CN113321832A - Environment-friendly degradable plastic packaging film and preparation method thereof - Google Patents
Environment-friendly degradable plastic packaging film and preparation method thereof Download PDFInfo
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- CN113321832A CN113321832A CN202110721689.7A CN202110721689A CN113321832A CN 113321832 A CN113321832 A CN 113321832A CN 202110721689 A CN202110721689 A CN 202110721689A CN 113321832 A CN113321832 A CN 113321832A
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- 239000012785 packaging film Substances 0.000 title claims abstract description 34
- 229920006280 packaging film Polymers 0.000 title claims abstract description 34
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 27
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229920002261 Corn starch Polymers 0.000 claims abstract description 15
- 239000008120 corn starch Substances 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 11
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 11
- 239000008116 calcium stearate Substances 0.000 claims abstract description 11
- 150000004645 aluminates Chemical class 0.000 claims abstract description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 30
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229920000881 Modified starch Polymers 0.000 claims description 10
- 239000004368 Modified starch Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 235000019426 modified starch Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- NCIYZALOQBXNLW-UHFFFAOYSA-N (3-fluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 NCIYZALOQBXNLW-UHFFFAOYSA-N 0.000 claims description 8
- JCQPONUUPNAEGZ-UHFFFAOYSA-N 4-aminobenzoyl chloride Chemical compound NC1=CC=C(C(Cl)=O)C=C1 JCQPONUUPNAEGZ-UHFFFAOYSA-N 0.000 claims description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012346 acetyl chloride Substances 0.000 claims description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 8
- 229920003023 plastic Polymers 0.000 abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229920002472 Starch Polymers 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000008107 starch Substances 0.000 abstract description 2
- 235000019698 starch Nutrition 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000010345 tape casting Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- 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
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- 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
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- 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)
Abstract
The invention discloses an environment-friendly degradable plastic packaging film and a preparation method thereof, belonging to the technical field of degradable packaging films, and the environment-friendly degradable plastic packaging film comprises the following raw materials in parts by weight: 40-60 parts of PBS resin, 30-40 parts of corn starch, 8.6-10.8 parts of nano silicon dioxide, 5.7-10.9 parts of calcium stearate, 3.5-7.9 parts of nano calcium carbonate, 0.2-0.8 part of aluminate and 10.2-12.4 parts of degradation promoter, wherein the environment-friendly degradable plastic packaging film is prepared by preparing starch for modification, mixing, extrusion, tape casting and stretching, the added degradation promoter contains a plurality of carbonyl groups, and the carbonyl compounds can absorb ultraviolet light of 270-300nm to generate free radicals for initiating the cracking of high molecular polymers and generate substances which can be absorbed by the environment such as carbon dioxide and the like, so that the cracking rate is promoted, and the aging of the plastic is promoted.
Description
Technical Field
The invention relates to the technical field of degradable packaging films, in particular to an environment-friendly degradable plastic packaging film and a preparation method thereof.
Background
Plastic films are films made of polyvinyl chloride, polyethylene, polypropylene, polystyrene and other thermoplastic resins, and are used for packaging and as film coatings. Plastic packages and plastic package products have a larger share in the market, and particularly, composite plastic flexible packages are widely applied to the fields of food, medicine, chemical industry and the like, wherein the proportion of the plastic packages is the largest, such as beverage packages, quick-frozen food packages, steamed and cooked food packages, fast food packages and the like, and the plastic packages and the plastic package products bring great convenience to the life of people.
Although the plastic film brings great benefits to people, as the plastic film is used, the plastic film cannot be degraded in time, so that a plurality of problems are brought to the life and the environment of people, and particularly, the environment is polluted greatly.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an environment-friendly degradable plastic packaging film and a preparation method thereof, which are used for solving the problems in the background art.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: an environment-friendly degradable plastic packaging film comprises the following raw materials in parts by weight: 40-60 parts of PBS resin, 30-40 parts of corn starch, 8.6-10.8 parts of nano silicon dioxide, 5.7-10.9 parts of calcium stearate, 3.5-7.9 parts of nano calcium carbonate, 0.2-0.8 part of aluminate and 10.2-12.4 parts of degradation accelerator;
the degradation promoter is prepared by the following steps:
step S1: adding p-xylene into a flask, adding anhydrous aluminum chloride at the temperature of 5-8 ℃, dropwise adding acetyl chloride into the flask while stirring under the ice bath condition, heating to 50 ℃ after dropwise adding is finished, stirring for reacting for 5-7h, and performing post-treatment after the reaction is finished, wherein the post-treatment step is as follows: pouring the resultant into mixture of crushed ice and dilute hydrochloric acid to decompose, standing for layering, filtering to remove lower layer, adding saturated NaHCO into upper layer solution3Adjusting organic phase to neutral, extracting with ethyl acetate for 3 times, washing the extract with saturated NaCl solution, drying with anhydrous calcium chloride, steaming to remove p-xylene at normal pressure, and vacuum-pumping with oil pumpDistilling to obtain an intermediate 1;
the reaction equation is as follows:
step S2: adding the intermediate 1 and deionized water into a flask, then adding potassium permanganate, performing reflux reaction for 2-3h at the temperature of 100 ℃ to obtain an intermediate 2, then adding the intermediate 2 and DMF into the flask, then adding thionyl chloride, introducing nitrogen, and performing reaction for 5-6h at the temperature of 60-65 ℃ to obtain an intermediate 3;
the reaction equation is as follows:
step S3: adding the intermediate 3 and chlorobenzene into a flask, uniformly stirring in ice bath, adding anhydrous aluminum chloride, stirring for 20min, reacting at room temperature for 1-2h, heating to 80 ℃, reacting for 8-12h, performing post-treatment after the reaction is finished, settling in ice hydrochloric acid, washing a filter cake after suction filtration by deionized water, a saturated sodium bicarbonate aqueous solution, anhydrous ethanol and deionized water in sequence, and drying at 70 ℃ to obtain an intermediate 4;
the reaction equation is as follows:
step S4: adding the intermediate 4, potassium carbonate and deionized water into a flask, stirring and mixing uniformly, adding tetraethylammonium bromide, and carrying out reflux reaction for 1-2 hours at the temperature of 110-120 ℃ to obtain an intermediate 5;
the reaction equation is as follows:
step S5: adding the intermediate 5, pyridine and tetrahydrofuran into a flask, stirring, adding p-aminobenzoyl chloride, introducing nitrogen, reacting for 3-4 hours at the temperature of 40-50 ℃, and obtaining an intermediate 6 after the reaction is finished;
step S6: adding the intermediate 6, cesium carbonate and 3-fluorobenzophenone into a flask, introducing nitrogen, adding DMF, carrying out reflux reaction at the temperature of 150 ℃ for 10-11h, and then carrying out a reaction by using a solvent with a volume ratio of 2: and (3) eluting the dichloromethane/petroleum ether solution of the solvent 1 to prepare the degradation accelerator.
The reaction equation is as follows:
further, the dosage ratio of the p-xylene, the anhydrous aluminum chloride and the acetyl chloride in the step S1 is 0.6 mol: 0.2 mol: 16 g.
Further, in the step S2, the dosage ratio of the intermediate 1 to the potassium permanganate is 0.1 g: 2g, the dosage ratio of the intermediate 2 to the thionyl chloride is 0.2 g: 3.5 g.
Further, in step S3, the ratio of the intermediate 3, chlorobenzene, and anhydrous aluminum chloride is 0.1 mol: 0.3 mol: 0.05 mol.
Further, in step S4, the ratio of the intermediate 4, potassium carbonate, deionized water, and tetraethylammonium bromide is 5 g: 0.5 g: 50mL of: 0.6 g.
Further, the intermediate 5, pyridine, tetrahydrofuran and p-aminobenzoyl chloride are used in a ratio of 0.05mol in step S5: 0.05 mol: 50mL of: 0.1 mol.
Further, in step S6, the ratio of the intermediate 6, cesium carbonate and 3-fluorobenzophenone is 0.5 mol: 0.6 mol: 1.1 mol.
A preparation method of an environment-friendly degradable plastic packaging film specifically comprises the following steps:
the method comprises the following steps: micronizing corn starch to 600-1200 meshes by using a jet mill, then placing the corn starch into a high-speed stirrer, and simultaneously adding aluminate to stir for 30min at 80-100 ℃ to obtain modified starch;
step two: adding the PBS resin and the degradation accelerant into a stirring kettle, mixing for 20min at the temperature of 50 ℃, then crushing and sieving with a 60-mesh sieve, sequentially adding the modified starch, the nano-silicon dioxide, the calcium stearate and the nano-calcium carbonate, and stirring and mixing for 30min at the temperature of 60 ℃ to obtain a mixture;
step three: extruding the mixture by using an extruder, preparing a film by using an ABA type extrusion casting die, and stretching by using a three-roll calender to obtain the environment-friendly degradable plastic packaging film, wherein the extrusion temperature of the extruder is 155-165 ℃, and the temperature of the extrusion casting die is 170-180 ℃.
(III) advantageous effects
The invention provides an environment-friendly degradable plastic packaging film and a preparation method thereof. Compared with the prior art, the method has the following beneficial effects: the invention uses PBS resin with degradable function and starch with biodegradable function as the basal body of the packaging film, has good degradation effect, and simultaneously prepares and adds a degradation accelerant, firstly, paraxylene and acetyl chloride react to prepare an intermediate 1, then methyl of the intermediate 1 is oxidized into carboxyl to obtain an intermediate 2, the intermediate 2 and thionyl chloride carry out acylation reaction to prepare an intermediate 3 with acyl chloride group, the intermediate 3 reacts with chlorobenzene under anhydrous aluminum chloride condition to prepare an intermediate 4, the intermediate 4 carries out hydrolysis reaction under alkaline condition to prepare an intermediate 5, then hydroxyl of the intermediate 5 reacts with acyl chloride of p-aminobenzoyl chloride to prepare an intermediate 6, the intermediate 6 and 3-fluorobenzophenone carry out substitution reaction to prepare the degradation accelerant, the degradation accelerant contains a plurality of carbonyl groups, and the carbonyl compound can absorb ultraviolet light of 270-300nm, the oxygen atom on the carbonyl and the carbon atom connected with the oxygen atom are polarized strongly, the polarized oxygen atom has the electronic characteristic of electron seeking, the carbon atom has the electronic characteristic of nucleus seeking, the C-C bond at the alpha position of the carbonyl can be cut off to generate carbonyl compound free radicals and low-carbon compound free radicals, the C-C bond at the gamma position can be broken to generate free radicals and low-carbon compounds, the free radicals can initiate the cracking of high molecular polymers, and the low-carbon compounds can degrade to generate substances such as carbon dioxide and the like which can be absorbed by the environment, the cracking rate is promoted, the plastic decomposition is promoted, and the finally prepared environment-friendly degradable plastic packaging film has excellent environment-friendly degradable performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
The degradation promoter is prepared by the following steps:
step S1: adding p-xylene into a flask, adding anhydrous aluminum chloride at the temperature of 5 ℃, then dropwise adding acetyl chloride into the flask while stirring under the ice bath condition, heating to 50 ℃ after dropwise adding is finished, stirring for reacting for 5 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment step is as follows: pouring the resultant into mixture of crushed ice and dilute hydrochloric acid to decompose, standing for layering, filtering to remove lower layer, adding saturated NaHCO into upper layer solution3Adjusting the organic phase of the solution to be neutral, extracting the solution for 3 times by using ethyl acetate, washing an extract by using a saturated NaCl solution, drying the extract by using anhydrous calcium chloride, evaporating and removing p-xylene at normal pressure, and then distilling the extract by using an oil pump under reduced pressure to prepare an intermediate 1;
step S2: adding the intermediate 1 and deionized water into a flask, then adding potassium permanganate, performing reflux reaction for 2 hours at the temperature of 100 ℃ to obtain an intermediate 2, then adding the intermediate 2 and DMF into the flask, then adding thionyl chloride, introducing nitrogen, and performing reaction for 5 hours at the temperature of 60 ℃ to obtain an intermediate 3;
step S3: adding the intermediate 3 and chlorobenzene into a flask, uniformly stirring in ice bath, adding anhydrous aluminum chloride, stirring for 20min, reacting at room temperature for 1h, heating to 80 ℃, reacting for 8h, performing post-treatment after the reaction is finished, settling in glacial hydrochloric acid, washing a filter cake after suction filtration by deionized water, a saturated sodium bicarbonate aqueous solution, anhydrous ethanol and deionized water in sequence, and drying at 70 ℃ to obtain an intermediate 4;
step S4: adding the intermediate 4, potassium carbonate and deionized water into a flask, stirring and mixing uniformly, adding tetraethylammonium bromide, and carrying out reflux reaction for 1 hour at the temperature of 110 ℃ to obtain an intermediate 5;
step S5: adding the intermediate 5, pyridine and tetrahydrofuran into a flask, stirring, adding p-aminobenzoyl chloride, introducing nitrogen, reacting for 3 hours at the temperature of 40 ℃, and obtaining an intermediate 6 after the reaction is finished;
step S6: adding the intermediate 6, cesium carbonate and 3-fluorobenzophenone into a flask, introducing nitrogen, adding DMF, carrying out reflux reaction at the temperature of 150 ℃ for 10 hours, and then carrying out reflux reaction by using a solvent with a volume ratio of 2: and (3) eluting the dichloromethane/petroleum ether solution of the solvent 1 to prepare the degradation accelerator.
Example 2
The degradation promoter is prepared by the following steps:
step S1: adding p-xylene into a flask, adding anhydrous aluminum chloride at the temperature of 6.5 ℃, then dropwise adding acetyl chloride into the flask while stirring under the ice bath condition, heating to 50 ℃ after dropwise adding is finished, stirring for reacting for 6 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment step is as follows: pouring the resultant into mixture of crushed ice and dilute hydrochloric acid to decompose, standing for layering, filtering to remove lower layer, adding saturated NaHCO into upper layer solution3Adjusting the organic phase of the solution to be neutral, extracting the solution for 3 times by using ethyl acetate, washing an extract by using a saturated NaCl solution, drying the extract by using anhydrous calcium chloride, evaporating and removing p-xylene at normal pressure, and then distilling the extract by using an oil pump under reduced pressure to prepare an intermediate 1;
step S2: adding the intermediate 1 and deionized water into a flask, then adding potassium permanganate, performing reflux reaction for 2.5 hours at the temperature of 100 ℃ to obtain an intermediate 2, then adding the intermediate 2 and DMF into the flask, then adding thionyl chloride, introducing nitrogen, and performing reaction for 5.5 hours at the temperature of 62.5 ℃ to obtain an intermediate 3;
step S3: adding the intermediate 3 and chlorobenzene into a flask, uniformly stirring in ice bath, adding anhydrous aluminum chloride, stirring for 20min, reacting at room temperature for 1.5h, heating to 80 ℃, reacting for 10h, performing post-treatment after the reaction is finished, settling in ice hydrochloric acid, washing a filter cake after suction filtration by deionized water, a saturated sodium bicarbonate aqueous solution, anhydrous ethanol and deionized water in sequence, and drying at 70 ℃ to obtain an intermediate 4;
step S4: adding the intermediate 4, potassium carbonate and deionized water into a flask, stirring and mixing uniformly, adding tetraethylammonium bromide, and carrying out reflux reaction for 1.5 hours at the temperature of 115 ℃ to obtain an intermediate 5;
step S5: adding the intermediate 5, pyridine and tetrahydrofuran into a flask, stirring, adding p-aminobenzoyl chloride, introducing nitrogen, reacting for 3.5 hours at the temperature of 45 ℃, and obtaining an intermediate 6 after the reaction is finished;
step S6: adding the intermediate 6, cesium carbonate and 3-fluorobenzophenone into a flask, introducing nitrogen, adding DMF, carrying out reflux reaction at the temperature of 150 ℃ for 10.5 hours, and then carrying out a reaction by using a solvent with a volume ratio of 2: and (3) eluting the dichloromethane/petroleum ether solution of the solvent 1 to prepare the degradation accelerator.
Example 3
The degradation promoter is prepared by the following steps:
step S1: adding p-xylene into a flask, adding anhydrous aluminum chloride at the temperature of 8 ℃, then dropwise adding acetyl chloride into the flask while stirring under the ice bath condition, heating to 50 ℃ after dropwise adding is finished, stirring for reacting for 7 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment step is as follows: pouring the resultant into mixture of crushed ice and dilute hydrochloric acid to decompose, standing for layering, filtering to remove lower layer, adding saturated NaHCO into upper layer solution3Adjusting the organic phase of the solution to be neutral, extracting the solution for 3 times by using ethyl acetate, washing an extract by using a saturated NaCl solution, drying the extract by using anhydrous calcium chloride, evaporating and removing p-xylene at normal pressure, and then distilling the extract by using an oil pump under reduced pressure to prepare an intermediate 1;
step S2: adding the intermediate 1 and deionized water into a flask, then adding potassium permanganate, performing reflux reaction for 3 hours at the temperature of 100 ℃ to obtain an intermediate 2, then adding the intermediate 2 and DMF into the flask, then adding thionyl chloride, introducing nitrogen, and performing reaction for 6 hours at the temperature of 65 ℃ to obtain an intermediate 3;
step S3: adding the intermediate 3 and chlorobenzene into a flask, uniformly stirring in ice bath, adding anhydrous aluminum chloride, stirring for 20min, reacting at room temperature for 2h, heating to 80 ℃, reacting for 12h, performing post-treatment after the reaction is finished, settling in glacial hydrochloric acid, washing a filter cake after suction filtration by deionized water, a saturated sodium bicarbonate aqueous solution, anhydrous ethanol and deionized water in sequence, and drying at 70 ℃ to obtain an intermediate 4;
step S4: adding the intermediate 4, potassium carbonate and deionized water into a flask, stirring and mixing uniformly, adding tetraethylammonium bromide, and carrying out reflux reaction for 2 hours at the temperature of 120 ℃ to obtain an intermediate 5;
step S5: adding the intermediate 5, pyridine and tetrahydrofuran into a flask, stirring, adding p-aminobenzoyl chloride, introducing nitrogen, reacting for 4 hours at the temperature of 50 ℃, and obtaining an intermediate 6 after the reaction is finished;
step S6: adding the intermediate 6, cesium carbonate and 3-fluorobenzophenone into a flask, introducing nitrogen, adding DMF, carrying out reflux reaction at the temperature of 150 ℃ for 11h, and then carrying out a reaction by using a solvent with a volume ratio of 2: and (3) eluting the dichloromethane/petroleum ether solution of the solvent 1 to prepare the degradation accelerator.
Example 4
An environment-friendly degradable plastic packaging film comprises the following raw materials in parts by weight: 40 parts of PBS resin, 30 parts of corn starch, 8.6 parts of nano silicon dioxide, 5.7 parts of calcium stearate, 3.5 parts of nano calcium carbonate, 0.2 part of aluminate and 10.2 parts of degradation accelerator prepared in example 2;
the environment-friendly degradable plastic packaging film is prepared by the following steps:
the method comprises the following steps: micronizing corn starch to 600 meshes by using a jet mill, then putting the corn starch into a high-speed stirrer, adding aluminate ester at the same time, and stirring for 30min at 80 ℃ to obtain modified starch;
step two: adding the PBS resin and the degradation accelerant prepared in the embodiment 2 into a stirring kettle, mixing for 20min at the temperature of 50 ℃, then crushing and sieving with a 60-mesh sieve, sequentially adding the modified starch, the nano-silica, the calcium stearate and the nano-calcium carbonate, and stirring and mixing for 30min at the temperature of 60 ℃ to obtain a mixture;
step three: extruding the mixture by using an extruder, preparing a film by using an ABA type extrusion casting die, and stretching by using a three-roll calender to obtain the environment-friendly degradable plastic packaging film, wherein the extrusion temperature of the extruder is 155 ℃, and the temperature of the extrusion casting die is 170 ℃.
Example 5
An environment-friendly degradable plastic packaging film comprises the following raw materials in parts by weight: 50 parts of PBS resin, 35 parts of corn starch, 9.7 parts of nano silicon dioxide, 8.3 parts of calcium stearate, 5.7 parts of nano calcium carbonate, 0.5 part of aluminate and 11.3 parts of degradation accelerator prepared in example 2;
the environment-friendly degradable plastic packaging film is prepared by the following steps:
the method comprises the following steps: micronizing corn starch to 800 meshes by using a jet mill, then putting the corn starch into a high-speed stirrer, adding aluminate ester at the same time, and stirring for 30min at 90 ℃ to obtain modified starch;
step two: adding the PBS resin and the degradation accelerant prepared in the embodiment 2 into a stirring kettle, mixing for 20min at the temperature of 50 ℃, then crushing and sieving with a 60-mesh sieve, sequentially adding the modified starch, the nano-silica, the calcium stearate and the nano-calcium carbonate, and stirring and mixing for 30min at the temperature of 60 ℃ to obtain a mixture;
step three: extruding the mixture by using an extruder, preparing a film by using an ABA type extrusion casting die, and stretching by using a three-roll calender to obtain the environment-friendly degradable plastic packaging film, wherein the extrusion temperature of the extruder is 160 ℃, and the temperature of the extrusion casting die is 175 ℃.
Example 6
An environment-friendly degradable plastic packaging film comprises the following raw materials in parts by weight: 60 parts of PBS resin, 40 parts of corn starch, 10.8 parts of nano silicon dioxide, 10.9 parts of calcium stearate, 7.9 parts of nano calcium carbonate, 0.8 part of aluminate and 12.4 parts of degradation accelerator prepared in example 2;
the environment-friendly degradable plastic packaging film is prepared by the following steps:
the method comprises the following steps: micronizing corn starch to 1200 meshes by using a jet mill, then putting into a high-speed stirrer, simultaneously adding aluminate, and stirring at 100 ℃ for 30min to obtain modified starch;
step two: adding the PBS resin and the degradation accelerant prepared in the embodiment 2 into a stirring kettle, mixing for 20min at the temperature of 50 ℃, then crushing and sieving with a 60-mesh sieve, sequentially adding the modified starch, the nano-silica, the calcium stearate and the nano-calcium carbonate, and stirring and mixing for 30min at the temperature of 60 ℃ to obtain a mixture;
step three: extruding the mixture by using an extruder, preparing a film by using an ABA type extrusion casting die, and stretching by using a three-roll calender to obtain the environment-friendly degradable plastic packaging film, wherein the extrusion temperature of the extruder is 165 ℃, and the temperature of the extrusion casting die is 180 ℃.
Comparative example: the degradation promoter prepared in example 2 was not added as compared with example 5.
The performance test of examples 4 to 6 and comparative example was performed, the packaging films prepared in examples 4 to 6 and comparative example were weighed after being balanced at room temperature, placed in an ultraviolet illumination box for ultraviolet irradiation, the linear distance from the ultraviolet lamp was maintained at 15 to 20cm, the temperature in the box was controlled at 40 ± 2 ℃, the film was turned over every 1 hour, and the weight loss rate after 240 hours of illumination was calculated, and the test results are shown in table 1, where the weight loss rate is (mass before illumination-mass after illumination)/mass before illumination × 100%.
TABLE 1
As can be seen from table 1, the comparative examples also have certain photodegradability properties, but examples 4 to 6 have better photodegradability properties than the comparative examples.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. An environmental protection degradable plastic packaging film which is characterized in that: the feed comprises the following raw materials in parts by weight: 40-60 parts of PBS resin, 30-40 parts of corn starch, 8.6-10.8 parts of nano silicon dioxide, 5.7-10.9 parts of calcium stearate, 3.5-7.9 parts of nano calcium carbonate, 0.2-0.8 part of aluminate and 10.2-12.4 parts of degradation accelerator;
the degradation promoter is prepared by the following steps:
step S1: adding p-xylene into a flask, adding anhydrous aluminum chloride at the temperature of 5-8 ℃, dropwise adding acetyl chloride into the flask while stirring under the ice bath condition, heating to 50 ℃ after dropwise adding, stirring for reacting for 5-7h, and performing post-treatment after the reaction is finished to obtain an intermediate 1;
step S2: adding the intermediate 1 and deionized water into a flask, then adding potassium permanganate, performing reflux reaction for 2-3h at the temperature of 100 ℃ to obtain an intermediate 2, then adding the intermediate 2 and DMF into the flask, then adding thionyl chloride, introducing nitrogen, and performing reaction for 5-6h at the temperature of 60-65 ℃ to obtain an intermediate 3;
step S3: adding the intermediate 3 and chlorobenzene into a flask, uniformly stirring in ice bath, then adding anhydrous aluminum chloride, stirring for 20min, reacting at room temperature for 1-2h, then heating to 80 ℃, reacting for 8-12h, and after the reaction is finished, performing post-treatment to obtain an intermediate 4;
step S4: adding the intermediate 4, potassium carbonate and deionized water into a flask, stirring and mixing uniformly, adding tetraethylammonium bromide, and carrying out reflux reaction for 1-2 hours at the temperature of 110-120 ℃ to obtain an intermediate 5;
step S5: adding the intermediate 5, pyridine and tetrahydrofuran into a flask, stirring, adding p-aminobenzoyl chloride, introducing nitrogen, and reacting at 40-50 ℃ for 3-4h to obtain an intermediate 6;
step S6: adding the intermediate 6, cesium carbonate and 3-fluorobenzophenone into a flask, introducing nitrogen, adding DMF, carrying out reflux reaction at the temperature of 150 ℃ for 10-11h, and then carrying out a reaction by using a solvent with a volume ratio of 2: and (3) eluting the dichloromethane/petroleum ether solution of the solvent 1 to prepare the degradation accelerator.
2. The environment-friendly degradable plastic packaging film according to claim 1, wherein: the dosage ratio of the p-xylene, the anhydrous aluminum chloride and the acetyl chloride in the step S1 is 0.6 mol: 0.2 mol: 16 g.
3. The environment-friendly degradable plastic packaging film according to claim 1, wherein: in step S2, the dosage ratio of the intermediate 1 to the potassium permanganate is 0.1 g: 2g, the dosage ratio of the intermediate 2 to the thionyl chloride is 0.2 g: 3.5 g.
4. The environment-friendly degradable plastic packaging film according to claim 1, wherein: in the step S3, the dosage ratio of the intermediate 3, the chlorobenzene and the anhydrous aluminum chloride is 0.1 mol: 0.3 mol: 0.05 mol.
5. The environment-friendly degradable plastic packaging film according to claim 1, wherein: in the step S4, the using amount ratio of the intermediate 4, the potassium carbonate, the deionized water and the tetraethyl ammonium bromide is 5 g: 0.5 g: 50mL of: 0.6 g.
6. The environment-friendly degradable plastic packaging film according to claim 1, wherein: the using ratio of the intermediate 5, the pyridine, the tetrahydrofuran and the p-aminobenzoyl chloride in the step S5 is 0.05 mol: 0.05 mol: 50mL of: 0.1 mol.
7. The environment-friendly degradable plastic packaging film according to claim 1, wherein: step S6, wherein the dosage ratio of the intermediate 6, the cesium carbonate and the 3-fluorobenzophenone is 0.5 mol: 0.6 mol: 1.1 mol.
8. The method for preparing the environment-friendly degradable plastic packaging film according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
the method comprises the following steps: micronizing corn starch to 600-1200 meshes by using a jet mill, then placing the corn starch into a high-speed stirrer, and simultaneously adding aluminate to stir for 30min at 80-100 ℃ to obtain modified starch;
step two: adding the PBS resin and the degradation accelerant into a stirring kettle, mixing for 20min at the temperature of 50 ℃, then crushing and sieving with a 60-mesh sieve, sequentially adding the modified starch, the nano-silicon dioxide, the calcium stearate and the nano-calcium carbonate, and stirring and mixing for 30min at the temperature of 60 ℃ to obtain a mixture;
step three: extruding the mixture by using an extruder, preparing a film by using an ABA type extrusion casting die, and stretching by using a three-roller calender to obtain the environment-friendly degradable plastic packaging film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116421892A (en) * | 2023-04-08 | 2023-07-14 | 深圳虹望奈喜美电器有限公司 | Full-cladding atomizing cover for plasma beauty instrument |
| CN116463562A (en) * | 2023-03-10 | 2023-07-21 | 无锡熠卿锋金属科技有限公司 | Low-carbon steel wire for high-cleaning-strength electrophoretic paint and production process thereof |
| CN116903979A (en) * | 2023-09-13 | 2023-10-20 | 台州黄岩泽钰新材料科技有限公司 | Antistatic starch-based biodegradable material and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535670A (en) * | 2018-11-16 | 2019-03-29 | 广东众塑降解材料有限公司 | A kind of Wholly-degradable emulation material and preparation method thereof |
| CN109988400A (en) * | 2019-04-18 | 2019-07-09 | 谷水英 | A kind of environment-friendly type degradable packaging composite film and preparation method thereof |
-
2021
- 2021-06-28 CN CN202110721689.7A patent/CN113321832A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535670A (en) * | 2018-11-16 | 2019-03-29 | 广东众塑降解材料有限公司 | A kind of Wholly-degradable emulation material and preparation method thereof |
| CN109988400A (en) * | 2019-04-18 | 2019-07-09 | 谷水英 | A kind of environment-friendly type degradable packaging composite film and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116463562A (en) * | 2023-03-10 | 2023-07-21 | 无锡熠卿锋金属科技有限公司 | Low-carbon steel wire for high-cleaning-strength electrophoretic paint and production process thereof |
| CN116421892A (en) * | 2023-04-08 | 2023-07-14 | 深圳虹望奈喜美电器有限公司 | Full-cladding atomizing cover for plasma beauty instrument |
| CN116421892B (en) * | 2023-04-08 | 2024-03-26 | 深圳虹望奈喜美电器有限公司 | Full-cladding atomizing cover for plasma beauty instrument |
| CN116903979A (en) * | 2023-09-13 | 2023-10-20 | 台州黄岩泽钰新材料科技有限公司 | Antistatic starch-based biodegradable material and preparation process thereof |
| CN116903979B (en) * | 2023-09-13 | 2023-12-08 | 台州黄岩泽钰新材料科技有限公司 | Antistatic starch-based biodegradable material and preparation process thereof |
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