4-7:1-3:1, mixing, removing bubbles by using ultrasound, processing the mixture into a fiber membrane by using a high-voltage electrostatic spinning machine, and pre-oxidizing and carbonizing the fiber membrane to obtain a banana nanofiber film;
the oxidant solution in the step (2) is prepared by mixing hydrogen peroxide, methyl orange, salix populi extract and water according to the mass ratio of 3-5:1-3:6-9: 30-35;
the biological enzyme solution in the step (2) is prepared by mixing pectinase, hemicellulase, lignin degrading enzyme, barbaloin and water according to the mass ratio of 2-4:2-4:1-3:5-9: 30-35;
the cellulose binary system in the step (3) comprises a lithium chloride/dimethylacetamide system or an ammonia/ammonium thiocyanate system.
2. The preparation method according to claim 1, wherein the lithium chloride/dimethylacetamide system is prepared by mixing lithium chloride, dimethylacetamide and water in a mass ratio of 4-6:1: 10-15.
3. The method according to claim 1, wherein the ammonia/ammonium thiocyanate system is prepared by mixing ammonium thiocyanate, ammonia and water in a mass ratio of 65-75:25-30: 1.
4. The production method according to claim 1, wherein the phosphorus pentoxide of step (4) is added in an amount of 1g/L to 3 g/L; the addition amount of boric acid is 0.5g/L-2 g/L.
5. The preparation method according to claim 1, wherein the process conditions of the high-voltage electrostatic spinning machine are as follows: the spinning voltage is 15kV-25kV, the flow rate of the spinning solution is 0.5-1mL/h, the rotating speed is 4000r/min-5000r/min, the relative humidity is 30% -40%, the spinning time is 4h-6h, and the spinning solution is received by a roller.
6. The method of claim 1, wherein the pre-oxidation is performed by: placing the fiber membrane in hot air with the pre-oxidation temperature of 250-300 ℃, and preserving heat for 3-5 h to complete the pre-oxidation process; the carbonization method comprises the following steps: and (3) placing the pre-oxidized fiber membrane in a carbonization furnace, heating at the speed of 4-6 ℃/min until the temperature is raised to 700-750 ℃, preserving the heat for 2-3 h at the temperature, then cooling at the speed of 4-6 ℃/min, and finishing the carbonization process when the temperature is reduced to room temperature.
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