CN109703143A - A kind of degradable barrier plastic packaging film and preparation method of stretch-proof - Google Patents
A kind of degradable barrier plastic packaging film and preparation method of stretch-proof Download PDFInfo
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Abstract
The invention belongs to the technical fields of barrier package film preparation, and in particular to a kind of degradable barrier plastic packaging film and preparation method of stretch-proof.Carbon dioxide copolymer and maleic anhydride is modified for raw material melt blending, extruding pelletization, product mixes extrusion with monodisperse silica microspheres, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator etc. rich in hydroxyl, prepares carbon dioxide copolymer barrier layer；Using crystalline polylactic acid as outer layer, converge in T-die in three layers of melt, form melt films, stretches, obtain the degradable barrier plastic packaging film of stretch-proof.The present invention is rich in the monodisperse silica microspheres of hydroxyl by being added in the carbon dioxide copolymer composite crosslinking of activated monomer and acid anhydrides sealing end, carry out blending and modifying, there is carbon dioxide copolymer macromolecular to be grafted on microsphere surface while initiation forms cross-linked structure, formation is wrapped around, tensile property is promoted, intermediate barrier layer is effectively improved.
Description
Technical field
The invention belongs to pack the technical field of film preparation, and in particular to a kind of degradable barrier plastics package of stretch-proof
Film and preparation method.
Background technique
Many traditional packaging films (such as PP, PE, PVC, PET), they have good heat sealability, printing, gold-plated attribute,
Barrier properties for gases and controllable coefficient of friction, but these materials do not have biodegradability, pollute environment.With complete raw
The exploitation of object degradable material, biodegradation material are gradually applied in packaging film, such as polylactic acid membrane (BOPLA film), but poly- cream
The barrier property of acid itself is poor, cannot individually use as barrier material.
Chinese patent 200980108671.7 discloses a kind of biodegradable composite oxygen barrier film, is by least two supports
Layer and the barrier layer being located between every two supporting layer composition, the composite oxygen barrier film are conducive to extend food and drug etc.
Shelf-life, shelf life；It can prevent the advantages of causing white pollution simultaneously, but it is using multi-layer co-extruded method
It prepares, the mechanical performance of film is poor, use scope is restricted.
The special application number 200510002129.7 of Chinese invention discloses a kind of high-block degradable membrane product and its manufacturing method,
Specifically a kind of degradable composite membrane prepared with carbon dioxide resin as barrier material.High-barrier of the present invention
Degradative membrane has the layer structure including at least two outer layers and a barrier layer, and barrier layer is nanometer polymer or degradable
Nanometer polymer;Outer layer is polyolefin or Degradable polyolefin.High-block degradable membrane of the present invention has good transparent
Property, gas barrier, heat sealability, impressionability, solve that domestic and international existing dry type is compound or coextruded plastic food-film bag does not have ring
The problem of guarantor's feature, meet generally use at present digestion resistant food package film, bag performance requirement, can light and/
Or it is degraded to small molecule material under biological effect, it is a kind of high-performance environment-friendly product.
Chinese invention patent application number 201510890282.1 discloses a kind of active controlled atmosphere fresh-keeping packing of control release
Material and preparation method thereof belongs to food and postharvest technology of fruits and vegetables field.Main component is that mass fraction is 0.5~10wt%
Natural antibacterial agent, the ethylene-vinyl acetate copolymer of 5~30wt%, 1~45wt% block copolymer and be not less than 40wt%
Polyolefin masterbatch.After granulation is blended in the material molten mixed in proportion, the manufactured packaging material through blown film or extrusion molding.
Packaging film using the material as fresh fruit of vegetables can provide more suitable humidity (RH70~98%) for fruits and vegetables and be suitable for
Oxygen and carbon dioxide controlled atmospheric packing atmosphere, and slow release natural antibacterial agent, with inhibit fruits and vegetables respiration and
The growth of fruit and vegetable surfaces mushroom has the function that extend the preserving fruit and vegetable utilizing phase.
Chinese invention patent application number 201810022510.7 discloses a kind of degradable packaging film, by following parts by weight
Several raw materials are made: 50-60 parts of seaweed, 20-30 parts of starch from sweet potato, and three 5-10 parts of chlorocyanamides, 10-15 parts of polyethylene, sorbose
It is 4-8 parts of alcohol, hydroxymethyl cellulose 2-5 parts, 0.5-3 parts of stabilizer modified.The present invention using seaweed and starch from sweet potato as primary raw material,
It is equipped with three chlorocyanamides, polyethylene, D-sorbite, modified hydroxymethyl cellulose again, the packaging film of production is environmentally friendly, nontoxic and have
Have the advantages that resistant to high temperatures, toughness is high, degradable.
Chinese invention patent application number 201810191024.8 discloses a kind of degradable environment-protective packaging film, is related to packing
Technical field of membrane, the present invention add Strong flour using sweet potato and seaweed as primary raw material, are aided with various auxiliary agents, make obtained
Packaging film has stronger physical mechanical property, selective penetrated property and antibacterial, antioxidation；And selected raw material green,
It is safe and environment-friendly, be easily degraded, so as to avoid white pollution, preserve the ecological environment.
CO2There is biodegradability with the pure diadactic structure high-molecular biologic degradable material of epoxy compounds polymerization,
The barrier property of good steam, oxygen is shown simultaneously, but due to physical property poor (such as poor tensile strength, black brittleness) and life
The residual of a large amount of catalyst during producing, is restricted the application of such biodegradation material, thus never extensive
Industrialization.
Summary of the invention
For existing carbon dioxide copolymer prepare barrier film be there are mechanical property with thermal stability is poor asks
Topic, the present invention propose the degradable barrier plastic packaging film and preparation method of a kind of stretch-proof.
To solve the above problems, the invention adopts the following technical scheme:
A kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, comprising the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, put into extruder after evenly mixing, it is molten at 120 ~ 160 DEG C
Melt blending and modifying, extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing investment extruder squeeze out
As centre barrier material；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 150 ~ 180 DEG C, polylactic acid layered material is obtained；
S4, being converged in T-die using three-layer co-extruded extruder, the intermediate barrier material that step S2 is obtained is used as middle layer,
The polylactic acid layers that step S3 is obtained are covered on the two sides of carbon dioxide copolymer barrier layer as surface layer, form melt films, cooling
Diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S1 step
The mass ratio of the carbon dioxide copolymer and maleic anhydride is 10~20:5~15.Carbon dioxide polymer material is with dioxy
Change carbon be primary raw material be chemically synthesized prepared by Green Polymer Material, carbon dioxide is turned harm into good become give up into
Treasured, fully biodegradable are the important Green Ecological Materials for saving and substituting petroleum resources；Carbon dioxide based polyalcohol be with
Carbon dioxide and hydrocarbon form for material copolymerization, and wherein carbon dioxide content accounts for 31%-50%.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S2 step
The radical initiator is at least one of cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S2 step
The carbon dioxide copolymer pellet of the blocking modification, monodisperse silica microspheres, activated monomer n-vinyl pyrrolidone,
Chain extender diisocyanate, radical initiator mass ratio be 20~40:5~15:3~10:3~8:0.1.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S2 step
The extrusion temperature condition of the extruder is 80 ~ 120 DEG C.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S3 step
The toughener be maleic anhydride grafted ethene-propylene copolymer, maleic anhydride grafted ethene-propylenediene terpolymer,
At least one of styrene, copolymer of butadiene；The antistatic agent is carbon black, graphite, graphene, carbon nanotube, leads
At least one of electric metal powder；The antioxidant is phenolic antioxidant；The phenolic antioxidant is hydroquinone, thiobis
At least one of phenol, triphenol；The slipping agent is at least one of erucyl amide, oleamide；The antiblocking agent is
At least one of silica, calcium carbonate, aluminium oxide, titanium dioxide, barium sulfate, talcum powder.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S3 step
The crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent mass ratio be 10~25:5~
10:3~8:2~6:5~8:3~10.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S4 step
The temperature of the cooling is 30~50 DEG C；The cross directional stretch is that diaphragm is preheated at 40~110 DEG C, preheating time 10~
40min, draw ratio are 2~6 times；The longitudinal stretching is that diaphragm is preheated at 40~85 DEG C, preheating time 10~
40min, draw ratio are 1~3 times；The temperature of the thermal finalization is 50 DEG C~160 DEG C.
Further, the preparation method of the degradable barrier plastic packaging film of above-mentioned a kind of stretch-proof, wherein in S4 step
The temperature of the thermal finalization is 50 DEG C~160 DEG C.
The present invention also provides a kind of a kind of degradable barrier plastics packages of stretch-proof that above-mentioned preparation method is prepared
Film is rich in the monodisperse dioxy of hydroxyl by being added in the carbon dioxide copolymer composite crosslinking of activated monomer and acid anhydrides sealing end
SiClx microballoon carries out reactively blending and is modified, has carbon dioxide copolymer macromolecular to connect while initiation forms cross-linked structure
On branch to microsphere surface, formation is wrapped around, and not only improves compatibility, enhances carbon dioxide copolymer and filling is inorganic micro-
Interface cohesive force between ball, also stabilizes morphosis, tensile property is promoted, to effectively improve intermediate barrier layer
Mechanical property and thermal stability, be conducive to realize scale application.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, comprising the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, after evenly mixing put into extruder in, temperature be 140 DEG C
Melt blending is modified, and extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；The carbon dioxide copolymer and horse
The mass ratio for carrying out acid anhydrides is 15:8；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing are put into extruder,
Temperature is 100 DEG C of reactive extrursions, obtains the carbon dioxide copolymer barrier layered material with cross-linked structure；The radical initiator
For cyclohexanone peroxide；Carbon dioxide copolymer pellet, monodisperse silica microspheres, the activated monomer N- of the blocking modification
Vinyl pyrrolidone, chain extender diisocyanate, radical initiator mass ratio be 30:10:5:6:0.1；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 170 DEG C, polylactic acid layers are obtained；The toughener is maleic anhydride
Grafted ethene-propylene copolymer；The antistatic agent is graphene；The antioxidant is thiobisphenol；The slipping agent is mustard
Sour amide；The antiblocking agent is silica；The crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent,
The mass ratio of antiblocking agent is 20:7:5:4:7:9；
As middle layer, the polylactic acid layers that step S3 is obtained are made for S4, the carbon dioxide copolymer for obtaining step S2 barrier layered material
For surface layer, the two sides of carbon dioxide copolymer barrier layer are covered on, three layers of melt converge in T-die, form melt films, cold
But diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof；
The temperature of the cooling is 40 DEG C；The cross directional stretch is that diaphragm is preheated at 70 DEG C, preheating time 30min, draw ratio 5
Times；The longitudinal stretching is that diaphragm is preheated at 50 DEG C, and preheating time 30min, draw ratio is 2 times；The temperature of the thermal finalization
Degree is 100 DEG C.
Embodiment 2
A kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, comprising the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, after evenly mixing put into extruder in, temperature be 150 DEG C
Melt blending is modified, and extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；The carbon dioxide copolymer and horse
The mass ratio for carrying out acid anhydrides is 13:12；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing are put into extruder,
Temperature is 90 DEG C of reactive extrursions, obtains the carbon dioxide copolymer barrier layered material with cross-linked structure；The radical initiator
For dibenzoyl peroxide；Carbon dioxide copolymer pellet, monodisperse silica microspheres, the activated monomer of the blocking modification
N-vinyl pyrrolidone, chain extender diisocyanate, radical initiator mass ratio be 25:12:8:5:0.1；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 150 ~ 180 DEG C, polylactic acid layers are obtained；The toughener is Malaysia
Anhydride grafted ethylene-propylenediene terpolymer；The antistatic agent is carbon nanotube；The antioxidant is hydroquinone；
The slipping agent is oleamide；The antiblocking agent is titanium dioxide；The crystalline polylactic acid, toughener, antistatic agent,
Antioxidant, slipping agent, antiblocking agent mass ratio be 22:9:7:4:7:8；
As middle layer, the polylactic acid layers that step S3 is obtained are made for S4, the carbon dioxide copolymer for obtaining step S2 barrier layered material
For surface layer, the two sides of carbon dioxide copolymer barrier layer are covered on, three layers of melt converge in T-die, form melt films, cold
But diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof；
The temperature of the cooling is 45 DEG C；The cross directional stretch is that diaphragm is preheated at 60 DEG C, preheating time 15min, and draw ratio is
5 times；The longitudinal stretching is that diaphragm is preheated at 55 DEG C, and preheating time 25min, draw ratio is 3 times；The temperature of the thermal finalization
Degree is 80 DEG C.
Embodiment 3
A kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, comprising the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, after evenly mixing put into extruder in, temperature be 130 DEG C
Melt blending is modified, and extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；The carbon dioxide copolymer and horse
The mass ratio for carrying out acid anhydrides is 14:8；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing are put into extruder,
Temperature is 90 DEG C of reactive extrursions, and obtaining, there is the carbon dioxide copolymer of cross-linked structure, which to obstruct radical initiator described in layered material, is
Tert-butyl hydroperoxide；Carbon dioxide copolymer pellet, monodisperse silica microspheres, the activated monomer N- of the blocking modification
Vinyl pyrrolidone, chain extender diisocyanate, radical initiator mass ratio be 23:10:7:4:0.9；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 160 DEG C, polylactic acid layers are obtained；The toughener is styrene；Institute
Stating antistatic agent is graphite；The antioxidant is thio triphenol；The slipping agent is erucyl amide；The antiblocking agent is talcum
Powder；The crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent mass ratio be 12:8:7:5:
6:9；
As middle layer, the polylactic acid layers that step S3 is obtained are made for S4, the carbon dioxide copolymer for obtaining step S2 barrier layered material
For surface layer, the two sides of carbon dioxide copolymer barrier layer are covered on, three layers of melt converge in T-die, form melt films, cold
But diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof；
The temperature of the cooling is 35 DEG C；The cross directional stretch is that diaphragm is preheated at 85 DEG C, preheating time 25min, draw ratio 4
Times；The longitudinal stretching is that diaphragm is preheated at 70 DEG C, and preheating time 30min, draw ratio is 2 times；The temperature of the thermal finalization
Degree is 110 DEG C.
Embodiment 4
A kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, comprising the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, after evenly mixing put into extruder in, temperature be 130 DEG C
Melt blending is modified, and extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；The carbon dioxide copolymer and horse
The mass ratio for carrying out acid anhydrides is 14:9；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing are put into extruder,
Temperature is 90 DEG C of reactive extrursions, obtains the carbon dioxide copolymer barrier layered material with cross-linked structure；The radical initiator
For dibenzoyl peroxide；Carbon dioxide copolymer pellet, monodisperse silica microspheres, the activated monomer of the blocking modification
N-vinyl pyrrolidone, chain extender diisocyanate, radical initiator mass ratio be 30:9:5:8:0.1；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 170 DEG C, polylactic acid layers are obtained；The toughener is maleic anhydride
Grafted ethene-propylene copolymer；The antistatic agent is carbon black；The antioxidant is hydroquinone；The slipping agent is erucic acid
Amide；The antiblocking agent is barium sulfate；It is the crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, anti-stick
Even the mass ratio of agent is 18:8:6:5:7:7；
As middle layer, the polylactic acid layers that step S3 is obtained are made for S4, the carbon dioxide copolymer for obtaining step S2 barrier layered material
For surface layer, the two sides of carbon dioxide copolymer barrier layer are covered on, three layers of melt converge in T-die, form melt films, cold
But diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof；
The temperature of the cooling is 45 DEG C；The cross directional stretch is that diaphragm is preheated at 70 DEG C, preheating time 23min, draw ratio 5
Times；The longitudinal stretching is that diaphragm is preheated at 60 DEG C, and preheating time 25min, draw ratio is 2 times；The temperature of the thermal finalization
Degree is 70 DEG C.
Embodiment 5
A kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, comprising the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, after evenly mixing put into extruder in, temperature be 145 DEG C
Melt blending is modified, and extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；The carbon dioxide copolymer and horse
The mass ratio for carrying out acid anhydrides is 16:7；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing investment extruder, in temperature
Degree is 80 ~ 120 DEG C of reactive extrursions, obtains the carbon dioxide copolymer barrier layered material with cross-linked structure；The free radical causes
Agent is tert-butyl hydroperoxide；The carbon dioxide copolymer pellet of the blocking modification, monodisperse silica microspheres, activity are single
Body n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator mass ratio be 22:9:8:7:2；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 170 DEG C, polylactic acid layers are obtained；The toughener is butadiene
Copolymer；The antistatic agent is conductive metal powder；The antioxidant is thiobisphenol；The slipping agent is erucyl amide；
The antiblocking agent is aluminium oxide；The crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent
Mass ratio be 17:6:7:5:7:8；
As middle layer, the polylactic acid layers that step S3 is obtained are made for S4, the carbon dioxide copolymer for obtaining step S2 barrier layered material
For surface layer, the two sides of carbon dioxide copolymer barrier layer are covered on, three layers of melt converge in T-die, form melt films, cold
But diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof；
The temperature of the cooling is 45 DEG C；The cross directional stretch is that diaphragm is preheated at 80 DEG C, preheating time 23min, draw ratio 4
Times；The longitudinal stretching is that diaphragm is preheated at 65 DEG C, and preheating time 26min, draw ratio is 2 times；The temperature of the thermal finalization
Degree is 120 DEG C.
Comparative example 1
A kind of preparation of barrier package film does not add in the carbon dioxide copolymer composite crosslinking that activated monomer is blocked with acid anhydrides
Enter the monodisperse silica microspheres rich in hydroxyl and carry out blending and modifying, remaining raw material and step are the same as embodiment 5.
The performance test for the barrier package film that Examples 1 to 5 and comparative example 1 obtain is as follows:
Tensile strength test reference " GB13022-1991 " film stretchability energy test method.
Percent thermal shrinkage test method is packed for polytene thermal-shrinkable film with reference to " GB/T 13519-2016 ".
Wherein, MD=longitudinal direction, TD=transverse direction；MD:Machine Direction, mechanical direction, that is, longitudinal meaning.
TD:Transverse Direction, perpendicular to mechanical direction, that is, the lateral meaning.
Table 1 is the test result of Examples 1 to 5 and comparative example 1.
Claims (10)
1. a kind of preparation method of the degradable barrier plastic packaging film of stretch-proof, which comprises the following steps:
S1, using carbon dioxide copolymer and maleic anhydride as raw material, put into extruder after evenly mixing, it is molten at 120 ~ 160 DEG C
Melt blending and modifying, extruding pelletization obtains the carbon dioxide copolymer pellet of acid anhydrides sealing end；
S2, by the carbon dioxide copolymer pellet of the obtained blocking modification of step S1 and rich in hydroxyl monodisperse silica it is micro-
Ball, activated monomer n-vinyl pyrrolidone, chain extender diisocyanate, radical initiator, mixing investment extruder squeeze out
As centre barrier material；
S3, crystalline polylactic acid, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent are uniformly mixed, by ingredient point
Corresponding extruder is not added to be melted, be plasticized between 150 ~ 180 DEG C, polylactic acid layered material is obtained；
S4, being converged in T-die using three-layer co-extruded extruder, the intermediate barrier material that step S2 is obtained is used as middle layer,
The polylactic acid layers that step S3 is obtained are covered on the two sides of carbon dioxide copolymer barrier layer as surface layer, form melt films, cooling
Diaphragm is obtained, cross directional stretch, longitudinal stretching are carried out, thermal finalization finally obtains the degradable barrier plastic packaging film of stretch-proof.
2. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
The mass ratio of carbon dioxide copolymer described in S1 step and maleic anhydride is 10~20:5~15.
3. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
Radical initiator described in S2 step be cyclohexanone peroxide, dibenzoyl peroxide, in tert-butyl hydroperoxide at least
It is a kind of.
4. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
Carbon dioxide copolymer pellet, monodisperse silica microspheres, the activated monomer N- vinyl of blocking modification described in S2 step
Pyrrolidones, chain extender diisocyanate, radical initiator mass ratio be 20~40:5~15:3~10:3~8:0.1.
5. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
The extrusion temperature of extruder described in S2 step is 80 ~ 120 DEG C.
6. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
Toughener described in S3 step is maleic anhydride grafted ethene-propylene copolymer, maleic anhydride grafted ethene-propylenediene three
At least one of membered copolymer, styrene, copolymer of butadiene；The antistatic agent is carbon black, graphite, graphene, carbon
At least one of nanotube, conductive metal powder；The antioxidant is phenolic antioxidant, and the phenolic antioxidant is to benzene two
At least one of phenol, thiobisphenol, triphenol；The slipping agent is at least one of erucyl amide, oleamide；It is described anti-
Adhesion agent is at least one of silica, calcium carbonate, aluminium oxide, titanium dioxide, barium sulfate, talcum powder.
7. a kind of preparation method of the degradable barrier plastic packaging film of stretch-proof according to claim 1 or 6, feature exist
It is in the mass ratio of, crystalline polylactic acid described in S3 step, toughener, antistatic agent, antioxidant, slipping agent, antiblocking agent
10~25:5~10:3~8:2~6:5~8:3~10.
8. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
Cooling temperature described in S4 step is 30~50 DEG C；The cross directional stretch is that diaphragm is preheated at 40~110 DEG C, when preheating
Between 10~40min, draw ratio be 2~6 times；The longitudinal stretching is that diaphragm is preheated at 40~85 DEG C, preheating time 10
~40min, draw ratio are 1~3 times；The temperature of the thermal finalization is 50 DEG C~160 DEG C.
9. the preparation method of the degradable barrier plastic packaging film of a kind of stretch-proof according to claim 1, which is characterized in that
The temperature of thermal finalization described in S4 step is 50 DEG C~160 DEG C.
10. a kind of degradable barrier plastics for stretch-proof that any one preparation method is prepared according to claim 1~9
Packaging film.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102501529A (en) * | 2011-11-18 | 2012-06-20 | 佛山佛塑料科技集团股份有限公司 | Biaxial drawing polylactic acid compound film with barrier property and preparation method thereof |
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