CN110437590A - A kind of starch-base biodegradation food package film and preparation method thereof that composite nano materials are modified - Google Patents

A kind of starch-base biodegradation food package film and preparation method thereof that composite nano materials are modified Download PDF

Info

Publication number
CN110437590A
CN110437590A CN201910664337.5A CN201910664337A CN110437590A CN 110437590 A CN110437590 A CN 110437590A CN 201910664337 A CN201910664337 A CN 201910664337A CN 110437590 A CN110437590 A CN 110437590A
Authority
CN
China
Prior art keywords
starch
composite nano
nano materials
film
food package
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910664337.5A
Other languages
Chinese (zh)
Other versions
CN110437590B (en
Inventor
熊汉国
熊舟翼
王朋凯
陈磊
丁士勇
李艳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong Agricultural University
Original Assignee
Huazhong Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong Agricultural University filed Critical Huazhong Agricultural University
Priority to CN201910664337.5A priority Critical patent/CN110437590B/en
Publication of CN110437590A publication Critical patent/CN110437590A/en
Application granted granted Critical
Publication of CN110437590B publication Critical patent/CN110437590B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • B65D65/466—Bio- or photodegradable packaging materials
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention discloses a kind of modified starch-base biodegradation food package films of composite nano materials, the present invention uses composite nano materials, and it is acted on by physical mechanical by starch micronization, using compound bio sill, the type of raw material and formula are largely optimized simultaneously, the interface compatibility of starch and bio-based materials is improved, so as to improve the tensile strength and elongation at break of film；Starch-base biodegradation food package film is prepared using twin-screw extrusion and film-blowing process, can be carried out in common plastics membrane production equipment, popularization easy to industrialized production.The starch-base biodegradation food package film that the present invention makes, compared with existing biology base packaging film, tensile strength and elongation at break etc. are significantly improved.

Description

A kind of starch-base biodegradation food package film and its system that composite nano materials are modified Preparation Method
Technical field
The invention belongs to packaging material for food technical fields, and in particular to a kind of starch base that composite nano materials are modified is raw Object degradation food package film and preparation method thereof.
Background technique
Currently, a large amount of plastics are used for food packaging.Polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene chloride It (PVDC) is most widely used packaging material for food, this kind of membrane material has the function of that oxygen is prevented to penetrate into, and can reach food The effect of fresh-keeping packaging.However, that there is safeties is bad, environmental performance is poor and to non-renewable petroleum resources for plastic foil The strong serious problem of society today of dependence, has become increasingly limited in food packaging applications.On the one hand, polyvinyl chloride thermostabilization Property and light resistance it is poor, 100 DEG C or more and long-time exposure in sunshine start to decomposite the hydrogen chloride gas being harmful to the human body, meanwhile, Belong to the environmental hormone substance of disturbance endocrine for the plasticizer di adipate (DEHA) etc. in polychloroethylene film, it can be with Induce canceration；On the other hand, plastic foil is discarded is difficult voluntarily to degrade, especially PE film in the natural environment, needs the centuries It can degrade, cause serious " white pollution " to ecological environment；Meanwhile plastics film raw material comes from petroleum, and belong to can not for petroleum Regenerated resources largely will aggravate energy crisis using plastic foil.Therefore, the substitute of plastic foil is found, is studied with natural material Material or biosynthetic dressing be raw material biological based food packaging film, be done step-by-step China's food packaging waste it is pollution-free, Seamless requirement.
Has the report of some biodegradable food package films at present, such as CN105968746A discloses a kind of oxidation stone The Based Full-degradable Plastics Film of black alkene barrier property enhancing, it is by polylactic acid, cornstarch, china-hemp fibers, silane coupling agent kh- 550, the raw materials such as glycerol, epoxychloropropane, polyethylene glycol, montmorillonite, graphene oxide, vinyltriethoxysilane are made, It is hydrophobic to mention by being uniformly dispersed to being added in the mixing of polylactic acid after graphene oxide, montmorillonite progress hydrophobically modified Height greatly improves the barrier property of coating, while also improving the thermal stability of film.CN201810993983.1 is disclosed A kind of controllable starch-base biodegradation agricultural mulching, it is sweet by PBAT+PLA or PBAT+PLA+MTPS or PBAT+PLA+MTPS+ Bagasse cellulose, chain extender, release agent composition.CN201810489943.3 disclose a kind of biology base Biodegradable mulch and its Preparation method, solve the problems, such as existing degradable mulch still rely on petroleum do raw material and degrade it is halfway, with 100 parts by weight Poidometer, contains following substance: 75-98 parts of biological base biodegradation resin, 0.5-5 parts of ultraviolet absorber, 0.5-5 parts Light stabilizer, 0.5-5 parts of antioxidant, 0.5-5 parts of end-capping reagent, 0.5-5 parts of opening agent.CN108440797A is disclosed A method of biodegradable mulch is prepared, includes the following steps: 1) to remove humic acid, the hemicellulose and wooden in biogas residue Element；2) by step 1), treated that biogas residue, starch, plasticizer and water are mixed to get blended liquid；3) blended liquid is successively passed through Homogeneous, gelatinization, emulsification and defoaming, obtain homogenizing fluid；4) homogenizing fluid is formed a film to get the biodegradable mulch.Shen Number a kind of anti-oxidant composite membrane of fish scale gelatin starch edibility please be disclosed for 201410625999.9 Chinese invention patent Preparation method, main component include maize amylose, tea polyphenols and fish scale gelatin.Preparation method are as follows: by fish scale gelatin and Maize amylose is added in green tea polyphenols extract, adds glycerol, is stirred evenly, and is prepared into through the tape casting film forming edible Property inoxidizability composite membrane.Application No. is 201310492147.2 Chinese invention patents to disclose a kind of edibility chitosan- Collagen antibacterial film and preparation method thereof, the film is by chitosan, collagen and dialdehyde starch composition, preparation method are as follows: Collagen is added to the water, heat treatment temperature be 60 DEG C to 70 DEG C under the conditions of stirring and dissolving, be added glycerol dialdehyde starch and Chitosan, the pH value for controlling solution is 5 to 6；Under the conditions of 60 DEG C to 70 DEG C, it is heat-treated 10 to 20 minutes, drying can be obtained Starch film].Application No. is 201410782417.8 Chinese invention patent disclose a kind of Chinese yam starch base edible film and Preparation method is added into the modification Chinese yam starch solution after gelatinization more using Modified by Carboxymethyl Cellulose Chinese yam starch Sugar and gelatin, stir evenly, form a film by the tape casting.
Currently, biomaterial used in the biodegradable food fresh keeping membrane prepared both at home and abroad is mostly hydroaropic substance, Water-proof and oil-proof performances are poor, easy embrittlement, and storage is difficult；Make edible packing membrane higher cost, on the market can not also with it is general Logical plastic food packing film competition；There is no thermoplasticity, film, spray film or casting technique molding (i.e. wet process) can only be used, product is thick Thin and uniformity is difficult to control；Technique is not perfect, and equipment does not match.Therefore, take physics and the green modification technique of chemistry to shallow lake Powder is modified, and improves its Water-proof and oil-proof and mechanical property；Select novel biomaterial and starch progress physical blending realisation Can be complementary, novel nano-material (such as graphene, graphene oxide, nano zine oxide, nano-titanium oxide) is developed to improve height The interface compatibility of Molecularly Imprinted Polymer and starch blending material is formed using film-blowing process, is reduced production cost, is improved film Performance is the direction studied both at home and abroad and development trend.
Summary of the invention
It is an object of the invention to overcome defect of the existing technology, provide a kind of composite nano material (graphene, Nano-TiO2, nanometer Zn o and Nano-meter SiO_22), very fine starch (600-1200 mesh) and compound bio sill (PLA, PBAT and PCL the starch-base biodegradation food package film and preparation method thereof) formed, compared with prior art, which has more Good mechanical strength.
Above-mentioned purpose is achieved through the following technical solutions:
A kind of modified starch-base biodegradation food package film of composite nano materials, it by following portions by weight raw material It is prepared:
100 parts of compound bio sill；
20-50 parts of starch；
2-10 parts of composite nano materials；
1-3 parts of processing aid；
0.2-2 parts of Aluminate；
0.2-0.8 parts of lauryl amine,
The compound bio sill is made of PLA, PBAT and PCL；
The composite nano materials are by graphene, nano-TiO2, nano-ZnO and Nano-meter SiO_22Composition；
The processing aid is made of Ployethylene Wax, stearic acid and paraffin；
Preferably, the weight ratio of PLA, PBAT, PCL three is 1:4:1.
Preferably, the partial size of the composite nano materials is 5-80nm, graphene, nanometer in the composite nano materials TiO2, nano-ZnO, Nano-meter SiO_22Four weight ratio is 0.1:2:1:1.
Preferably, the Ployethylene Wax, stearic acid, paraffin three weight ratio be 1:2:1.
A method of the starch-base biodegradation food package film that the composite nano materials described in preparing are modified, including with Lower step:
1) starch is passed through into air-flow disintegrating machine micronization to 600-1200 mesh, be then placed in high-speed mixer, simultaneously Be added Aluminate 80~100 DEG C stirring 10-30 minutes, obtain be modified very fine starch；
2) composite nano materials and lauryl amine are stirred 10-30 minutes under ultrasonic conditions, fills nanocomposite Dispersion obtains modified composite nano materials；
3) the modification composite nano materials obtained modification very fine starch that step 1) obtains, step 2) and compound life Object sill, processing aid mix 10~30 minutes in high-speed mixer at 70-90 DEG C together, obtain mixed material；
4) mixed material of step 3) is placed in double screw extruder and is squeezed out, it is cooling through mould shape, it draws and cuts Cut, finally on inflation film manufacturing machine blown film to get.
Preferably, each section of the double screw extruder of heating temperature T1-T10 is respectively 80 DEG C, 100 DEG C, 110 DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 150 DEG C and 110 DEG C, engine speed be 15-30 revs/min, material pressure 2.1-3.5MPA； The blown film condition: each section of heating temperature T1-T4 and die head are respectively 120 DEG C, 170 DEG C, 170 DEG C, 160 DEG C and 150 DEG C, traction Speed is 4.3 revs/min, winds 8.15 revs/min.
The beneficial effects of the present invention are:
The present invention uses composite nano materials (graphene: nano-TiO2: nano-ZnO and Nano-meter SiO_22), and pass through physical machine Tool is acted on starch micronization, is largely optimized using compound bio sill, while to the type of raw material and formula, is mentioned The interface compatibility of high starch and bio-based materials prepares starch-base biodegradation food using twin-screw extrusion and film-blowing process Packaging film, so as to improve the tensile strength and elongation at break of film.
The starch-base biodegradation food package film that the present invention makes stretches compared with existing biology base packaging film Intensity and elongation at break etc. significantly improve, and tensile strength increase rate exists in 50-150% or more, elongation at break increase rate 200-500% or more, the present invention can replace the common plastics based food packaging films such as common polythene completely, produce to solve waste plastics Raw " white pollution ", opens up a new way.The present invention also has the characteristics that simple process and low cost simultaneously.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1
A kind of starch-base biodegradation food package film that composite nano materials are modified, it is prepared from the following materials:
The preparation method is as follows:
1) starch is then placed in high-speed mixer by air-flow disintegrating machine micronization to 600 mesh, while aluminium is added Acid esters stirs 10 minutes at 100 DEG C, obtains modified very fine starch；
2) composite nano materials and lauryl amine that partial size is 5-80nm are stirred 10 minutes under ultrasonic conditions, makes nanometer Composite material is fully dispersed, obtains modified composite nano materials；
3) the modification composite nano materials and biology base obtained modification very fine starch that step 1) obtains, step 2) Composite material, processing aid mix 30 minutes in high-speed mixer at 70 DEG C together, obtain mixed material；
4) mixed material of step 3) is placed in double screw extruder and is squeezed out, it is cooling through mould shape, it draws and cuts Cut, finally on inflation film manufacturing machine blown film to get.
The heating temperature T1-T10 of each section of the double screw extruder is respectively 80 DEG C, 100 DEG C, 110 DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 150 DEG C and 110 DEG C, engine speed be 15-30 revs/min, material pressure 2.1-3.5MPA.It is described to blow Film condition: each section of heating temperature T1-T4 and die head are respectively 120 DEG C, 170 DEG C, 170 DEG C, 160 DEG C and 150 DEG C, and hauling speed is 4.3 revs/min, wind 8.15 revs/min.
Embodiment 2
A kind of starch-base biodegradation food package film that composite nano materials are modified, it is prepared by following raw materials:
The preparation method is as follows:
1) starch is passed through into air-flow disintegrating machine micronization to 1200 mesh, is then placed in high-speed mixer, is added simultaneously Aluminate stirs 30 minutes at 80 DEG C, obtains modified very fine starch；
2) composite nano materials and lauryl amine that partial size is 5-80nm are stirred 15 minutes under ultrasonic conditions, makes nanometer Composite material is fully dispersed, obtains modified composite nano materials；
3) the modification composite nano materials obtained modification very fine starch that step 1) obtains, step 2) and compound life Object sill, processing aid mix 10 minutes in high-speed mixer at 90 DEG C together, obtain mixed material；
4) mixed material of step 3) is placed in double screw extruder and is squeezed out, it is cooling through mould shape, it draws and cuts Cut, finally on inflation film manufacturing machine blown film to get.
Embodiment 3
A kind of starch-base biodegradation food package film that composite nano materials are modified, it is prepared by following raw materials:
The preparation method is as follows:
1) starch is passed through into air-flow disintegrating machine micronization to 1000 mesh, is then placed in high-speed mixer, is added simultaneously Aluminate stirs 15 minutes at 90 DEG C, obtains modified very fine starch；
2) composite nano materials and lauryl amine that partial size is 5-80nm are stirred 30 minutes under ultrasonic conditions, makes nanometer Composite material is fully dispersed, obtains modified composite nano materials；
3) the modification composite nano materials and biology base obtained modification very fine starch that step 1) obtains, step 2) Composite material, processing aid mix 15 minutes in high-speed mixer at 80 DEG C together, obtain mixed material；
4) mixed material of step 3) is placed in double screw extruder and is squeezed out, it is cooling through mould shape, it draws and cuts Cut, finally on inflation film manufacturing machine blown film to get.
Comparative example 1
A kind of starch-base biodegradation food package film that composite nano materials are modified, it is prepared by following raw materials:
Preparation method is same as Example 3.
Comparative example 2
A kind of starch-base biodegradation food package film that composite nano materials are modified, it is prepared by following raw materials:
Preparation method is same as Example 3.
Comparative example 3
Starch does not carry out micronization processing, and other steps are same as Example 3.
Comparative example 4
Preparation method is same as Example 3.
1. mechanical strength measures
Detection method: GB/T 1040.1-2006 is referred to.
Testing result: it is shown in Table 1.
The mechanical strength measurement result of 1 Biodegradable films of table
Tensile strength/Mpa Elongation at break/%
Embodiment 1 35.9 478
Embodiment 2 36.6 481
Embodiment 3 49.5 551
Comparative example 1 21.5 189
Comparative example 2 23.8 156
Comparative example 3 18.3 167
Comparative example 4 21.8 188
2. degradation effect detects
Detection method: GB/T19277 is referred to.
Testing result: 2 are shown in Table.
The degradation rate measurement result of 2 Biodegradable films of table
Degradation rate (%)
Embodiment 1 92
Embodiment 2 97
Embodiment 3 99
Comparative example 1 71
Comparative example 2 75
Comparative example 3 72
Comparative example 4 75
3. effect of food preservation measures
Detection method: determine that fresh-keeping effect, specific method refer to GB 47892-2010 with total plate count.
Testing result: 3 are shown in Table.
Fresh-keeping effect (25 DEG C) of 3 Biodegradable films of table to dried beef
Longest fresh keeping time (moon)
Embodiment 1 24
Embodiment 2 25
Embodiment 3 30
Comparative example 1 11
Comparative example 2 9
Comparative example 3 8
Comparative example 4 10
From the experimental results showed that, the present invention uses composite nano materials, and starch is carried out micronization and modification, Largely optimized using compound bio sill, while to the type of raw material and formula, improves bio-based composite material Interface compatibility to improve the mechanical strength of biomembrane, and has all biodegradability energy, has the fresh-keeping effect fabulous to food Fruit.

Claims (6)

1. a kind of modified starch-base biodegradation food package film of composite nano materials, which is characterized in that it is by following weight The raw material of number is prepared:
100 parts of compound bio sill；
20-50 parts of starch；
2-10 parts of composite nano materials；
1-3 parts of processing aid；
0.2-2 parts of Aluminate；
0.2-0.8 parts of lauryl amine,
The compound bio sill is made of PLA, PBAT and PCL；
The composite nano materials are by graphene, nano-TiO2, nano-ZnO and Nano-meter SiO_22Composition；
The processing aid is made of Ployethylene Wax, stearic acid and paraffin.
2. the modified starch-base biodegradation food package film of composite nano materials as described in claim 1, it is characterised in that: The weight ratio of PLA, PBAT, PCL three is 1:4:1.
3. the modified starch-base biodegradation food package film of composite nano materials as described in claim 1, it is characterised in that: The partial size of the composite nano materials is 5-80nm, graphene, nano-TiO in the composite nano materials2, nano-ZnO, nanometer SiO2Four weight ratio is 0.1:2:1:1.
4. the modified starch-base biodegradation food package film of composite nano materials as described in claim 1, it is characterised in that: The Ployethylene Wax, stearic acid, paraffin three weight ratio be 1:2:1.
5. a kind of prepare the modified starch-base biodegradation food packet of composite nano materials described in claim 1-4 any one The method for filling film, it is characterised in that the following steps are included:
1) starch is passed through into air-flow disintegrating machine micronization to 600-1200 mesh, is then placed in high-speed mixer, is added simultaneously Aluminate 80~100 DEG C stirring 10-30 minutes, obtain modified very fine starch；
2) composite nano materials and lauryl amine are stirred 10-30 minutes under ultrasonic conditions, divides nanocomposite sufficiently It dissipates, obtains modified composite nano materials；
3) the modification composite nano materials and compound bio base for obtaining modification very fine starch that step 1) obtains, step 2) Material, processing aid mix 10~30 minutes in high-speed mixer at 70-90 DEG C together, obtain mixed material；
4) mixed material of step 3) is placed in double screw extruder and is squeezed out, cooling through mould shape, traction and cutting, most Afterwards on inflation film manufacturing machine blown film to get.
6. the preparation method of the modified starch-base biodegradation food package film of composite nano materials as claimed in claim 5, Be characterized in that: the heating temperature T1-T10 of each section of the double screw extruder is respectively 80 DEG C, 100 DEG C, 110 DEG C, 130 DEG C, 150 DEG C, 170 DEG C, 170 DEG C, 160 DEG C, 150 DEG C and 110 DEG C, engine speed be 15-30 revs/min, material pressure 2.1-3.5MPA；It is described to blow Film condition: each section of heating temperature T1-T4 and die head are respectively 120 DEG C, 170 DEG C, 170 DEG C, 160 DEG C and 150 DEG C, and hauling speed is 4.3 revs/min, wind 8.15 revs/min.
CN201910664337.5A 2019-07-23 2019-07-23 Composite nano material modified starch-based biodegradable food packaging film and preparation method thereof Active CN110437590B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910664337.5A CN110437590B (en) 2019-07-23 2019-07-23 Composite nano material modified starch-based biodegradable food packaging film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910664337.5A CN110437590B (en) 2019-07-23 2019-07-23 Composite nano material modified starch-based biodegradable food packaging film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110437590A true CN110437590A (en) 2019-11-12
CN110437590B CN110437590B (en) 2020-07-31

Family

ID=68431103

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910664337.5A Active CN110437590B (en) 2019-07-23 2019-07-23 Composite nano material modified starch-based biodegradable food packaging film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110437590B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111361256A (en) * 2020-04-08 2020-07-03 保定茂华塑料制品有限公司 Biodegradable packaging film special for aviation and preparation method thereof
CN112550930A (en) * 2021-01-04 2021-03-26 安徽沪通环保包装科技有限公司 Convenient square-bottom bag and manufacturing method thereof
CN113005641A (en) * 2021-02-08 2021-06-22 武汉轻工大学 Preparation method of antioxidant starch composite nanofiber food packaging film
CN115612182A (en) * 2022-11-07 2023-01-17 广西民族大学 CMC/starch/ZnO/anthocyanin intelligent active packaging film and preparation method thereof
CN116409545A (en) * 2023-04-12 2023-07-11 淮阴师范学院 Degradable preservative film for fruit and vegetable transportation and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900148A (en) * 2005-07-18 2007-01-24 华中农业大学 Nano SiO2 modified starch base full biodegradable film and preparing method
CN103304851A (en) * 2013-07-07 2013-09-18 华东理工大学 High-starch-content waterproof totally-decomposed composite material and preparation method thereof
WO2015054685A1 (en) * 2013-10-11 2015-04-16 Ohio State Innovation Foundation Filler-natural rubber composites
CN104861210A (en) * 2015-04-30 2015-08-26 亿帆鑫富药业股份有限公司 Starch-base fully biodegradable resin with steady hydrophobic property and preparation method thereof
CN105968746A (en) * 2016-03-01 2016-09-28 安徽猛牛彩印包装有限公司 Oxidized graphene fully-degradable plastic film with good barrier property and manufacturing method of plastic film
EP3241677A1 (en) * 2016-05-03 2017-11-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermoformable multi-layer composite with oxygen barrier and protein-containing formulation for producing the multi-layer composite
CN108192302A (en) * 2018-02-05 2018-06-22 东莞市鑫海环保材料有限公司 A kind of biodegradation material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1900148A (en) * 2005-07-18 2007-01-24 华中农业大学 Nano SiO2 modified starch base full biodegradable film and preparing method
CN103304851A (en) * 2013-07-07 2013-09-18 华东理工大学 High-starch-content waterproof totally-decomposed composite material and preparation method thereof
WO2015054685A1 (en) * 2013-10-11 2015-04-16 Ohio State Innovation Foundation Filler-natural rubber composites
CN104861210A (en) * 2015-04-30 2015-08-26 亿帆鑫富药业股份有限公司 Starch-base fully biodegradable resin with steady hydrophobic property and preparation method thereof
CN105968746A (en) * 2016-03-01 2016-09-28 安徽猛牛彩印包装有限公司 Oxidized graphene fully-degradable plastic film with good barrier property and manufacturing method of plastic film
EP3241677A1 (en) * 2016-05-03 2017-11-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermoformable multi-layer composite with oxygen barrier and protein-containing formulation for producing the multi-layer composite
CN108192302A (en) * 2018-02-05 2018-06-22 东莞市鑫海环保材料有限公司 A kind of biodegradation material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111361256A (en) * 2020-04-08 2020-07-03 保定茂华塑料制品有限公司 Biodegradable packaging film special for aviation and preparation method thereof
CN112550930A (en) * 2021-01-04 2021-03-26 安徽沪通环保包装科技有限公司 Convenient square-bottom bag and manufacturing method thereof
CN113005641A (en) * 2021-02-08 2021-06-22 武汉轻工大学 Preparation method of antioxidant starch composite nanofiber food packaging film
CN115612182A (en) * 2022-11-07 2023-01-17 广西民族大学 CMC/starch/ZnO/anthocyanin intelligent active packaging film and preparation method thereof
CN116409545A (en) * 2023-04-12 2023-07-11 淮阴师范学院 Degradable preservative film for fruit and vegetable transportation and preparation method and application thereof

Also Published As

Publication number Publication date
CN110437590B (en) 2020-07-31

Similar Documents

Publication Publication Date Title
CN110437590A (en) A kind of starch-base biodegradation food package film and preparation method thereof that composite nano materials are modified
CN102504345B (en) Disposable controlled completely-degradable plastic packing bag and preparation method thereof
CN105440606A (en) Preparation method of fully biodegradable starch/polylactic acid base resin
CN108456407A (en) A kind of degradable package material and preparation method thereof
CN108929527B (en) PBAT/modified starch full-biodegradable film with high ductility and high barrier property as well as preparation method and application thereof
CN102604164A (en) Master batch capable of fully and biologically degrading plastic film and preparation method thereof
CN102408587A (en) Environmentally-friendly controllable degradation agricultural film and preparation method thereof
CN105504704B (en) Monoethanolamine activates sodium-based montmorillonite/polymer composite biodegradable blown film resin and preparation method
CN114316542B (en) High-strength biodegradable plastic and preparation method thereof
CN109825045A (en) A kind of graphene composite biomass enhancing PBS/PBAT biological degradable composite material and preparation method thereof
CN104910426A (en) Full-degradable plastic film taking surface hydrophobically modified starch as base material and preparation method thereof
CN102432942A (en) Non-starch biodegradable plastic film
CN107814979A (en) A kind of preparation method of self-reinforcing polyvinyl alcohol/modified starch Biodegradable mulch
CN107629304A (en) A kind of bio-based ecological plastic film and preparation method thereof
CN111057289A (en) LDPE/corn starch/TiO2Antibacterial composite membrane and preparation method thereof
CN107488298A (en) A kind of bio-based complete degradable plastic masterbatch, its preparation method and application
CN112175361B (en) High-barrier stretch-resistant antibacterial film type degradable material and preparation method thereof
CN112063126B (en) Completely biodegradable starch composite mulching film and preparation method thereof
CN106433044A (en) Modified bagasse strengthening PBAT/starch complete biodegradation composite material and preparing method and application thereof
CN107586440A (en) A kind of dried beef environmental protection freshness protection package and preparation method thereof
CN106751628B (en) A kind of polylactic acid membrane and preparation method thereof
CN109181284A (en) A kind of complete biodegradable high-barrier polyamide-based composite film material and preparation method thereof
CN110228261B (en) Degradable disposable plastic film and manufacturing method thereof
CN107189114A (en) A kind of preparation method of nano modification starch polyethylene alcohol complete-degradable plastic
CN116589810A (en) Degradable agricultural film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant