CN104861246B - A kind of preparation method with barrier degradation plastic laminated film - Google Patents

A kind of preparation method with barrier degradation plastic laminated film Download PDF

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CN104861246B
CN104861246B CN201410699594.XA CN201410699594A CN104861246B CN 104861246 B CN104861246 B CN 104861246B CN 201410699594 A CN201410699594 A CN 201410699594A CN 104861246 B CN104861246 B CN 104861246B
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film
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preparation
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pbm
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CN104861246A (en
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朱凤超
王雪
田雪涛
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Tianjin Jinsheng Plastic Product Polytron Technologies Inc
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Tianjin Jinsheng Plastic Product Polytron Technologies Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Abstract

The invention discloses a kind of preparation method with barrier degradation plastic laminated film, the preparation method is from ripe in the market degradation plastic masterbatch PBM and Pullulan polysaccharide and film-grade LDPE and adds antioxidant, ultra-violet absorber for raw material, a kind of three-layer plastic compound film with good oxygen barrier, degradability and mechanical property is prepared using tannic acid modified Pullulan polysaccharide, and then using the three-layer co-extruded blown film techniques of plastic sheeting.Laminated film internal layer of the present invention, middle level, three layers of outer layer are respectively LDPE/PBM/Pullulan, PBM/Pullulan and LDPE/PBM/Pullulan.The present invention is a kind of to have barrier degradation plastic laminated film, the meeting automatic classifying in the presence of oxygen-enriched and microorganism, film after discarded can be by the degradable digestion of microorganism in nature, ldpe film oxygen barrier property compared with same thickness can improve 70% 80%, the ldpe film of mechanical property and same thickness is substantially suitable, simple production process of the present invention, production efficiency is high, industrializing implementation is easy.

Description

A kind of preparation method with barrier degradation plastic laminated film
Technical field
It is specially a kind of with barrier degradation plastic laminated film the invention belongs to plastic film material field Preparation method.
Background technology
It is excellent barrier that food, medicine preservation require that packaging material has, and its composition is broken with oxygen in air-prevention It is bad.Higher food, pharmaceutical packing are required to barrier, conventional plastic packing film material is different degrees of because having to breathe freely Property and the quality for having a strong impact on packaging.At present, to the packaging of barrier material still using the conventional packaging materials such as glass, aluminium foil as It is main, or these materials are used in combination with high polymer material.This causes packing cost high, and material recovery is difficult, pollutes environment.Cause This, inexpensive, the environmentally friendly high oxygen barrier material of development of new is paid attention to by countries in the world height.
Currently, after plastic package material use, discarded packaging material problem of environmental pollution has caused the height of countries in the world Degree is paid attention to, and realizes the environment friendly of packaging material and turns into the direction of packaging material scientific research most attraction and challenge One of.
Biodegradable plastic is one of the effective way for administering plastic refuse environmental pollution, from the packaging bag of food to Agricultural film, then to the shell of electric equipment products, it is biodegradable from non-returnable container, edible products to product durable in use Plastics just progressively replace conventional plastic materials, and market prospects are very wide.
Starch is a kind of abundance, cheap natural macromolecular material, is also a kind of inexhaustible Renewable resource, it can be biodegradable in a variety of environmental conditions, final catabolite CO2And H2O can pass through plant Photosynthesis is recycled, and any pollution will not be caused to environment.Therefore, starch is widely used in grinding for degradation plastic Study carefully and product development, and have been achieved for great progress.Currently, commercially available PBM masterbatch is exactly using starch as original A kind of degradation plastic masterbatch of material, is the biodegradation material that a kind of utilization agro-ecology resource is main material production.PBM Starch, vegetable fat etc. are used for main Material synthesis fully-degradable natural high polymer material, then it is specially treated after, with water solubility High polymer material and a small amount of resin compounded are formed.PBM masterbatch outward appearance is the thermoplastic granulates shape masterbatch of slightly caoutchouc elasticity, is had Hot blow is swollen property and tensility, processability are good and with excellent tensile strength and fracture strength, more similar biological drop Solve resin mechanical property good.
Pullulan polysaccharide is the exocellular polysaccharide that Aureobasidium pullulans fermentation is produced, and its basic structure is that α-Isosorbide-5-Nitrae-glycosidic bond connects The straight-chain dextran that the maltotriose repeat unit being connected into is polymerized with α -1,6- glycosidic bonds, mean molecule quantity is 2 ×105, structure unique Pullulan imparts its unique and excellent performance, and such as fiberising capacity is strong, good moldability and by force Oxygen barrier etc..Therefore, Pullulan polysaccharide can be used as the packaging material with biodegradability and strong oxygen barrier.But It is that Pullulan polysaccharide packaging materials enbrittle greatly, the defect of material mechanical performance difference, this causes its application to be restricted. Therefore, although patent GB1494253 and GB834175 disclose application of the Pullulan polysaccharide in thermoplastics art, The defect that Pullulan polysaccharide fragility is big, material mechanical performance is poor can not be solved.
Patent CN101717533A discloses a kind of anti-electrostatic degradable film material and preparation method thereof, and thin-film material is It is made up of following raw material：LDPE, LLDPE, starch base degradable plastic raw material, antistatic master granule.Patent CN1418906A is disclosed A kind of double double degradation plastic films and its production method.But, degradable films disclosed in this two patented technologies do not have Have good barrier.
To realize plastic sheeting degradability and barrier good combination, inventor's early stage discloses a kind of oxygen barrier and can The plastic sheeting (CN103160012A) of degraded, its raw material components be respectively low density polyethylene (LDPE) (LDPE), PBM masterbatch, Pullulan polysaccharide, antioxidant, ultra-violet absorber.Ensure the good mechanical property of film using LDPE fundamental characteristics；Profit With the degradability of PBM and Pullulan polysaccharide, the environment friendly of thin-film material is realized；Using Pullulan polysaccharide it is high every Oxygen, improves the oxygen barrier effect of thin-film material；By the use of in PBM masterbatch starch and Pullulan polysaccharide as glucide in structure On similitude, improve the overall compatibility of PBM and Pullulan polysaccharide materials；By controlling LDPE/PBM/Pullulan bodies The blending proportioning of system, can be achieved the regulation and control to barrier and degradability etc..But, further study show that, the oxygen barrier and can Though the plastic sheeting of degraded is barrier and degradability improves a lot compared with ldpe film, from the application point of view, barrier Further raising is still needed to degradability.In LDPE/PBM/Pullulan systems, increase PB and Pullulan content, especially It is the increase of Pullulan content, though barrier and degradability can be improved, the overall mechanical property reduction of film, application It is very restricted.
The content of the invention
For existing utilization LDPE/PBM/Pullulan systems prepare oxygen barrier and present in degredation plastic film every Oxygen and degradability still need to further to improve, improve barrier and degradability so that the deficiency such as thin film mechanical performance reduction, The technical problem that the present invention is intended to solve is：Using tannic acid modified Pullulan polysaccharide, so it is three-layer co-extruded using plastic sheeting Blown film techniques, a kind of three-layer co-extruded composite plastic film with good oxygen barrier, degradability and mechanical property of extrusion-blown modling Preparation method.
In order to achieve the above object, technical solution of the present invention is as follows：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) the preparation of Pullulan polysaccharide is modified：Weigh Pullulan polysaccharide 100Kg, add 100L concentration 2000~ It is uniformly dissolved in 3000mg/L tannic acid solution, air blast drying pelletizing obtains tannic acid modified Pullulan polysaccharide；
(2) the preparation of three-layer thin-film raw material：Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 50 ~70Kg, tannic acid modified Pullulan polysaccharide 20~40Kg, 2~4Kg of antioxidant, 0.5~1Kg of ultra-violet absorber, by with LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed side in conventional high-speed mixer Close 25-35 minute, the then extruding pelletization in double-screw extruding pelletizing machine, four sections of extruding granulator barrel back segment temperature point is controlled System, is controlled at 180~200 DEG C, the four sections of controls of barrel front-end temperature point are controlled in 200~230 DEG C, head temperature respectively respectively It is divided to two sections of controls, controls respectively at 220~240 DEG C；
Middle level raw material is matched somebody with somebody by PBM masterbatch 100Kg, 50~80Kg of tannic acid modified Pullulan polysaccharide, 2~4Kg of antioxidant Than being mixed 25-35 minutes in conventional high-speed mixer, then extruding pelletization, extruding pelletization in double-screw extruding pelletizing machine The four sections of controls of machine barrel back segment temperature point, are controlled at 180~200 DEG C, the four sections of controls of barrel front-end temperature point are controlled respectively respectively At 200~230 DEG C, head temperature is divided to two sections of controls, controls respectively at 220~240 DEG C；
(3) three-layer co-extruded blown film：Using common three-layer co-extruded film blowing device, the pellet co-extrusion that (2) step is prepared is respectively adopted Blown film, three extruder barrel back segment temperature using four sections of controls, are controlled in 180~200 DEG C, barrel front-end temperature respectively Using four sections of controls, control respectively at 210~230 DEG C, co-extruding machine head temperature is divided to two sections of controls, controls respectively 220~240 DEG C, blow-up ratio is 1.5~2.0,20~40r/min of screw speed, 10~50m/min of hauling speed.
Moreover, (1) described Pullulan polysaccharide is exocellular polysaccharide that Aureobasidium pullulans fermentation is produced to step, it is tied substantially Structure is the straight-chain dextrorotation Portugal that the maltotriose repeat unit that α -1,4- glycosidic bonds are connected into is polymerized with α -1,6- glycosidic bonds Glycan, mean molecule quantity is 2 × 105。
Moreover, (2) described internal layer and outer layer are LDPE/PBM/Pullulan layers to step, intermediate layer is PBM/ Pullulan layers.
Moreover, (2) described LDPE is general thin level low density polyethylene (LDPE) to step.
Moreover, (2) described PBM masterbatch is to utilize the biodegradable material that agro-ecology resource is main material production to step Material, be use starch, vegetable fat etc. for the fully-degradable natural high polymer material of main Material synthesis it is specially treated after, with water Soluble macromolecular material and a small amount of resin compounded are formed, at present, and in the market has many sale, and outward appearance is the heat of slightly caoutchouc elasticity Plastic particle shape masterbatch.
Moreover, (2) described antioxidant is general antioxidant to step, it can be antioxidant 1010, irgasfos 168 etc., can press down Make or delay thin-film material thermal oxide in atmosphere.
Can be phenyl salicylate, ultraviolet moreover, (2) described ultra-violet absorber is general ultra-violet absorber to step Light absorbers UV-531 etc., can prevent destruction of the ultraviolet light to thin-film material.
Advantages and positive effects of the present invention are：
1st, a kind of preparation method with barrier degradation plastic laminated film of the present invention, be combined by three-layer thin-film and Into internal layer is identical with outer layer raw material, is LDPE/PBM/Pullulan components, and intermediate layer is PBM/Pullulan components.The present invention From modified starch degradation plastic masterbatch PBM ripe in the market and tannic acid modified Pullulan polysaccharide and film-grade LDPE is blended.Ensure the good mechanical property of film using LDPE fundamental characteristics；Utilize dropping for PBM and Pullulan polysaccharide Xie Xing, realizes the environment friendly of thin-film material；Using the high barrier of Pullulan polysaccharide, the oxygen barrier effect of thin-film material is improved Really；Starch and similitude of the Pullulan polysaccharide as glucide in structure by the use of in PBM masterbatch, improve PBM with The overall compatibility of Pullulan polysaccharide materials.
2nd, the present invention is modified using tannic acid to Pullulan polysaccharide, and described tannic acid is also known as tannic acid, is yellowish Color, without crystalline flour end, belongs to the complex compound of multi-phenol, the rich content in nature is cheap and easy to get to light brown.Tannin After acid is polysaccharide-modified to Pullulan, the compatibility of Pullulan polysaccharide and LDPE and PBM is remarkably improved, interface cohesion is improved Intensity, therefore the mechanical property of system can be significantly improved.Meanwhile, tannic acid is modified to Pullulan polysaccharide can be in increase system The addition of Pullulan polysaccharide, therefore have notable help to the barrier and degradability for improving film.
3rd, the present invention is prepared using three-layer co-extruded blown film techniques it is a kind of with barrier degradation plastic laminated film, it is interior Layer ensures the good mechanical property of film with outer layer, and the barrier and degradability of film, three-layer co-extruded blown film are strengthened in intermediate layer This three layers can be combined together by technology well, and film integrity is good.Moreover, the present invention uses three-layer co-extruded blown film techniques Current technology is very ripe, simple production process, and production efficiency is high, industrializing implementation is easy.
4th, a kind of preparation method with barrier degradation plastic laminated film of the invention, using the technology of the present invention The laminated film of preparation meeting automatic classifying in the presence of oxygen-enriched and microorganism, the film after discarding can be by microorganism in nature Degradable digestion, ultimately generates carbon dioxide and water, and the ldpe film oxygen barrier property compared with same thickness can improve 70%- 80%, the ldpe film of mechanical property and same thickness is substantially suitable.
Embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention Scope, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this The various changes carried out on the premise of invention spirit and scope to the material component in these embodiments and consumption or change Belong to protection scope of the present invention.
Embodiment 1：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) preparation of modified Pullulan polysaccharide.Pullulan polysaccharide 100Kg are weighed, 100L concentration 2500mg/L is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 70Kg, tannic acid modified Pullulan polysaccharide 20Kg, irgasfos 168 are that 4Kg, ultraviolet absorbent UV-531 are 1Kg.By formula LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed in conventional high-speed mixer 25 minutes, the then extruding pelletization in double-screw extruding pelletizing machine.The four sections of controls of extruding granulator barrel back segment temperature point, respectively For 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, head Two sections of temperature are respectively 230 DEG C, 230 DEG C；
Middle level raw material is by PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50Kg, antioxidant 4Kg proportionings, normal Mixing 35 minutes in high-speed mixer are advised, then the extruding pelletization in double-screw extruding pelletizing machine.Extruding granulator barrel back segment Points of four sections controls of temperature, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, two sections of temperature of head are respectively 230 DEG C, 230 DEG C；
(3) three-layer co-extruded blown film.Using common three-layer co-extruded film blowing device, the pellet that step (2) preparation is respectively adopted is total to Extrusion film.Three extruder barrel back segment temperature are using four sections of controls, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, material Cylinder four sections of temperature of leading portion are respectively 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C.Co-extruding machine head temperature is divided to two sections of controls, respectively 230 ℃、230℃.Blow-up ratio 1.5, screw speed 40r/min, hauling speed 30m/min.
Embodiment 2：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) preparation of modified Pullulan polysaccharide.Pullulan polysaccharide 100Kg are weighed, 100L concentration 2000mg/L is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 50Kg, tannic acid modified Pullulan polysaccharide 40Kg, irgasfos 168 is 4Kg, and ultraviolet absorbent UV-531 is 1Kg.By formula LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed in conventional high-speed mixer 30 minutes, the then extruding pelletization in double-screw extruding pelletizing machine.The four sections of controls of extruding granulator barrel back segment temperature point, respectively For 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, head Two sections of temperature are respectively 230 DEG C, 230 DEG C；
Middle level raw material is by PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50Kg, antioxidant 4Kg proportionings, normal Mixing 35 minutes in high-speed mixer are advised, then the extruding pelletization in double-screw extruding pelletizing machine.Extruding granulator barrel back segment Points of four sections controls of temperature, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, two sections of temperature of head are respectively 230 DEG C, 230 DEG C；
(3) three-layer co-extruded blown film.Using common three-layer co-extruded film blowing device, the pellet that step (2) preparation is respectively adopted is total to Extrusion film.Three extruder barrel back segment temperature are using four sections of controls, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, material Cylinder four sections of temperature of leading portion are respectively 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C.Co-extruding machine head temperature is divided to two sections of controls, respectively 230 ℃、230℃.Blow-up ratio 2, screw speed 40r/min, hauling speed 10m/min.
Embodiment 3：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) preparation of modified Pullulan polysaccharide.Pullulan polysaccharide 100Kg are weighed, 100L concentration 3000mg/L is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 60Kg, tannic acid modified Pullulan polysaccharide 30Kg, irgasfos 168 is 3Kg, and ultraviolet absorbent UV-531 is 1Kg.By formula LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed in conventional high-speed mixer 35 minutes, the then extruding pelletization in double-screw extruding pelletizing machine.The four sections of controls of extruding granulator barrel back segment temperature point, respectively For 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, head Two sections of temperature are respectively 230 DEG C, 240 DEG C；
Middle level raw material is by PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50Kg, antioxidant 4Kg proportionings, normal Mixing 35 minutes in high-speed mixer are advised, then the extruding pelletization in double-screw extruding pelletizing machine.Extruding granulator barrel back segment Points of four sections controls of temperature, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, two sections of temperature of head are respectively 230 DEG C, 240 DEG C；
(3) three-layer co-extruded blown film.Using common three-layer co-extruded film blowing device, the pellet that step (2) preparation is respectively adopted is total to Extrusion film.Three extruder barrel back segment temperature are using four sections of controls, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, material Cylinder four sections of temperature of leading portion are respectively 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C.Co-extruding machine head temperature is divided to two sections of controls, respectively 230 ℃、240℃.Blow-up ratio 1.8, screw speed 30r/min, hauling speed 50m/min.
Embodiment 4：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) preparation of modified Pullulan polysaccharide.Pullulan polysaccharide 100Kg are weighed, 100L concentration 2700mg/L is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 50Kg, tannic acid modified Pullulan polysaccharide 40Kg, irgasfos 168 is 4Kg, and ultraviolet absorbent UV-531 is 0.5Kg.By with LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed side in conventional high-speed mixer Close 25 minutes, the then extruding pelletization in double-screw extruding pelletizing machine.The four sections of controls of extruding granulator barrel back segment temperature point, point Wei not be 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, machine First two sections of temperature are respectively 220 DEG C, 220 DEG C；
Middle level raw material is by PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 80Kg, antioxidant 2Kg proportionings, normal Mixing 35 minutes in high-speed mixer are advised, then the extruding pelletization in double-screw extruding pelletizing machine.Extruding granulator barrel back segment Points of four sections controls of temperature, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, two sections of temperature of head are respectively 230 DEG C, 230 DEG C；.
(3) three-layer co-extruded blown film.Using common three-layer co-extruded film blowing device, the pellet that step (2) preparation is respectively adopted is total to Extrusion film.Three extruder barrel back segment temperature are using four sections of controls, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, material Cylinder four sections of temperature of leading portion are respectively 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C.Co-extruding machine head temperature is divided to two sections of controls, respectively 220 ℃、220℃.Blow-up ratio 2.0, screw speed 20r/min, hauling speed 15m/min.
Embodiment 5：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) preparation of modified Pullulan polysaccharide.Pullulan polysaccharide 100Kg are weighed, 100L concentration 2900mg/L is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 70Kg, tannic acid modified Pullulan polysaccharide 40Kg, irgasfos 168 is 4Kg, and ultraviolet absorbent UV-531 is 1Kg.By formula LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed in conventional high-speed mixer 30 minutes, the then extruding pelletization in double-screw extruding pelletizing machine.The four sections of controls of extruding granulator barrel back segment temperature point, respectively For 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, head Two sections of temperature are respectively 220 DEG C, 220 DEG C；
Middle level raw material is by PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 75Kg, antioxidant 3Kg proportionings, normal Mixing 35 minutes in high-speed mixer are advised, then the extruding pelletization in double-screw extruding pelletizing machine.Extruding granulator barrel back segment Points of four sections controls of temperature, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, two sections of temperature of head are respectively 230 DEG C, 230 DEG C；
(3) three-layer co-extruded blown film.Using common three-layer co-extruded film blowing device, the pellet that step (2) preparation is respectively adopted is total to Extrusion film.Three extruder barrel back segment temperature are using four sections of controls, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, material Cylinder four sections of temperature of leading portion are respectively 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C.Co-extruding machine head temperature is divided to two sections of controls, respectively 230 ℃、230℃.Blow-up ratio 1.8, screw speed 20r/min, hauling speed 40m/min.
Embodiment 6：
A kind of preparation method with barrier degradation plastic laminated film, comprises the following steps：
(1) preparation of modified Pullulan polysaccharide.Pullulan polysaccharide 100Kg are weighed, 100L concentration 2900mg/L is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer layer raw material, and its component is LDPE 100Kg, PBM masterbatch 60Kg, tannic acid modified Pullulan polysaccharide 30Kg, irgasfos 168 is 3Kg, and ultraviolet absorbent UV-531 is 1Kg.By formula LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed in conventional high-speed mixer 30 minutes, the then extruding pelletization in double-screw extruding pelletizing machine.The four sections of controls of extruding granulator barrel back segment temperature point, respectively For 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, head Two sections of temperature are respectively 220 DEG C, 220 DEG C；
Middle level raw material is by PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 75Kg, antioxidant 2Kg proportionings, normal Mixing 30 minutes in high-speed mixer are advised, then the extruding pelletization in double-screw extruding pelletizing machine.Extruding granulator barrel back segment Points of four sections controls of temperature, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, four sections of temperature of barrel leading portion are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, two sections of temperature of head are respectively 230 DEG C, 230 DEG C；
(3) three-layer co-extruded blown film.Using common three-layer co-extruded film blowing device, the pellet that step (2) preparation is respectively adopted is total to Extrusion film.Three extruder barrel back segment temperature are using four sections of controls, respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, material Cylinder four sections of temperature of leading portion are respectively 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C.Co-extruding machine head temperature is divided to two sections of controls, respectively 230 ℃、230℃.Blow-up ratio 1.5, screw speed 30r/min, hauling speed 50m/min.

Claims (6)

1. a kind of preparation method with barrier degradation plastic laminated film, it is characterised in that：Its step is：
(1) the preparation of Pullulan polysaccharide is modified：Pullulan polysaccharide 100Kg are weighed, 2000~3000mg/L of 100L concentration is added Tannic acid solution in be uniformly dissolved, air blast drying pelletizing, obtain tannic acid modified Pullulan polysaccharide；
(2) the preparation of three-layer thin-film raw material：Internal layer is identical with outer layer raw material, its component be LDPE 100Kg, PBM masterbatch 50~ 70Kg, tannic acid modified Pullulan polysaccharide 20~40Kg, 2~4Kg of antioxidant, 0.5~1Kg of ultra-violet absorber, by formula LDPE, PBM masterbatch, modified Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed in conventional high-speed mixer 25-35 minutes, the then extruding pelletization in double-screw extruding pelletizing machine, the four sections of controls of extruding granulator barrel back segment temperature point, Control respectively at 180~200 DEG C, the four sections of controls of barrel front-end temperature point are controlled at 200~230 DEG C, head temperature is divided to two respectively Section control, is controlled at 220~240 DEG C respectively；
Middle level raw material is matched by PBM masterbatch 100Kg, 50~80Kg of tannic acid modified Pullulan polysaccharide, 2~4Kg of antioxidant, Mixed 25-35 minutes in conventional high-speed mixer, the then extruding pelletization in double-screw extruding pelletizing machine, extruding granulator barrel The four sections of controls of back segment temperature point, are controlled at 180~200 DEG C, the four sections of controls of barrel front-end temperature point are controlled 200 respectively respectively ~230 DEG C, head temperature is divided to two sections of controls, controls respectively at 220~240 DEG C；
(3) three-layer co-extruded blown film：Using common three-layer co-extruded film blowing device, the pellet coextrusion film blowing that (2) step is prepared is respectively adopted, Three extruder barrel back segment temperature using four sections of controls, are controlled at 180~200 DEG C, barrel front-end temperature is also adopted respectively With four sections of controls, control respectively at 210~230 DEG C, co-extruding machine head temperature is divided to two sections of controls, controls respectively at 220~240 DEG C, Blow-up ratio is 1.5~2.0,20~40r/min of screw speed, 10~50m/min of hauling speed.
2. the preparation method according to claim 1 with barrier degradation plastic laminated film, it is characterised in that： (1) described Pullulan polysaccharide is exocellular polysaccharide that Aureobasidium pullulans fermentation is produced to step, and its basic structure is α-Isosorbide-5-Nitrae-glucosides The straight-chain dextran that the maltotriose repeat unit that key is connected into is polymerized with α -1,6- glycosidic bonds, mean molecule quantity For 2 × 105。
3. the preparation method according to claim 1 with barrier degradation plastic laminated film, it is characterised in that： (2) described LDPE is general thin level low density polyethylene (LDPE) to step.
4. the preparation method according to claim 1 with barrier degradation plastic laminated film, it is characterised in that： (2) described PBM masterbatch is commercial goods to step.
5. the preparation method according to claim 1 with barrier degradation plastic laminated film, it is characterised in that： (2) described antioxidant is antioxidant 1010 or irgasfos 168 to step.
6. the preparation method according to claim 1 with barrier degradation plastic laminated film, it is characterised in that： (2) described ultra-violet absorber is phenyl salicylate or ultraviolet absorbent UV-531 to step.
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CN103160012A (en) * 2013-04-01 2013-06-19 天津超平新材料科技有限公司 Oxygen-separating and degradable thin plastic film
CN103205045A (en) * 2013-04-01 2013-07-17 天津超平新材料科技有限公司 Preparation method for oxygen separating degradable plastic thin film
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CN103205045A (en) * 2013-04-01 2013-07-17 天津超平新材料科技有限公司 Preparation method for oxygen separating degradable plastic thin film
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