CN114437521A - Processing technology of degradable composite packaging film based on PBAT - Google Patents
Processing technology of degradable composite packaging film based on PBAT Download PDFInfo
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- 229920006280 packaging film Polymers 0.000 title claims abstract description 42
- 239000012785 packaging film Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000005516 engineering process Methods 0.000 title claims abstract description 18
- 238000012545 processing Methods 0.000 title claims abstract description 17
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 13
- 238000002156 mixing Methods 0.000 claims abstract description 52
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011146 organic particle Substances 0.000 claims abstract description 36
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 34
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000945 filler Substances 0.000 claims abstract description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 29
- 239000003063 flame retardant Substances 0.000 claims abstract description 29
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 229920002472 Starch Polymers 0.000 claims abstract description 19
- -1 polybutylene adipate-terephthalate Polymers 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 235000019698 starch Nutrition 0.000 claims abstract description 19
- 239000008107 starch Substances 0.000 claims abstract description 18
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims abstract description 13
- 238000005469 granulation Methods 0.000 claims abstract description 12
- 230000003179 granulation Effects 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 3
- 238000007664 blowing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 112
- 229920001661 Chitosan Polymers 0.000 claims description 42
- 102000011632 Caseins Human genes 0.000 claims description 41
- 108010076119 Caseins Proteins 0.000 claims description 41
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 37
- 239000005018 casein Substances 0.000 claims description 32
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 32
- 235000021240 caseins Nutrition 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 25
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000011780 sodium chloride Substances 0.000 claims description 19
- 238000000071 blow moulding Methods 0.000 claims description 18
- 239000007853 buffer solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000008055 phosphate buffer solution Substances 0.000 claims description 9
- 229940080237 sodium caseinate Drugs 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 238000004108 freeze drying Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000005022 packaging material Substances 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- UZBRNILSUGWULW-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione;hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.O=C1OCCCCOC(=O)C2=CC=C1C=C2 UZBRNILSUGWULW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005966 aza-Michael addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08J2489/00—Characterised by the use of proteins; Derivatives 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a processing technology of a degradable composite packaging film based on PBAT. The preparation method of the degradable composite packaging film comprises the following steps: step 1: uniformly mixing starch, polybutylene adipate-terephthalate, modified filler, degradable flame retardant and glycerol; step 2: putting the mixture into a double-screw extruder for melt blending, and extruding and granulating for one time; secondary extrusion granulation; obtaining master batches; and blowing the master batch into a film to obtain the degradable composite packaging film. In the technical scheme, the polyethylene glycol is used for modifying the surface of the calcium carbonate, so that the affinity of the calcium carbonate in a matrix is enhanced, and the dispersibility of the calcium carbonate is improved; the surface of the organic particle is modified by itaconic acid to form a degradable flame retardant with a pyrrolidone structure, and the flame retardance and the mechanical strength are enhanced by cooperating with calcium carbonate; thus preparing the degradable composite packaging film based on the PBAT.
Description
Technical Field
The invention relates to the technical field of packaging films, in particular to a processing technology of a degradable composite packaging film based on PBAT.
Background
With the progress of the times and the improvement of the living standard, the online retail industry brings convenience to people; the retail industry on the supporting line develops the express industry, at present, the express industry in China has rapidly increased in the past 10 years, and due to the acceleration of express life operation, the express packaging material is widely researched. Among them, today, the degradation of packaging materials is very important, because the final trend of packaging materials is toward the disposal of garbage, the problems of environmental pollution and ecological balance damage can be caused.
Wherein, the packaging film is one of the compositions of the packaging material; common packaging materials usually use polyethylene and other substances, and special methods such as biodegradation are needed for the packaging materials, and the common chemical degradation and natural degradation performance are poor; and poly (butylene adipate terephthalate) (PBAT) is aliphatic-aromatic copolyester with low crystallization rate, low crystallization rate and aliphatic ester bond, and has the performances of biodegradability, natural degradation and full degradation. However, pure PBAT packaging films have low strength and high cost, which limits their wide application. The strength of the film is generally enhanced by mixing starch, filler or other substances with the film; however, hydrophilic substances such as starches have poor compatibility with PBAT, and problems also exist with respect to dispersibility and compatibility of fillers; in addition, the flame retardance of the packaging material is also widely concerned, the flame retardance is improved, and the improvement of express delivery safety is one of the problems to be solved.
In conclusion, the preparation of the degradable composite packaging film based on the PBAT has important significance in solving the problems.
Disclosure of Invention
The invention aims to provide a processing technology of a degradable composite packaging film based on PBAT, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of a degradable composite packaging film based on PBAT comprises the following steps:
step 1: uniformly mixing starch, polybutylene adipate-terephthalate, modified filler, degradable flame retardant and glycerol;
step 2: putting the mixture into a double-screw extruder for melt blending, and extruding and granulating for one time; secondary extrusion granulation; obtaining master batches; and blowing the master batch into a film to obtain the degradable composite packaging film.
Preferably, the raw materials of the degradable composite packaging film comprise the following components: by weight, 20-35 parts of starch, 60-65 parts of polybutylene adipate-terephthalate, 4-6 parts of modified filler, 6-8 parts of degradable flame retardant and 10-12 parts of glycerol.
Preferably, the preparation method of the modified filler comprises the following steps: placing porous calcium carbonate in 10-12 wt% of polyethylene glycol solution for uniform dispersion; adding 5-6 wt% of sodium hypophosphite solution and uniformly stirring; and drying to obtain the modified filler.
Preferably, the modified filler comprises the following raw materials: 5-8 parts of porous calcium carbonate, 1-2 parts of polyethylene glycol and 0.5-1 part of sodium hypophosphite by weight; the polyethylene glycol is PEG-400 or PEG-600.
Preferably, the preparation method of the degradable flame retardant comprises the following steps: ultrasonically dispersing degradable organic particles in water to obtain 2-3 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, reacting for 20-24 hours at the set temperature of 80-100 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
Preferably, the addition amount of the itaconic acid is 6-8 times of the mass of the degradable organic particles.
Preferably, the preparation method of the degradable organic particles comprises the following steps: uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution; and setting the rotating speed to be 150-200 rmp, mixing and stirring for 2-4 hours, washing and drying to obtain the degradable organic particles.
Preferably, the preparation method of the chitosan solution comprises the following steps: dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.1-0.2% w/v chitosan solution; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into a phosphate buffer solution with the pH value of 5.6, and stirring for 6 hours to obtain a casein solution with the concentration of 0.08-0.12% w/v; the concentration of the sodium chloride solution is 0.04M; the amount added was 10% of the total volume of the two solutions.
Optimally, in the step 1, the temperature of the mixing speed is 60-80 ℃, and the rotating speed is 600-800 rmp; in the step 2, the granulation temperature is 160-180 ℃; the blow molding temperature is 150-170 ℃.
The degradable composite packaging film is prepared by the processing technology of the PBAT-based degradable composite packaging film.
In the technical scheme, the polyethylene glycol is used for modifying the surface of the calcium carbonate, so that the affinity of the calcium carbonate in a matrix is enhanced, and the dispersibility of the calcium carbonate is improved; the surface of the organic particle is modified by itaconic acid to form a degradable flame retardant with a pyrrolidone structure, and the flame retardance and the mechanical strength are enhanced by cooperating with calcium carbonate; thus preparing the degradable composite packaging film based on the PBAT.
(1) In the scheme, the low-molecular-weight polyethylene glycol-400/600 is used as a calcium carbonate surface modifier, so that the dispersibility of calcium carbonate is improved, and the rest starch has affinity. Meanwhile, hypophosphite is loaded on the surface of the poly (vinyl alcohol) and contains sodium which is positive charge, and hydrogen bonding force exists between the poly (vinyl alcohol) and the hypophosphite), so that the loading of the hypophosphite is convenient for improving the dispersibility of the hypophosphite and the poly (adipic acid-butylene terephthalate) in the follow-up process.
Further, it should be noted that: the hydrophilicity of the polyethylene glycol promotes the immersion of water, and can promote the degradation of PBAT. The low molecular weight polyethylene glycol has low viscosity, and is favorable for the dispersion uniformity.
(2) In the scheme, the degradable organic particles are prepared by utilizing the electrostatic interaction between casein and chitosan under the pH of 5.6; since both casein and chitosan have degradability, the formed particles are degradable. Meanwhile, the added sodium chloride improves the ion complexing strength and enhances the stability of the particles; the surface grafting of itaconic acid in the subsequent process is facilitated, and the degradable flame retardant with the pyrrolidone structure is formed. Meanwhile, due to the hydrogen bond effect between amino groups and other groups, the hydrophobicity of the particles is increased, and the packaging film has certain water resistance.
In the further reaction, itaconic acid is also natural unsaturated dicarboxylic acid and has degradability, amino groups exist in chitosan and casein, the particles formed by complexing also have amino groups, the amino groups and carboxyl groups of the itaconic acid form an aza-Michael addition reaction, and the reactivity is improved by the reaction in water. Meanwhile, the addition amount of the itaconic acid in the scheme is excessive, which is beneficial to the reaction, meanwhile, the itaconic acid can be dehydrated to generate cyclic anhydride or ester (because the chitosan contains hydroxyl, but less, because hydrogen bonding force exists), and unreacted itaconic acid also exists.
(3) The dispersibility of the degradable flame retardant in the matrix is enhanced by utilizing the ester in the degradable flame retardant; the cyclic anhydride generated by the cyclic anhydride can form ester bonds with hydroxyl in starch and hydroxyl in modified filler by using carbonyl, so that the similar compatibility of the two in PBAT is enhanced, and the dispersion uniformity is enhanced. The unreacted itaconic acid is dehydrated to generate cyclic anhydride in the high-temperature extrusion process; then under the mediation of hypophosphite existing in the modified filler, starch-itaconic acid ester is formed with hydroxyl in the starch, thereby playing the role of a compatilizer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
step 1: (1) ultrasonically dispersing 1.5 parts of PEG-600 in water to form a 12 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.8 part of sodium hypophosphite into water to form a 5 wt% sodium hypophosphite solution for later use; placing 6 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; adding a sodium hypophosphite solution and uniformly stirring; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.15% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH 5.6, stirring for 6 hours to obtain casein solution with 0.09% w/v for later use; uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution with the concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotating speed at 170rmp, mixing and stirring for 3 hours, washing and drying to obtain the degradable organic particles. Ultrasonically dispersing degradable organic particles in water to obtain 2 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, setting the adding amount of the itaconic acid to be 8 times of that of the degradable organic particles, reacting for 24 hours at the set temperature of 90 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 32 parts of starch, 62 parts of polybutylene adipate-terephthalate, 5 parts of modified filler, 7 parts of degradable flame retardant and 12 parts of glycerol at the mixing speed and the temperature of 75 ℃ and the rotating speed of 800rmp to obtain a mixture;
step 2: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 170 ℃ for one time, and standing; performing secondary extrusion granulation at 170 ℃ to obtain master batches; blow molding the mixture at the blow molding temperature of 160 ℃ to form a film, thus obtaining the degradable composite packaging film.
Example 2:
step 1: (1) ultrasonically dispersing 1 part of PEG-600 in water to form 10 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.5 part of sodium hypophosphite into water to form a 5 wt% sodium hypophosphite solution for later use; placing 5 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; adding a sodium hypophosphite solution and uniformly stirring; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.1% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH 5.6, stirring for 6 hours to obtain casein solution with 0.08% w/v for later use; uniformly mixing chitosan solution and casein solution with equal volume amount, and adding sodium chloride solution with concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotating speed at 150rmp, mixing and stirring for 2 hours, washing and drying to obtain the degradable organic particles. Ultrasonically dispersing degradable organic particles in water to obtain 2 wt% of dispersion liquid; adding itaconic acid to uniformly disperse, wherein the addition amount of the itaconic acid is 6 times of that of the degradable organic particles, reacting for 20 hours at the set temperature of 80 ℃ in a nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 20 parts of starch, 60 parts of polybutylene adipate-terephthalate, 4 parts of modified filler, 6 parts of degradable flame retardant and 10 parts of glycerol at the mixing speed and the temperature of 60 ℃ and the rotating speed of 600rmp to obtain a mixture;
step 2: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 160 ℃ for one time, and standing; performing secondary extrusion granulation at 160 ℃ to obtain master batches; and carrying out blow molding on the mixture at the blow molding temperature of 150 ℃ to form a film, thus obtaining the degradable composite packaging film.
Example 3:
step 1: (1) ultrasonically dispersing 2 parts of PEG-400 in water to form a 12 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.5-1 part of sodium hypophosphite into water to form a 6 wt% sodium hypophosphite solution for later use; placing 8 parts of porous calcium carbonate in 12 wt% polyethylene glycol solution for uniform dispersion; adding 6 wt% of sodium hypophosphite solution and stirring uniformly; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.2% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH value of 5.6, stirring for 6 hours to obtain 0.12% w/v casein solution for later use; uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution with the concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotation speed at 200rmp, mixing and stirring for 4 hours, washing and drying to obtain the degradable organic particles. Ultrasonically dispersing degradable organic particles in water to obtain 3 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, setting the adding amount of the itaconic acid to be 8 times of that of the degradable organic particles, reacting for 24 hours at the set temperature of 100 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 35 parts of starch, 65 parts of polybutylene adipate-terephthalate, 6 parts of modified filler, 8 parts of degradable flame retardant and 12 parts of glycerol at a mixing speed of 80 ℃ and a rotating speed of 800rmp to obtain a mixture;
and 2, step: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 180 ℃ for one time, and standing; performing secondary extrusion granulation at 180 ℃ to obtain master batches; blow molding the mixture at the blow molding temperature of 170 ℃ to form a film, thus obtaining the degradable composite packaging film.
Comparative example 1: in the scheme, polyethylene glycol 400 is replaced by polyethylene glycol 2000, and the rest is the same as the example 1;
step 1: (1) ultrasonically dispersing 1.5 parts of PEG-2000 in water to form a 12 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.8 part of sodium hypophosphite into water to form a 5 wt% sodium hypophosphite solution for later use; placing 6 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; adding a sodium hypophosphite solution and uniformly stirring; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.15% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH 5.6, stirring for 6 hours to obtain casein solution with 0.09% w/v for later use; uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution with the concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotating speed at 170rmp, mixing and stirring for 3 hours, washing and drying to obtain the degradable organic particles. Ultrasonically dispersing degradable organic particles in water to obtain 2 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, setting the adding amount of the itaconic acid to be 8 times of that of the degradable organic particles, reacting for 24 hours at the set temperature of 90 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 32 parts of starch, 62 parts of polybutylene adipate-terephthalate, 5 parts of modified filler, 7 parts of degradable flame retardant and 12 parts of glycerol at the mixing speed and the temperature of 75 ℃ and the rotating speed of 800rmp to obtain a mixture;
step 2: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 170 ℃ for one time, and standing; performing secondary extrusion granulation at 170 ℃ to obtain master batches; blow molding the mixture at the blow molding temperature of 160 ℃ to form a film, thus obtaining the degradable composite packaging film.
Comparative example 2: in this scheme, no hypophosphite was added, and the rest was the same as in example 1;
step 1: (1) ultrasonically dispersing 1.5 parts of PEG-600 in water to form a 12 wt% polyethylene glycol solution for later use; placing 6 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.15% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH value of 5.6, stirring for 6 hours to obtain 0.09% w/v casein solution for later use; uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution with the concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotating speed at 170rmp, mixing and stirring for 3 hours, washing and drying to obtain the degradable organic particles. Ultrasonically dispersing degradable organic particles in water to obtain 2 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, setting the adding amount of the itaconic acid to be 8 times of that of the degradable organic particles, reacting for 24 hours at the set temperature of 90 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 32 parts of starch, 62 parts of polybutylene adipate-terephthalate, 5 parts of modified filler, 7 parts of degradable flame retardant and 12 parts of glycerol at the mixing speed and the temperature of 75 ℃ and the rotating speed of 800rmp to obtain a mixture;
step 2: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 170 ℃ for one time, and standing; extruding and granulating for the second time at 170 ℃; obtaining master batches; blow molding the mixture at the blow molding temperature of 160 ℃ to form a film, thus obtaining the degradable composite packaging film.
Comparative example 3: itaconic acid modification is not carried out on the degradable organic particles; otherwise, the same as example 1;
step 1: (1) ultrasonically dispersing 1.5 parts of PEG-600 in water to form a 12 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.8 part of sodium hypophosphite into water to form a 5 wt% sodium hypophosphite solution for later use; placing 6 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; adding a sodium hypophosphite solution and uniformly stirring; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.15% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH 5.6, stirring for 6 hours to obtain casein solution with 0.09% w/v for later use; uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution with the concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotating speed at 170rmp, mixing and stirring for 3 hours, washing and drying to obtain the degradable organic particles.
(3) Uniformly mixing 32 parts of starch, 62 parts of polybutylene adipate-terephthalate, 5 parts of modified filler, 7 parts of degradable organic particles and 12 parts of glycerol at a mixing speed of 75 ℃ and a rotating speed of 800rmp to obtain a mixture;
step 2: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 170 ℃ for one time, and standing; performing secondary extrusion granulation at 170 ℃ to obtain master batches; blow molding the mixture at the blow molding temperature of 160 ℃ to form a film, thus obtaining the degradable composite packaging film.
Comparative example 4: the amount of itaconic acid added was 4 times the mass of the degradable organic particles, and the rest was the same as in example 1.
Step 1: (1) ultrasonically dispersing 1.5 parts of PEG-600 in water to form a 12 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.8 part of sodium hypophosphite into water to form a 5 wt% sodium hypophosphite solution for later use; placing 6 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; adding a sodium hypophosphite solution and uniformly stirring; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.15% w/v chitosan solution for later use; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into phosphate buffer solution with pH 5.6, stirring for 6 hours to obtain casein solution with 0.09% w/v for later use; uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution with the concentration of 0.04M; the adding amount of the sodium chloride solution is 10 percent of the total volume of the two solutions; setting the rotating speed at 170rmp, mixing and stirring for 3 hours, washing and drying to obtain the degradable organic particles. Ultrasonically dispersing degradable organic particles in water to obtain 2 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, setting the addition of the itaconic acid to be 4 times of that of the degradable organic particles, reacting for 24 hours at the set temperature of 90 ℃ in a nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 32 parts of starch, 62 parts of polybutylene adipate-terephthalate, 5 parts of modified filler, 7 parts of degradable flame retardant and 12 parts of glycerol at the mixing speed and the temperature of 75 ℃ and the rotating speed of 800rmp to obtain a mixture;
step 2: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 170 ℃ for one time, and standing; performing secondary extrusion granulation at 170 ℃ to obtain master batches; blow molding the mixture at the blow molding temperature of 160 ℃ to form a film, thus obtaining the degradable composite packaging film.
Comparative example 5: the degradable organic particles were replaced with chitosan particles, and the rest was the same as in example 1;
step 1: (1) ultrasonically dispersing 1.5 parts of PEG-600 in water to form a 12 wt% polyethylene glycol solution for later use; ultrasonically dispersing 0.8 part of sodium hypophosphite into water to form a 5 wt% sodium hypophosphite solution for later use; placing 6 parts of porous calcium carbonate in a polyethylene glycol solution for uniform dispersion; adding a sodium hypophosphite solution and uniformly stirring; and (5) freeze-drying to obtain the modified filler.
(2) Dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.15% w/v chitosan solution; mixing the chitosan solution with 4mg/L TPP solution at a volume ratio of 5:1, reacting at 60 ℃ for 20 minutes, filtering and drying to obtain chitosan particles. Ultrasonically dispersing chitosan particles in water to obtain 2 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, setting the adding amount of the itaconic acid to be 8 times of that of the degradable organic particles, reacting for 24 hours at the set temperature of 90 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
(3) Uniformly mixing 32 parts of starch, 62 parts of polybutylene adipate-terephthalate, 5 parts of modified filler, 7 parts of degradable flame retardant and 12 parts of glycerol at the mixing speed and the temperature of 75 ℃ and the rotating speed of 800rmp to obtain a mixture;
and 2, step: putting the mixture into a double-screw extruder for melt blending, extruding and granulating at 170 ℃ for one time, and standing; performing secondary extrusion granulation at 170 ℃ to obtain master batches; and blow-molding the mixture at the blow-molding temperature of 160 ℃ to form a film, thus obtaining the degradable composite packaging film.
Experiment: taking the degradable composite packaging films prepared in the examples and the comparative examples for relevant tests; the mechanical property test is detected according to GB/T1040.0-2006, and the tensile strength is obtained; the degradation performance is detected according to GB/T19277, and the degradation rate is obtained after degradation is carried out for 90 days; and the flame retardant performance is detected by referring to GB/T2406.2-2009 to obtain the limit oxygen index. Specific numerical values are shown in the following table.
| Examples | Tensile strength/MPa | Percent of degradation/%) | Flame retardancy/%) |
| Example 1 | 52.3 | 97 | 35.6 |
| Example 2 | 50.3 | 98 | 34.8 |
| Example 3 | 51.6 | 95 | 35.5 |
| Comparative example 1 | 51.0 | 98 | 35.1 |
| Comparative example 2 | 49.2 | 94 | 33.8 |
| Comparative example 3 | 31.1 | 97 | 32.5 |
| Comparative example 4 | 42.3 | 98 | 33.0 |
| Comparative example 5 | 50.8 | 94 | 34.9 |
And (4) conclusion: the data in examples 1-3 show that the prepared composite packaging film has good mechanical properties; and after 90 days, the degradation rate can reach 98 percent; the flame retardance is up to 35%. Has excellent performance.
Comparing the data of comparative examples 1-5 with example 1, it can be found that: in comparative example 1, the molecular weight of polyethylene glycol was increased, the tensile strength was decreased, and the degradability was slightly increased; the reason is that: the polyethylene glycol has increased molecular weight, increased viscosity and reduced uniformity in the matrix, so that the tensile strength is slightly reduced, while the hydrophilicity is enhanced due to the increased abundance of hydroxyl groups, so that the degradation rate is slightly increased, but the change is small. In comparative example 2, since hypophosphite was not added, dehydration of itaconic acid was reduced, ester bond ratio was reduced, and compatibility was reduced. At the same time, the flame retardancy and degradation rate decrease because the acidic groups in the hypophosphite enhance the degradability, while the phosphorus element enhances the flame retardancy. In comparative example 3, since no modification with itaconic acid was used, the tensile strength was greatly reduced because the compatibility was seriously reduced. Similarly, when the amount of itaconic acid added in example 4 is reduced, there is a significant decrease in tensile strength due to: the itaconic acid is dehydrated to form cyclic anhydride, which contains carbonyl group and can form ester bond with hydroxyl in starch and hydroxyl in modified filler, thereby enhancing the similar compatibility of the two in PBAT and enhancing the dispersion uniformity. Further, flame retardancy is also decreased because itaconic acid may react with amino group to form a squarylium pyrrolidone structure, which has flame retardancy. In comparative example 5, since chitosan particles were used instead of degradable organic particles, the degradation rate and flame retardancy were decreased, since chitosan nanoparticles have stronger structure and increased degradation resistance, while the degradation was simpler using casein and its electrostatic assembly; meanwhile, phosphorus and calcium in casein have flame retardance, and although the TPP is added into the chitosan, the addition amount is small.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A processing technology of a degradable composite packaging film based on PBAT is characterized in that: the method comprises the following steps:
step 1: uniformly mixing starch, polybutylene adipate-terephthalate, modified filler, degradable flame retardant and glycerol;
step 2: putting the mixture into a double-screw extruder for melt blending, and extruding and granulating for one time; secondary extrusion granulation; obtaining master batches; and blowing the master batch into a film to obtain the degradable composite packaging film.
2. The processing technology of the degradable composite packaging film based on the PBAT of claim 1 is characterized in that: the degradable composite packaging film comprises the following raw materials: by weight, 20-35 parts of starch, 60-65 parts of polybutylene adipate-terephthalate, 4-6 parts of modified filler, 6-8 parts of degradable flame retardant and 10-12 parts of glycerol.
3. The processing technology of the degradable composite packaging film based on the PBAT of claim 1 is characterized in that: the preparation method of the modified filler comprises the following steps: placing porous calcium carbonate in 10-12 wt% of polyethylene glycol solution for uniform dispersion; adding 5-6 wt% of sodium hypophosphite solution and uniformly stirring; and drying to obtain the modified filler.
4. The processing technology of the degradable composite packaging film based on the PBAT of claim 1 is characterized in that: the modified filler comprises the following raw materials: 5-8 parts of porous calcium carbonate, 1-2 parts of polyethylene glycol and 0.5-1 part of sodium hypophosphite by weight; the polyethylene glycol is PEG-400 or PEG-600.
5. The processing technology of the degradable composite packaging film based on the PBAT of claim 1 is characterized in that: the preparation method of the degradable flame retardant comprises the following steps: ultrasonically dispersing degradable organic particles in water to obtain 2-3 wt% of dispersion liquid; adding itaconic acid, dispersing uniformly, reacting for 20-24 hours at the set temperature of 80-100 ℃ in the nitrogen atmosphere, cooling, and drying to obtain the degradable flame retardant.
6. The processing technology of the degradable composite packaging film based on the PBAT of claim 5 is characterized in that: the addition amount of the itaconic acid is 6-8 times of that of the degradable organic particles.
7. The processing technology of the degradable composite packaging film based on the PBAT of claim 5 is characterized in that: the preparation method of the degradable organic particles comprises the following steps: uniformly mixing chitosan solution and casein solution with equal volume, and adding sodium chloride solution; and setting the rotating speed to be 150-200 rmp, mixing and stirring for 2-4 hours, washing and drying to obtain the degradable organic particles.
8. The processing technology of the degradable composite packaging film based on the PBAT of claim 7 is characterized in that: the preparation method of the chitosan solution comprises the following steps: dispersing chitosan powder into 0.01M acetic acid buffer solution with pH value of 5.6, and stirring overnight to obtain 0.1-0.2% w/v chitosan solution; the preparation method of the casein solution comprises the following steps: dispersing sodium caseinate into a phosphate buffer solution with the pH value of 5.6, and stirring for 6 hours to obtain a casein solution with the concentration of 0.08-0.12% w/v; the concentration of the sodium chloride solution is 0.04M; the amount added was 10% of the total volume of the two solutions.
9. The processing technology of the degradable composite packaging film based on the PBAT of claim 1 is characterized in that: in the step 1, the mixing speed temperature is 60-80 ℃, and the rotating speed is 600-800 rmp; in the step 2, the granulation temperature is 160-180 ℃; the blow molding temperature is 150-170 ℃.
10. The degradable composite packaging film prepared by the processing technology of the PBAT-based degradable composite packaging film according to any one of claims 1-9.
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