CN109703143B - Stretch-proof degradable barrier plastic packaging film and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of barrier packaging film preparation, and particularly relates to a stretch-proof degradable barrier plastic packaging film and a preparation method thereof. Melting, blending and modifying a carbon dioxide copolymer and maleic anhydride serving as raw materials, extruding and granulating, mixing and extruding a product with hydroxyl-rich monodisperse silicon dioxide microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate, a free radical initiator and the like to prepare a carbon dioxide copolymer barrier layer; and (3) taking crystalline polylactic acid as an outer layer, converging three layers of melts in a T-shaped die head to form a melt film, and stretching to obtain the stretch-proof degradable barrier plastic packaging film. According to the invention, the monodisperse silicon dioxide microspheres rich in hydroxyl groups are added during the composite crosslinking of the active monomer and the carbon dioxide copolymer terminated by anhydride, and blending modification is carried out, so that carbon dioxide copolymer macromolecules are grafted onto the surfaces of the microspheres to form winding coating while a crosslinking structure is formed, the tensile property is improved, and the barrier property of the middle barrier layer is effectively improved.
Description
Technical Field
The invention belongs to the technical field of packaging film preparation, and particularly relates to a stretch-proof degradable barrier plastic packaging film and a preparation method thereof.
Background
Many conventional packaging films (such as PP, PE, PVC, PET) have good heat sealability, printability, metallisation, gas barrier properties and a controllable coefficient of friction, but none of these materials have biodegradability and are environmentally friendly. With the development of fully biodegradable materials, the biodegradable materials are gradually applied to packaging films, such as polylactic acid films (BOPLA films), but polylactic acid itself has poor barrier properties and cannot be used as a barrier material alone.
Chinese patent 200980108671.7 discloses a biodegradable composite oxygen barrier film, which is composed of at least two support layers and a barrier layer arranged between every two support layers, and the composite oxygen barrier film is beneficial to prolonging the shelf life and shelf life of food, medicines and the like; meanwhile, the white pollution can be prevented, but the film is prepared by adopting a multi-layer co-extrusion method, so that the mechanical property of the film is poor, and the application range is limited.
The Chinese patent application No. 200510002129.7 discloses a high-barrier degradable film product and a manufacturing method thereof, in particular to a degradable composite film prepared by using carbon dioxide resin as a barrier material. The high-barrier degradable film has a layered structure at least comprising two outer layers and a barrier layer, wherein the barrier layer is a nano polymer or a degradable nano polymer, and the outer layer is polyolefin or degradable polyolefin. The high-barrier degradation film has good transparency, air resistance, heat sealing property and printability, solves the problem that the existing dry type composite or co-extruded plastic food film bags at home and abroad do not have the characteristic of environmental protection, meets the performance requirements of the currently and commonly adopted high-temperature cooking resistant food packaging films and bags, can be degraded into small molecular materials under the action of light and/or biology, and is a high-performance environment-friendly product.
The Chinese patent application No. 201510890282.1 discloses a controlled-release active modified atmosphere fresh-keeping packaging material and a preparation method thereof, belonging to the technical field of food and fruit and vegetable fresh-keeping. The main components are 0.5-10 wt% of natural antibacterial agent, 5-30 wt% of ethylene-vinyl acetate copolymer, 1-45 wt% of block copolymer and not less than 40 wt% of polyolefin master batch. The materials mixed according to the proportion are melted, blended and granulated, and then are blown or extruded to form the packaging material. The material is used as a packaging film of fresh fruits and vegetables, can provide a relatively suitable humidity (RH 70-98%) and a suitable atmosphere packaging atmosphere of oxygen and carbon dioxide for the fruits and vegetables, and slowly releases a natural antibacterial agent to inhibit the respiration of the fruits and vegetables and the growth of fungi on the surfaces of the fruits and vegetables, so that the effect of prolonging the fresh-keeping period of the fruits and vegetables is achieved.
The Chinese patent application No. 201810022510.7 discloses a degradable packaging film, which is prepared from the following raw materials in parts by weight: 50-60 parts of seaweed, 20-30 parts of sweet potato starch, 5-10 parts of trichlorocyanamide, 10-15 parts of polyethylene, 4-8 parts of sorbitol, 2-5 parts of modified hydroxymethyl cellulose and 0.5-3 parts of a stabilizer. The invention takes seaweed and sweet potato starch as main raw materials, and is matched with trichlorocyanamide, polyethylene, sorbitol and modified hydroxymethyl cellulose, and the produced packaging film is environment-friendly and nontoxic, and has the advantages of high temperature resistance, high toughness and degradability.
The invention discloses a degradable environment-friendly packaging film, which relates to the technical field of packaging films, and is characterized in that sweet potatoes and seaweed are used as main raw materials, high-gluten flour is added, and various auxiliary agents are added, so that the prepared packaging film has strong physical and mechanical properties, selective permeability, antibacterial and antioxidant effects; and the selected raw materials are green, safe, environment-friendly and easy to degrade, thereby avoiding white pollution and protecting the ecological environment.
CO2The high molecular biodegradable material with a pure binary structure polymerized with the epoxy compound has biodegradability and simultaneously shows good water vapor and oxygen barrier properties, but the application of the biodegradable material is limited due to poor physical properties (such as poor tensile strength and low-temperature brittleness) and residues of a large amount of catalysts in the production process, so that large-scale industrialization is not realized.
Disclosure of Invention
Aiming at the problem that the barrier film prepared from the existing carbon dioxide copolymer has poor mechanical property and thermal stability, the invention provides a stretch-proof degradable barrier plastic packaging film and a preparation method thereof.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a stretch-proof degradable barrier plastic packaging film comprises the following steps:
s1, uniformly mixing the carbon dioxide copolymer and maleic anhydride serving as raw materials, putting the mixture into an extruder, carrying out melt blending modification at 120-160 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and free radical initiator, and putting the mixture into an extruder to extrude the mixture to serve as an intermediate barrier material;
s3, uniformly mixing crystalline polylactic acid, a toughening agent, an antistatic agent, an antioxidant, a slipping agent and an anti-blocking agent, and respectively adding the ingredients into corresponding extruders to perform melting and plasticizing at 150-180 ℃ to obtain a polylactic acid layer material;
and S4, converging in a T-shaped die by using a three-layer co-extrusion extruder, taking the intermediate barrier material obtained in the step S2 as an intermediate layer, taking the polylactic acid layer obtained in the step S3 as a surface layer, covering the two sides of the carbon dioxide copolymer barrier layer to form a molten film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally setting to finally obtain the stretch-proof degradable barrier plastic packaging film.
Further, the preparation method of the stretch-proof degradable barrier plastic packaging film comprises the step of S1, wherein the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 10-20: 5-15. The carbon dioxide polymer material is a green high molecular material prepared by taking carbon dioxide as a main raw material and synthesizing the carbon dioxide by a chemical method, turns the harm of the carbon dioxide into the benefit and changes the carbon dioxide into the valuable, can be completely biodegraded, and is an important green ecological material for saving and replacing petroleum resources; the carbon dioxide-based polymer is prepared by copolymerizing carbon dioxide and hydrocarbon serving as raw materials, wherein the content of the carbon dioxide accounts for 31-50%.
Further, in the above method for preparing a stretch-proof degradable barrier plastic packaging film, the radical initiator in the step S2 is at least one of cyclohexanone peroxide, dibenzoyl peroxide and tert-butyl hydroperoxide.
Further, the preparation method of the stretch-proof degradable barrier plastic packaging film comprises the step of S2, wherein the mass ratio of the end-capped modified carbon dioxide copolymer granules, the monodisperse silica microspheres, the active monomer N-vinyl pyrrolidone, the chain extender diisocyanate and the free radical initiator is 20-40: 5-15: 3-10: 3-8: 0.1.
Further, in the preparation method of the stretch-proof degradable barrier plastic packaging film, the extrusion temperature condition of the extruder in the step S2 is 80-120 ℃.
Further, in the above preparation method of the stretch-proof degradable barrier plastic packaging film, in the step S3, the toughening agent is at least one of a maleic anhydride grafted ethylene-propylene copolymer, a maleic anhydride grafted ethylene-propylene-diene terpolymer, a copolymer of styrene and butadiene; the antistatic agent is at least one of carbon black, graphite, graphene, carbon nanotubes and conductive metal powder; the antioxidant is a phenol antioxidant; the phenolic antioxidant is at least one of hydroquinone, thiobisphenol and triphenol; the slipping agent is at least one of erucamide and oleamide; the anti-blocking agent is at least one of silicon dioxide, calcium carbonate, aluminum oxide, titanium dioxide, barium sulfate and talcum powder.
Further, the preparation method of the stretch-proof degradable barrier plastic packaging film comprises the step of S3, wherein the mass ratio of the crystalline polylactic acid, the toughening agent, the antistatic agent, the antioxidant, the slipping agent and the anti-blocking agent is 10-25: 5-10: 3-8: 2-6: 5-8: 3-10.
Further, in the preparation method of the stretch-proof degradable barrier plastic packaging film, the cooling temperature in the step S4 is 30-50 ℃; the transverse stretching is to preheat the membrane at 40-110 ℃, the preheating time is 10-40 min, and the stretching multiple is 2-6 times; the longitudinal stretching is to preheat the membrane at 40-85 ℃, the preheating time is 10-40 min, and the stretching multiple is 1-3 times; the heat setting temperature is 50-160 ℃.
Further, in the preparation method of the stretch-proof degradable barrier plastic packaging film, the heat setting temperature in the step S4 is 50-160 ℃.
The invention also provides a stretch-proof degradable barrier plastic packaging film prepared by the preparation method, wherein monodisperse silica microspheres rich in hydroxyl groups are added during composite crosslinking of an active monomer and an anhydride-terminated carbon dioxide copolymer to perform reactive blending modification, carbon dioxide copolymer macromolecules are grafted to the surfaces of the microspheres to form winding coating while initiating formation of a crosslinked structure, so that the compatibility is improved, the interface bonding force between the carbon dioxide copolymer and filled inorganic microspheres is enhanced, the morphological structure is stabilized, the tensile property is improved, the mechanical property and the thermal stability of an intermediate barrier layer are effectively improved, and large-scale application is facilitated.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A preparation method of a stretch-proof degradable barrier plastic packaging film comprises the following steps:
s1, taking the carbon dioxide copolymer and maleic anhydride as raw materials, uniformly mixing, then putting into an extruder, carrying out melt blending modification at the temperature of 140 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride; the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 15: 8;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and free radical initiator, putting into an extruder, and reacting and extruding at 100 ℃ to obtain a carbon dioxide copolymer barrier layer material with a cross-linked structure; the free radical initiator is cyclohexanone peroxide; the mass ratio of the end-capped modified carbon dioxide copolymer granules to the monodisperse silicon dioxide microspheres to the active monomer N-vinyl pyrrolidone to the chain extender diisocyanate to the free radical initiator is 30:10:5:6: 0.1;
s3, uniformly mixing the crystalline polylactic acid, the flexibilizer, the antistatic agent, the antioxidant, the slipping agent and the anti-blocking agent, and respectively adding the ingredients into corresponding extruders to melt and plasticize at 170 ℃ to obtain a polylactic acid layer; the toughening agent is a maleic anhydride grafted ethylene-propylene copolymer; the antistatic agent is graphene; the antioxidant is thiobisphenol; the slipping agent is erucamide; the anti-blocking agent is silicon dioxide; the mass ratio of the crystalline polylactic acid to the toughening agent to the antistatic agent to the antioxidant to the slipping agent to the anti-blocking agent is 20:7:5:4:7: 9;
s4, taking the carbon dioxide copolymer barrier layer material obtained in the step S2 as a middle layer, taking the polylactic acid layer obtained in the step S3 as a surface layer, covering the two sides of the carbon dioxide copolymer barrier layer, converging three layers of melts in a T-shaped die to form a melt film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally shaping to finally obtain the stretch-proof degradable barrier plastic packaging film; the cooling temperature is 40 ℃; the transverse stretching is to preheat the membrane at 70 ℃, the preheating time is 30min, and the stretching multiple is 5 times; the longitudinal stretching is to preheat the membrane at 50 ℃, the preheating time is 30min, and the stretching multiple is 2 times; the heat-setting temperature was 100 ℃.
Example 2
A preparation method of a stretch-proof degradable barrier plastic packaging film comprises the following steps:
s1, taking the carbon dioxide copolymer and maleic anhydride as raw materials, uniformly mixing, then putting into an extruder, carrying out melt blending modification at the temperature of 150 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride; the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 13: 12;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and free radical initiator, putting into an extruder, and reacting and extruding at 90 ℃ to obtain a carbon dioxide copolymer barrier layer material with a cross-linked structure; the free radical initiator is dibenzoyl peroxide; the mass ratio of the end-capped modified carbon dioxide copolymer granules to the monodisperse silicon dioxide microspheres to the active monomer N-vinyl pyrrolidone to the chain extender diisocyanate to the free radical initiator is 25:12:8:5: 0.1;
s3, uniformly mixing crystalline polylactic acid, a toughening agent, an antistatic agent, an antioxidant, a slipping agent and an anti-blocking agent, and respectively adding the ingredients into corresponding extruders to perform melting and plasticizing at 150-180 ℃ to obtain a polylactic acid layer; the toughening agent is a maleic anhydride grafted ethylene-propylene-diene terpolymer; the antistatic agent is a carbon nano tube; the antioxidant is hydroquinone; the slipping agent is oleamide; the anti-blocking agent is titanium dioxide; the mass ratio of the crystalline polylactic acid to the toughening agent to the antistatic agent to the antioxidant to the slipping agent to the anti-blocking agent is 22:9:7:4:7: 8;
s4, taking the carbon dioxide copolymer barrier layer material obtained in the step S2 as a middle layer, taking the polylactic acid layer obtained in the step S3 as a surface layer, covering the two sides of the carbon dioxide copolymer barrier layer, converging three layers of melts in a T-shaped die to form a melt film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally shaping to finally obtain the stretch-proof degradable barrier plastic packaging film; the cooling temperature is 45 ℃; the transverse stretching is to preheat the membrane at 60 ℃, the preheating time is 15min, and the stretching multiple is 5 times; the longitudinal stretching is to preheat the membrane at 55 ℃, the preheating time is 25min, and the stretching multiple is 3 times; the heat-setting temperature was 80 ℃.
Example 3
A preparation method of a stretch-proof degradable barrier plastic packaging film comprises the following steps:
s1, taking the carbon dioxide copolymer and maleic anhydride as raw materials, uniformly mixing, then putting into an extruder, carrying out melt blending modification at the temperature of 130 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride; the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 14: 8;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and a free radical initiator, putting the mixture into an extruder, and reacting and extruding the mixture at the temperature of 90 ℃ to obtain a carbon dioxide copolymer barrier layer material with a cross-linked structure, wherein the free radical initiator is tert-butyl hydroperoxide; the mass ratio of the end-capped modified carbon dioxide copolymer granules to the monodisperse silica microspheres to the active monomer N-vinyl pyrrolidone to the chain extender diisocyanate to the free radical initiator is 23:10:7:4: 0.9;
s3, uniformly mixing the crystalline polylactic acid, the flexibilizer, the antistatic agent, the antioxidant, the slipping agent and the anti-blocking agent, and respectively adding the ingredients into corresponding extruders to perform melting and plasticizing at 160 ℃ to obtain a polylactic acid layer; the toughening agent is styrene; the antistatic agent is graphite; the antioxidant is thiotriphenol; the slipping agent is erucamide; the anti-adhesion agent is talcum powder; the mass ratio of the crystalline polylactic acid to the toughening agent to the antistatic agent to the antioxidant to the slipping agent to the anti-blocking agent is 12:8:7:5:6: 9;
s4, taking the carbon dioxide copolymer barrier layer material obtained in the step S2 as a middle layer, taking the polylactic acid layer obtained in the step S3 as a surface layer, covering the two sides of the carbon dioxide copolymer barrier layer, converging three layers of melts in a T-shaped die to form a melt film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally shaping to finally obtain the stretch-proof degradable barrier plastic packaging film; the cooling temperature is 35 ℃; the transverse stretching is to preheat the membrane at 85 ℃, the preheating time is 25min, and the stretching multiple is 4 times; the longitudinal stretching is to preheat the membrane at 70 ℃, the preheating time is 30min, and the stretching multiple is 2 times; the heat-setting temperature was 110 ℃.
Example 4
A preparation method of a stretch-proof degradable barrier plastic packaging film comprises the following steps:
s1, taking the carbon dioxide copolymer and maleic anhydride as raw materials, uniformly mixing, then putting into an extruder, carrying out melt blending modification at the temperature of 130 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride; the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 14: 9;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and free radical initiator, putting into an extruder, and reacting and extruding at 90 ℃ to obtain a carbon dioxide copolymer barrier layer material with a cross-linked structure; the free radical initiator is dibenzoyl peroxide; the mass ratio of the end-capped modified carbon dioxide copolymer granules to the monodisperse silica microspheres to the active monomer N-vinyl pyrrolidone to the chain extender diisocyanate to the free radical initiator is 30:9:5:8: 0.1;
s3, uniformly mixing the crystalline polylactic acid, the flexibilizer, the antistatic agent, the antioxidant, the slipping agent and the anti-blocking agent, and respectively adding the ingredients into corresponding extruders to melt and plasticize at 170 ℃ to obtain a polylactic acid layer; the toughening agent is a maleic anhydride grafted ethylene-propylene copolymer; the antistatic agent is carbon black; the antioxidant is hydroquinone; the slipping agent is erucamide; the anti-blocking agent is barium sulfate; the mass ratio of the crystalline polylactic acid to the toughening agent to the antistatic agent to the antioxidant to the slipping agent to the anti-blocking agent is 18:8:6:5:7: 7;
s4, taking the carbon dioxide copolymer barrier layer material obtained in the step S2 as a middle layer, taking the polylactic acid layer obtained in the step S3 as a surface layer, covering the two sides of the carbon dioxide copolymer barrier layer, converging three layers of melts in a T-shaped die to form a melt film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally shaping to finally obtain the stretch-proof degradable barrier plastic packaging film; the cooling temperature is 45 ℃; the transverse stretching is to preheat the membrane at 70 ℃, the preheating time is 23min, and the stretching multiple is 5 times; the longitudinal stretching is to preheat the membrane at 60 ℃, the preheating time is 25min, and the stretching multiple is 2 times; the heat-setting temperature was 70 ℃.
Example 5
A preparation method of a stretch-proof degradable barrier plastic packaging film comprises the following steps:
s1, taking the carbon dioxide copolymer and maleic anhydride as raw materials, uniformly mixing, then putting into an extruder, carrying out melt blending modification at the temperature of 145 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride; the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 16: 7;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and free radical initiator, putting into an extruder, and reacting and extruding at the temperature of 80-120 ℃ to obtain a carbon dioxide copolymer barrier layer material with a cross-linked structure; the free radical initiator is tert-butyl hydroperoxide; the mass ratio of the end-capped modified carbon dioxide copolymer granules to the monodisperse silicon dioxide microspheres to the active monomer N-vinyl pyrrolidone to the chain extender diisocyanate to the free radical initiator is 22:9:8:7: 2;
s3, uniformly mixing the crystalline polylactic acid, the flexibilizer, the antistatic agent, the antioxidant, the slipping agent and the anti-blocking agent, and respectively adding the ingredients into corresponding extruders to melt and plasticize at 170 ℃ to obtain a polylactic acid layer; the toughening agent is a copolymer of butadiene; the antistatic agent is conductive metal powder; the antioxidant is thiobisphenol; the slipping agent is erucamide; the anti-blocking agent is aluminum oxide; the mass ratio of the crystalline polylactic acid to the toughening agent to the antistatic agent to the antioxidant to the slipping agent to the anti-blocking agent is 17:6:7:5:7: 8;
s4, taking the carbon dioxide copolymer barrier layer material obtained in the step S2 as a middle layer, taking the polylactic acid layer obtained in the step S3 as a surface layer, covering the two sides of the carbon dioxide copolymer barrier layer, converging three layers of melts in a T-shaped die to form a melt film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally shaping to finally obtain the stretch-proof degradable barrier plastic packaging film; the cooling temperature is 45 ℃; the transverse stretching is to preheat the membrane at 80 ℃, the preheating time is 23min, and the stretching multiple is 4 times; the longitudinal stretching is to preheat the membrane at 65 ℃, the preheating time is 26min, and the stretching multiple is 2 times; the heat-setting temperature was 120 ℃.
Comparative example 1
A barrier packaging film is prepared by blending modification without adding hydroxyl-rich monodisperse silica microspheres during composite crosslinking of an active monomer and an anhydride-terminated carbon dioxide copolymer, and the other raw materials and steps are the same as those in example 5.
The performance tests of the barrier packaging films obtained in examples 1 to 5 and comparative example 1 were as follows:
the tensile strength test refers to a film tensile property test method of GB 13022-1991.
The thermal shrinkage test method refers to GB/T13519-2016 (Standard for testing the thermal shrinkage of polyethylene) for packaging.
Wherein MD = machine direction and TD = transverse direction; MD: machine Direction, i.e. the longitudinal Direction. TD: transverse Direction, perpendicular to the machine Direction, i.e. in the Transverse sense.
Table 1 shows the test results of examples 1 to 5 and comparative example 1.
Claims (8)
1. A preparation method of a stretch-proof degradable barrier plastic packaging film is characterized by comprising the following steps:
s1, uniformly mixing the carbon dioxide copolymer and maleic anhydride serving as raw materials, putting the mixture into an extruder, carrying out melt blending modification at 120-160 ℃, and carrying out extrusion granulation to obtain carbon dioxide copolymer granules with end capped by anhydride; the mass ratio of the carbon dioxide copolymer to the maleic anhydride is 10-20: 5-15;
s2, mixing the end-capped modified carbon dioxide copolymer granules obtained in the step S1 with hydroxyl-rich monodisperse silica microspheres, active monomer N-vinyl pyrrolidone, chain extender diisocyanate and free radical initiator, and putting the mixture into an extruder to extrude the mixture to serve as an intermediate barrier material; the mass ratio of the end-capped modified carbon dioxide copolymer granules to the monodisperse silica microspheres to the active monomer N-vinyl pyrrolidone to the chain extender diisocyanate to the free radical initiator is 20-40: 5-15: 3-10: 3-8: 0.1;
s3, uniformly mixing crystalline polylactic acid, a toughening agent, an antistatic agent, an antioxidant, a slipping agent and an anti-blocking agent, adding into an extruder, and melting and plasticizing at 150-180 ℃ to obtain a polylactic acid layer material;
and S4, converging in a T-shaped die by using a three-layer co-extrusion extruder, taking the intermediate barrier material obtained in the step S2 as an intermediate layer, taking the polylactic acid layer material obtained in the step S3 as a surface layer, covering the two sides of the intermediate layer to form a molten film, cooling to obtain a membrane, transversely stretching, longitudinally stretching, and thermally shaping to finally obtain the stretch-proof degradable barrier plastic packaging film.
2. The method of claim 1, wherein the radical initiator in step S2 is at least one of cyclohexanone peroxide, dibenzoyl peroxide, and tert-butyl hydroperoxide.
3. The method for preparing the stretch-proof degradable barrier plastic packaging film according to claim 1, wherein the extrusion temperature of the extruder in the step S2 is 80-120 ℃.
4. The method for preparing the stretch-proof degradable barrier plastic packaging film according to claim 1, wherein the toughening agent in the step S3 is at least one of a maleic anhydride grafted ethylene-propylene copolymer and a maleic anhydride grafted ethylene-propylene-diene terpolymer; the antistatic agent is at least one of carbon black, graphite, graphene, carbon nanotubes and conductive metal powder; the antioxidant is a phenol antioxidant, and the phenol antioxidant is at least one of hydroquinone, thiobisphenol and triphenol; the slipping agent is at least one of erucamide and oleamide; the anti-blocking agent is at least one of silicon dioxide, calcium carbonate, aluminum oxide, titanium dioxide, barium sulfate and talcum powder.
5. The preparation method of the stretch-proof degradable barrier plastic packaging film according to claim 1 or 4, wherein the mass ratio of the crystalline polylactic acid, the toughening agent, the antistatic agent, the antioxidant, the slipping agent and the anti-blocking agent in the step S3 is 10-25: 5-10: 3-8: 2-6: 5-8: 3-10.
6. The method for preparing the stretch-proof degradable barrier plastic packaging film according to claim 1, wherein the cooling temperature in the step S4 is 30-50 ℃; the transverse stretching is to preheat the membrane at 40-110 ℃, the preheating time is 10-40 min, and the stretching multiple is 2-6 times; the longitudinal stretching is to preheat the membrane at 40-85 ℃, the preheating time is 10-40 min, and the stretching multiple is 1-3 times; the heat setting temperature is 50-160 ℃.
7. The method for preparing the stretch-proof degradable barrier plastic packaging film according to claim 1, wherein the heat setting temperature in the step S4 is 50-160 ℃.
8. A stretch-proof degradable barrier plastic packaging film prepared according to the preparation method of any one of claims 1-7.
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