CN109354722A - A kind of preparation method of modified nanometer cellulose enhancing thermoplastic starch food package film - Google Patents
A kind of preparation method of modified nanometer cellulose enhancing thermoplastic starch food package film Download PDFInfo
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- CN109354722A CN109354722A CN201811355227.2A CN201811355227A CN109354722A CN 109354722 A CN109354722 A CN 109354722A CN 201811355227 A CN201811355227 A CN 201811355227A CN 109354722 A CN109354722 A CN 109354722A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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Abstract
The invention discloses a kind of preparation methods of modified nanometer cellulose enhancing starch composite food package film, belong to composite food package thin film preparation process technology, the present invention is that raw material prepares nano-cellulose using manioc waste, and food level soybean oil is that esterifying agent carries out hydrophobically modified to nano-cellulose；It the use of tapioca is substrate, glycerol adds modified nano-cellulose as reinforcing agent, prepare starch-based food packaging film by casting filming therapy as plasticiser.Modified nanometer cellulose enhancing thermoplastic starch composite food package film prepared by the present invention has cheap, high production efficiency, it is functional, the advantages of green environmental protection degradable, and modified nanometer cellulose enhancing thermoplastic starch film substantially improves the deficiency that starch film intensity is low, hygroscopic, avoids the pollution of non-degradable On Environment of Food Package.
Description
Technical field
The invention belongs to Food Packaging technology field, in particular to a kind of modified nanometer cellulose enhances starch complex food
The preparation method of packaging film.
Background technique
Due to the complicated particularity of problem of environmental pollution, undesirable packaging material not only endangers human survival, Community health,
The market boom is also influenced simultaneously, researcher has been devoted to find a kind of recyclable packaging material of green non-pollution.Starch
It is that a kind of source is wide, price is low, raw material that can be degradable, uses starch as raw material, petroleum base packing timber can be greatly reduced
Expect bring problem of environmental pollution, and can be with save the cost.But thermoplastic starch has strongly hydrophilic, therefore thermoplastic starch
Powder material poor water resistance is easy the moisture absorption, and ambient humidity is affected to the properties of material, limits thermoplastic starch film
It is widely applied.
Contain a large amount of cellulose and starch in manioc waste, but this part resource advantage does not obtain adequately developing benefit
With.Wherein cellulose is to pass through linear polymer made of β-Isosorbide-5-Nitrae glucosides key connection, cellulose day as glucose unit
Right reticular structure makes cellulose have stronger mechanical property, and in fiber cellulose reinforced plastic, cellulose enhances starch etc.
With more application research.Since a large amount of easily hydrophilic hydroxyls are contained on cellulose grain surface, it is easy between cellulose fine particle
Reunited by the interaction of hydrogen bond, therefore limits its application.At present to the method for cellulose surface chemical modification
There are sulfonation, esterification, etherificate, graft copolymerization, crosslinking etc..Wherein fatty acid and stearic acid are answered when carrying out esterification modification to cellulose
With more esterifying agent, esterifying agent is reacted with the hydroxyl of nano-cellulose, and hydrophobic grouping is introduced on cellulosic molecule, from
And the hydrophily of nano-cellulose can be improved.
Composite material is prepared using modified cellulose enhancing thermoplastic starch, the mechanics of starch membrane material can be greatly improved
Performance and hydrophobicity, cellulose is similar with starch molecular structure to have good compatibility.And there has been no utilize food at present
Grade modifying agent is modified nano-cellulose, and is added in starch the relevant report for preparing composite food package film.
Summary of the invention
The object of the present invention is to provide a kind of modified nanometer cellulose enhancing starch composite food package film preparation method,
Tapioca is substrate, and glycerol is as plasticizer, and manioc waste modified nanometer cellulose is as reinforcing agent, prepared complex food
Packaging film have function admirable, it is green safe can be degradable, meet the performance requirement of environmentally friendly packing material.
The present invention solves the above problems by using following technical solution: the composite food package film according to following components and
It is prepared by the weight percent of film shared by each component:
Tapioca 65~80%
Plasticizer 19~32%
Reinforcing agent 1~3%
Above-mentioned plasticizer be glycerol or epoxidized soybean oil,
Above-mentioned reinforcing agent is modified nanometer cellulose,
Above-mentioned modified nanometer cellulose, the preparation method comprises the following steps:
(1) distilled water is added with 1:10 ratio in manioc waste to boil, is gelatinized starch sufficiently, is cooled to 60 DEG C；Manioc waste is added
The alphalise starch enzyme solution of the 10-20% of quality, 45 DEG C of ultrasonic treatment 40-60min of 100W；100 DEG C of enzyme deactivation 5-10min are heated to, are taken
40-50 times of manioc waste quality distills the supreme layer aqueous solution of water washing for clarification, and 80 DEG C drying to constant weight, is sealed spare；
(2) step (1) is taken treated manioc waste, the NaOH solution of 5-10%, 60- are added according to the ratio of solid-liquid ratio 1:10
80 DEG C of alkaline hydrolysis 80-120min take 40-50 times of manioc waste quality to distill water washing to neutrality, and 80 DEG C drying to constant weight, sealing
It saves backup；
(3) manioc waste dried in step (2) is taken, the sulfuric acid solution mixing of 60-65% is added with 1:20 solid-liquid ratio.It will mixing
Solution is fitted into high speed disperser (setting revolving speed 2000-5000r/min), and 100-150min is stirred at room temperature.Stirring terminates
Afterwards, 40-50 times of distilled water centrifuge washing 2-3 times rear vacuum freeze drying 40-60h of manioc waste quality is taken, obtained manioc waste is received
Rice cellulose；
(4) the soybean oil ethanol solution that soybean oil concentration is 3-8wt% is prepared, is 60-80 DEG C of heating water bath 2-5min in temperature；
(5) nano-cellulose made from step (3) is taken, the soybean oil ethyl alcohol that step (4) preparation is added in solid-liquid ratio 1:4 ratio is molten
Liquid, 480W ultrasound 5-10min；
(6) 100-120 DEG C of oil bath heating 1-2h, dehydrated alcohol centrifuge washing 2-3 times, spontaneously dries at room temperature, is sealed, i.e.,
Modified nanometer cellulose is made.
Above-mentioned composite food package film the preparation method comprises the following steps:
(1) starch is added to the water in the ratio of solid-liquid ratio 1:20, after being sufficiently gelatinized at 85-95 DEG C, plasticizer is added, continues
Stir 20-30min；
(2) plasticizer modified nanometer cellulose is added in the water of 10-30 times of quality, 480W room temperature ultrasound 20-50min is added
Continue that 20-40min is mixed into the starch solution of step (1), so that film liquid be made into.In whipping process, sealing is paid attention to
To prevent the loss of moisture in heating process；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 45-65 DEG C.
Composite food package film prepared by the present invention has a characteristic that
(1) primary raw material, plasticizer, the reinforcing agent etc. used in the present invention are natural reproducible resource, and source is wide, price
It is cheap；
(2) composite food package film prepared by the present invention can be degradable, green non-pollution；
(3) composite food package film prepared by the present invention is nontoxic, can be used for food packaging, has edibility；
(4) enhancing of the composite food package film prepared by the present invention by nano-cellulose, the tensile strength compared with pure starch film
50-75% can be improved, 50-70% can be improved in elasticity modulus, and light transmittance reaches 50-85%, moisture-vapor transmission 0.3-0.4
×10-11g·cm/cm2SPa has good mechanical strength, flexibility, transparency and barrier property.It can make according to demand
The packaging film of standby different mechanical strengths, the packaging suitable for different food products such as candy, cake, instant noodles；
(5) composite food package film simple process prepared by the present invention, production cost is low, good market prospect.
Detailed description of the invention
Fig. 1 is the preparation flow of composite food package film prepared by the present invention.Manioc waste is received by enzymatic hydrolysis and acidolysis processing
Rice cellulose, then obtains modified nanometer cellulose with soybean oil modified, afterwards with thermoplastic wood sweet potato starch casting film-forming, is prepared into
To composite food package film.
Specific embodiment
The technical solution of patent in order to better understand the present invention, is described in detail below with reference to example, but this is not
It limits the scope of the invention.
Embodiment one:
The preparation of reinforcing agent:
(1) it takes and 500g boiling boiling is added in 50g manioc waste, be gelatinized starch sufficiently, be cooled to 60 DEG C；Manioc waste quality is added
The alphalise starch enzyme solution of 7.5g, 45 DEG C of ultrasonic treatment 45min of 100W；100 DEG C of enzyme deactivation 5min are heated to, 2000ml distillation washing is taken
Washing to upper layer aqueous solution is clarification, and 80 DEG C drying to constant weight, is sealed spare；
(2) step (1) is taken treated manioc waste, 7% NaOH solution, 70 DEG C of alkali are added according to the ratio of solid-liquid ratio 1:10
90min is solved, 2000ml distills water washing to neutrality, and 80 DEG C drying to constant weight, is sealed spare；
(3) manioc waste dried in step (2) is taken, 63% sulfuric acid solution mixing is added with 1:20 solid-liquid ratio.By mixed solution
It is fitted into high speed disperser (setting revolving speed 4500r/min), 120min is stirred at room temperature.After stirring, 2000ml distillation
Vacuum freeze drying 48h after water centrifuge washing 2-3 times, is made manioc waste nano-cellulose；
(4) the soybean oil ethanol solution that soybean oil concentration is 5wt% is prepared, is 70 DEG C of heating water bath 2min in temperature；
(5) nano-cellulose made from appropriate step (3) is taken, the soybean oil second of step (4) preparation is added in solid-liquid ratio 1:4 ratio
Alcoholic solution, 480W ultrasound 5min；
(6) 110 DEG C of oil bath heating 1h, dehydrated alcohol centrifuge washing 2-3 times are spontaneously dried at room temperature, are sealed, obtain and change
Property nano-cellulose.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 95 DEG C, 7.5g glycerol is added, persistently stirs 20min；
(2) 0.75g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 30min, is added to the starch of step (1)
Stirring 30min is continuesd to mix in solution at 95 DEG C, film liquid is made into.In whipping process, pay attention to sealing to prevent in heating process
The loss of moisture；；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 50 DEG C.
Embodiment two:
The preparation of reinforcing agent: its method is identical as the method that embodiment one uses.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 85 DEG C, 6.32g glycerol is added, persistently stirs 20min；
(2) 0.33g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 30min, is added to the starch of step (1)
Stirring 30min is continuesd to mix in solution at 95 DEG C, film liquid is made into.In whipping process, pay attention to sealing to prevent in heating process
The loss of moisture；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 45 DEG C.
Embodiment three:
The preparation of reinforcing agent: its method is identical as the method that embodiment one uses.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 95 DEG C, 10.64g glycerol is added, persistently stirs 30min；
(2) 1.0g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 50min, is added to the starch of step (1)
Stirring 40min is continuesd to mix in solution at 95 DEG C, film liquid is made into.In whipping process, pay attention to sealing to prevent in heating process
The loss of moisture；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 65 DEG C.
Example IV:
The preparation of reinforcing agent: its method is identical as the method that embodiment one uses.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 95 DEG C, 7.5g epoxidized soybean oil is added, it is lasting to stir
20min；
(2) 0.75g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 30min, is added to the starch of step (1)
Stirring 30min is continuesd to mix in solution at 95 DEG C, film liquid is made into.In whipping process, pay attention to sealing to prevent in heating process
The loss of moisture；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 50 DEG C.
Embodiment five:
The preparation of reinforcing agent:
(1) it takes and 500g boiling boiling is added in 50g manioc waste, be gelatinized starch sufficiently, be cooled to 60 DEG C；Manioc waste quality is added
The alphalise starch enzyme solution of 5.0g, 45 DEG C of ultrasonic treatment 40min of 100W；It is heated to 100 DEG C of enzyme deactivations 5min, 2500ml and distills water washing
It is clarification to upper layer aqueous solution, 80 DEG C drying to constant weight, is sealed spare；
(2) step (1) is taken treated manioc waste, 5% NaOH solution, 80 DEG C of alkali are added according to the ratio of solid-liquid ratio 1:10
120min is solved, 2500ml distills water washing to neutrality, and 80 DEG C drying to constant weight, is sealed spare；
(3) manioc waste dried in step (2) is taken, 60% sulfuric acid solution mixing is added with 1:20 solid-liquid ratio.By mixed solution
It is fitted into high speed disperser (setting revolving speed 5000r/min), 100min is stirred at room temperature.After stirring, 2500ml distillation
Vacuum freeze drying 40h after water centrifuge washing 2-3 times, is made manioc waste nano-cellulose；
(4) the soybean oil ethanol solution that soybean oil concentration is 3wt% is prepared, is 60 DEG C of heating water bath 5min in temperature；
(5) nano-cellulose made from appropriate step (3) is taken, the soybean oil second of step (4) preparation is added in solid-liquid ratio 1:4 ratio
Alcoholic solution, 480W ultrasound 5min；
(6) 100 DEG C of oil bath heating 2h, dehydrated alcohol centrifuge washing 2-3 times are spontaneously dried at room temperature, are sealed, obtain and change
Property nano-cellulose.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 95 DEG C, 7.5 glycerol is added, persistently stir 20min；
(2) 0.75g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 30min, is added to the starch of step (1)
Stirring 30min is continuesd to mix in solution at 95 DEG C, so that film liquid be made into.In whipping process, notice that sealing is heated to prevent
The loss of moisture in journey；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 50 DEG C.
Embodiment six:
The preparation of reinforcing agent: its method is identical as the method that embodiment five uses.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 85 DEG C, 6.3g glycerol is added, persistently stirs 20min；
(2) 0.33g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 30min, is added to the starch of step (1)
Stirring 30min is continuesd to mix in solution at 95 DEG C, so that film liquid be made into.In whipping process, notice that sealing is heated to prevent
The loss of moisture in journey；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 45 DEG C.
Embodiment seven:
The preparation of reinforcing agent:
(1) it takes and 500g boiling boiling is added in 50g manioc waste, be gelatinized starch sufficiently, be cooled to 60 DEG C；Manioc waste quality is added
The alphalise starch enzyme solution of 10g, 45 DEG C of ultrasonic treatment 60min of 100W；It is heated to 100 DEG C of enzyme deactivations 10min, 2500ml and distills water washing
It is clarification to upper layer aqueous solution, 80 DEG C drying to constant weight, is sealed spare；
(2) step (1) is taken treated manioc waste, 10% NaOH solution, 60 DEG C of alkali are added according to the ratio of solid-liquid ratio 1:10
80min is solved, 2500ml distills water washing to neutrality, and 80 DEG C drying to constant weight, is sealed spare；
(3) manioc waste dried in step (2) is taken, 65% sulfuric acid solution mixing is added with 1:20 solid-liquid ratio.By mixed solution
It is fitted into high speed disperser (setting revolving speed 2000r/min), 150min is stirred at room temperature.After stirring, 2500ml distillation
Vacuum freeze drying 60h after water centrifuge washing 2-3 times, is made manioc waste nano-cellulose；
(4) the soybean oil ethanol solution that soybean oil concentration is 8wt% is prepared, is 80 DEG C of heating water bath 2min in temperature；
(5) nano-cellulose made from appropriate step (3) is taken, the soybean oil second of step (4) preparation is added in solid-liquid ratio 1:4 ratio
Alcoholic solution, 480W ultrasound 10min；
(6) 120 DEG C of oil bath heating 1h, dehydrated alcohol centrifuge washing 2-3 times are spontaneously dried at room temperature, are sealed, obtain and change
Property nano-cellulose.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 95 DEG C, 7.5 glycerol is added, persistently stir 20min；
(2) 0.75g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 30min, is added to the starch of step (1)
Stirring 30min is continuesd to mix in solution at 95 DEG C, so that film liquid be made into.In whipping process, notice that sealing is heated to prevent
The loss of moisture in journey；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 50 DEG C.
Embodiment eight:
The preparation of reinforcing agent: its method is identical as the method that embodiment seven uses.
The preparation of composite food package film:
(1) 25g starch is taken, 500g water is added, after being sufficiently gelatinized at 95 DEG C, 10.5 g glycerol is added, persistently stir 30min；
(2) 1.0g modified nanometer cellulose is added in 10g water, 480W room temperature ultrasound 50min, is added to the starch of step (1)
Stirring 40min is continuesd to mix in solution at 95 DEG C, so that film liquid be made into.In whipping process, notice that sealing is heated to prevent
The loss of moisture in journey；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 65 DEG C.
The above content is it cannot be assumed that present invention specific implementation is only limited to these instructions, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
It is as shown in table 1 to the properties test result of the film of example 1-8 preparation:
Claims (4)
1. a kind of preparation method of modified nanometer cellulose enhancing starch composite food package film, it is characterised in that its component and each
The percentage of film weight shared by component are as follows:
Tapioca 65~80%
Plasticizer 19~32%
Reinforcing agent 1~3%.
2. composite food package film according to claim 1, which is characterized in that the plasticizer is glycerol or epoxy soybean
Oil.
3. composite food package film according to claim 1, which is characterized in that the reinforcing agent is modified manioc waste nanometer
Cellulose, preparation step are as follows:
(1) distilled water is added with 1:10 ratio in manioc waste to boil, is gelatinized starch sufficiently, is cooled to 60 DEG C；Manioc waste is added
The alphalise starch enzyme solution of the 10-20% of quality, 45 DEG C of ultrasonic treatment 40-60min of 100W；100 DEG C of enzyme deactivation 5-10min are heated to, are taken
40-50 times of manioc waste quality distills the supreme layer aqueous solution of water washing for clarification, and 80 DEG C drying to constant weight, is sealed spare；
(2) step (1) is taken treated manioc waste, the NaOH solution of 5-10%, 60- are added according to the ratio of solid-liquid ratio 1:10
80 DEG C of alkaline hydrolysis 80-120min, taking 40-50 times of manioc waste quality to distill water washing, drying to constant weight to neutral pH=7,80 DEG C,
It is sealed spare；
(3) manioc waste dried in step (2) is taken, the sulfuric acid solution mixing of 60-65% is added with 1:20 solid-liquid ratio, will mix
Solution is fitted into high speed disperser (setting revolving speed 2000-5000r/min), 100-150min is stirred at room temperature, stirring terminates
Afterwards, 40-50 times of distilled water centrifuge washing 2-3 times rear vacuum freeze drying 40-60h of manioc waste quality is taken, obtained manioc waste is received
Rice cellulose；
(4) the soybean oil ethanol solution that soybean oil concentration is 3-8wt% is prepared, is 60-80 DEG C of heating water bath 2-5min in temperature；
(5) nano-cellulose made from step (3) is taken, the soybean oil ethyl alcohol that step (4) preparation is added in solid-liquid ratio 1:4 ratio is molten
Liquid, 480W ultrasound 5-10min；
(6) 100-120 DEG C of oil bath heating 1-2h, dehydrated alcohol centrifuge washing 2-3 times, spontaneously dries at room temperature, is sealed, i.e.,
Modified manioc waste nano-cellulose is made.
4. composite food package film according to claim 1, which is characterized in that its preparation step is as follows:
(1) starch is added to the water in the ratio of solid-liquid ratio 1:20, after being sufficiently gelatinized at 85-95 DEG C, plasticizer is added, continues
Stir 20-30min；
(2) plasticizer modified nanometer cellulose is added in the water of 10-30 times of quality, 480W room temperature ultrasound 20-50min is added
Continue that 20-40min is mixed into the starch solution of step (1), so that film liquid be made into, in whipping process, pays attention to sealing
To prevent the loss of moisture in heating process；
(3) film liquid of preparation is cast on organic glass, film forming is dried at 45-65 DEG C.
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Cited By (5)
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| CN109749108A (en) * | 2019-02-28 | 2019-05-14 | 华南理工大学 | A kind of edible tapioca composite package film and its preparation method and application |
| CN110306291A (en) * | 2019-07-24 | 2019-10-08 | 李光宽 | A kind of antibacterial green edible food package film and preparation method thereof |
| CN110396768A (en) * | 2019-07-23 | 2019-11-01 | 李光宽 | A kind of food packaging digestion resistant modified PE film and preparation method thereof |
| CN111320774A (en) * | 2020-04-17 | 2020-06-23 | 武汉轻工大学 | Preparation method of starch composite membrane |
| CN113817194A (en) * | 2021-10-29 | 2021-12-21 | 江南大学 | Hydrophobic thermoplastic degradable microcrystalline cellulose/starch film and preparation method thereof |
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