CN104861246A - Preparation method for degradable plastic composite film with oxygen separation performance - Google Patents

Preparation method for degradable plastic composite film with oxygen separation performance Download PDF

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CN104861246A
CN104861246A CN201410699594.XA CN201410699594A CN104861246A CN 104861246 A CN104861246 A CN 104861246A CN 201410699594 A CN201410699594 A CN 201410699594A CN 104861246 A CN104861246 A CN 104861246A
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pbm
preparation
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CN104861246B (en
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朱凤超
王雪
田雪涛
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TIANJIN CITY JINSHENGYU PLASTIC PRODUCTS CO Ltd
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TIANJIN CITY JINSHENGYU PLASTIC PRODUCTS CO Ltd
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    • 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
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    • 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
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    • 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
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    • 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)

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Abstract

The invention discloses a preparation method for a degradable plastic composite film with an oxygen separation performance. In the preparation method, degradable plastic master batch PBM mature in the present market, Pullulan polysaccharide and film-level LDPE are employed as raw material with addition of anti-oxidants and ultraviolet ray absorbers, tannic acid is employed for modifying Pullulan polysaccharide, further the plastic film three-layer co-extrusion film blowing technology is employed, and a three-layer plastic composite film with good oxygen separation performance, degradability and mechanical properties is prepared. The inner layer, the middle layer and the outer layer of the composite film are LDPE/PBM/Pullulan, PBM/Pullulan and LDPE/PBM/Pullulan respectively. The composite film can decompose automatically under action of oxygen enrichment and microbes, a wasted film can be degraded and digested completely by microbes in nature, the oxygen separation performance of the composite film can be raised by 70%-80% compared with the oxygen separation performance of an LDPE film with the same thickness, and the mechanical properties of the composite film are almost the same as mechanical properties of an LDPE film with the same thickness. The composite film is advantaged by simple production technology, high production efficiency and easy industrial enforcement.

Description

A kind of preparation method with barrier degradable plastics laminated film
Technical field
The invention belongs to plastic film material field, be specially a kind of preparation method with barrier degradable plastics laminated film.
Background technology
It is excellent barrier that food, medicine preservation require wrapping material to have, with the destruction of oxygen in air-prevention to its composition.To the higher food of barrier requirement, pharmaceutical packing, conventional plastic packaging film material has a strong impact on the quality of packaging because of the ventilation property had in various degree.At present, to the packaging of barrier material still based on the conventional packaging material such as glass, aluminium foil, or these materials are combined with macromolecular material.This makes packing cost high, salvage material difficulty, contaminate environment.Therefore, development of new high oxygen barrier material that is inexpensive, environmental protection is subject to the attention of countries in the world height.
Current, after Plastic Packaging Materials uses, discarded wrapping material problem of environmental pollution has caused the great attention of countries in the world, and the environment friendly realizing wrapping material has become one of wrapping material scientific research most magnetism and challenging direction.
Biodegradable plastic is one of effective way of administering plastic refuse environmental pollution, from the packing bag of food to agricultural film, arrive the shell of electric equipment products again, from non-returnable container, edible products to product durable in use, biodegradable plastic just progressively replaces conventional plastic materials, and market outlook are very wide.
Starch is a kind of abundance, cheap natural macromolecular material, and be also a kind of inexhaustible renewable resources, it can be biodegradable in a variety of environmental conditions, final degraded product CO 2and H 2o can carry out recirculation by the photosynthesis of plant, can not cause any pollution to environment.Therefore, starch is widely used in research and the product development of degradable plastics, and has achieved great progress.Current, PBM masterbatch on sale on market is exactly take starch as a kind of degradable plastics masterbatch of raw material, is a kind of biodegradable material utilizing agro-ecology resource to be main material production.PBM adopts starch, Vegetable oil lipoprotein etc. for main raw material synthesis fully-degradable natural macromolecular material, then after special processing, forms with water-soluble high-molecular material and a small amount of resin compounded.PBM masterbatch outward appearance is the thermoplastic granulates shape masterbatch of slightly caoutchouc elasticity, has the swollen property of hot blow and tensility, and processability is good and have excellent tensile strength and breaking tenacity, and more similar Biodegradable resin mechanical property is good.
Pullulan polysaccharide is the exocellular polysaccharide that Aureobasidium pullulans fermentation produces, and its basic structure is the straight-chain dextran that trisaccharide maltose repeating unit that α-Isosorbide-5-Nitrae-glycosidic link connects into is polymerized with α-1,6-glycosidic link, and molecular-weight average is 2 × 10 5, the structure of Pullulan uniqueness imparts its unique and excellent performance, as strong in fiberising capacity, good moldability and by force oxygen barrier etc.Therefore, Pullulan polysaccharide can be used as the wrapping material use with biodegradability and strong oxygen barrier.But Pullulan polysaccharide wrapping material enbrittle greatly, the defect of material mechanical performance difference, this makes its application be restricted.Therefore, although patent GB1494253 and GB834175 discloses the application of Pullulan polysaccharide in thermoplastics art, the defect that Pullulan polysaccharide fragility is large, material mechanical performance is poor cannot solve.
Patent CN101717533A discloses a kind of anti-electrostatic degradable film material and preparation method thereof, and thin-film material is made up of following raw material: LDPE, LLDPE, starch base degradable plastic raw material, antistatic master granule.Patent CN1418906A discloses two a kind of double degradation plastic film and production method thereof.But degradable films disclosed in these two patented technologies does not all have good barrier.
For realizing plastics film degradability and barrier good combination, contriver discloses a kind of oxygen barrier and degredation plastic film (CN103160012A) early stage, and its feed composition is respectively Low Density Polyethylene (LDPE), PBM masterbatch, Pullulan polysaccharide, oxidation inhibitor, UV light absorber.The fundamental characteristics of LDPE is utilized to ensure the mechanical property that film is good; Utilize the degradability of PBM and Pullulan polysaccharide, realize the environment friendly of thin-film material; Utilize the height of Pullulan polysaccharide barrier, improve the oxygen barrier effect of thin-film material; Starch and Pullulan polysaccharide in PBM masterbatch is utilized as glucide similarity structurally, to improve the consistency of PBM and Pullulan polysaccharide material entirety; By the blended proportioning of control LDPE/PBM/Pullulan system, the regulation and control to barrier and degradability etc. can be realized.But, study discovery further, though this oxygen barrier and the barrier and degradability of degredation plastic film comparatively ldpe film improve a lot, from application point, barrier and degradability still needs further raising.In LDPE/PBM/Pullulan system, increase the content of PB and Pullulan, the especially increase of the content of Pullulan, though can improve barrier and degradability, the mechanical property of film integral reduces, and application is very restricted.
Summary of the invention
Oxygen barrier is prepared and barrier and degradability existing for degredation plastic film still needs further raising, improves barrier and degradability and make the deficiencies such as thin film mechanical performance reduction for the existing LDPE/PBM/Pullulan of utilization system, the technical problem that quasi-solution of the present invention is determined is: utilize tannic acid modified Pullulan polysaccharide, and then adopt the three-layer co-extruded blown film techniques of plastics film, a kind of preparation method with the three-layer co-extruded composite plastic film of good oxygen barrier, degradability and mechanical property of extrusion-blown modling.
In order to achieve the above object, technical solution of the present invention is as follows:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) the preparation of modification Pullulan polysaccharide: take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2000 ~ 3000mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide;
(2) the preparation of three-layer thin-film raw material: internal layer is identical with outer raw material, its component is LDPE 100Kg, PBM masterbatch 50 ~ 70Kg, tannic acid modified Pullulan polysaccharide 20 ~ 40Kg, oxidation inhibitor 2 ~ 4Kg, UV light absorber 0.5 ~ 1Kg, by formula by LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber mixes 25-35 minute in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine, extruding granulator barrel back segment temperature divides four sections of controls, control at 180 ~ 200 DEG C respectively, barrel front-end temperature divides four sections of controls, control at 200 ~ 230 DEG C respectively, head temperature divides two sections of controls, control at 220 ~ 240 DEG C respectively,
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50 ~ 80Kg, oxidation inhibitor 2 ~ 4Kg proportioning, 25-35 minute is mixed in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine, extruding granulator barrel back segment temperature divides four sections of controls, control at 180 ~ 200 DEG C respectively, barrel front-end temperature divides four sections of controls, controls at 200 ~ 230 DEG C respectively, head temperature divides two sections of controls, controls at 220 ~ 240 DEG C respectively;
(3) three-layer co-extruded blown film: adopt common three-layer co-extruded film blowing device, adopt the pellet coextrusion film blowing that (2) step is prepared respectively, three extruder barrel back segment temperature all adopt four sections of controls, control at 180 ~ 200 DEG C respectively, and barrel front-end temperature also all adopts four sections of controls, control at 210 ~ 230 DEG C respectively, co-extruding machine head temperature divides two sections of controls, controls at 220 ~ 240 DEG C respectively, and blow-up ratio is 1.5 ~ 2.0, screw speed 20 ~ 40r/min, pulling speed 10 ~ 50m/min.
And, the (1) described Pullulan polysaccharide of step is the exocellular polysaccharide that Aureobasidium pullulans fermentation produces, and its basic structure is that the trisaccharide maltose repeating unit that connects into of α-Isosorbide-5-Nitrae-glycosidic link is with α-1, the straight-chain dextran that 6-glycosidic link is polymerized, molecular-weight average is 2 × 10 5.
And the internal layer that step is (2) described and skin are LDPE/PBM/Pullulan layer, and middle layer is PBM/Pullulan layer.
And the (2) described LDPE of step is general thin level Low Density Polyethylene.
And, the (2) described PBM masterbatch of step is the biodegradable material utilizing agro-ecology resource to be main material production, be adopt starch, Vegetable oil lipoprotein etc. to synthesize for main raw material fully-degradable natural macromolecular material after special processing, form with water-soluble high-molecular material and a small amount of resin compounded, at present, market has a lot of sale, outward appearance is the thermoplastic granulates shape masterbatch of slightly caoutchouc elasticity.
And the (2) described oxidation inhibitor of step is general oxidation inhibitor, can be antioxidant 1010, irgasfos 168 etc., can suppress or delay thin-film material thermooxidizing in atmosphere.
And the (2) described UV light absorber of step is general UV light absorber, can be salol, ultraviolet absorbent UV-531 etc., UV-light can be prevented the destruction of thin-film material.
Advantage of the present invention and positively effect are:
1, a kind of preparation method with barrier degradable plastics laminated film of the present invention, be composited by three-layer thin-film, internal layer is identical with outer raw material, and be LDPE/PBM/Pullulan component, middle layer is PBM/Pullulan component.The present invention selects treated starch degradable plastics masterbatch PBM ripe in the market and tannic acid modified Pullulan polysaccharide and film-grade LDPE blended.The fundamental characteristics of LDPE is utilized to ensure the mechanical property that film is good; Utilize the degradability of PBM and Pullulan polysaccharide, realize the environment friendly of thin-film material; Utilize the height of Pullulan polysaccharide barrier, improve the oxygen barrier effect of thin-film material; Starch and Pullulan polysaccharide in PBM masterbatch is utilized as glucide similarity structurally, to improve the consistency of PBM and Pullulan polysaccharide material entirety.
2, the present invention adopts Weibull to carry out modification to Pullulan polysaccharide, and described Weibull, also known as tannic acid, is faint yellow last without crystalline flour to light brown, belongs to the complex compound of multi-phenol, at occurring in nature rich content, cheap and easy to get.After Weibull is polysaccharide-modified to Pullulan, the consistency of Pullulan polysaccharide and LDPE and PBM can be significantly improved, improve interface bond strength, therefore significantly can improve the mechanical property of system.Meanwhile, Weibull carries out modification to Pullulan polysaccharide can the addition of Pullulan polysaccharide in increase system, therefore has remarkable help to the barrier and degradability improving film.
3, the present invention adopts three-layer co-extruded blown film techniques to prepare a kind ofly to have barrier degradable plastics laminated film, internal layer ensures with outer the mechanical property that film is good, barrier and the degradability of middle layer strengthening film, these three layers can combine by three-layer co-extruded blown film techniques well, and film integrity is good.And the present invention adopts the current technology of three-layer co-extruded blown film techniques very ripe, production technique is simple, and production efficiency is high, industrializing implementation is easy.
4, a kind of preparation method with barrier degradable plastics laminated film of the present invention, adopt the laminated film prepared of the technology of the present invention can automatic classifying under the effect of oxygen enrichment and microorganism, film after discarded can by the degradable digestion of occurring in nature microorganism, final generation carbonic acid gas and water, can improve 70%-80% compared with the ldpe film oxygen barrier performance of same thickness, the ldpe film of mechanical property and same thickness is substantially suitable.
Embodiment
The present invention is described below by concrete embodiment.Unless stated otherwise, technique means used in the present invention is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention only limited by claims.To those skilled in the art, under the prerequisite not deviating from essence of the present invention and scope, the various change carry out the material component in these embodiments and consumption or change also belong to protection scope of the present invention.
Embodiment 1:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) preparation of modification Pullulan polysaccharide.Take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2500mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer raw material, and its component is LDPE 100Kg, PBM masterbatch 70Kg, tannic acid modified Pullulan polysaccharide 20Kg, irgasfos 168 are 4Kg, ultraviolet absorbent UV-531 is 1Kg.LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber are mixed 25 minutes in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine by formula.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C;
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50Kg, oxidation inhibitor 4Kg proportioning, mixes 35 minutes, then extruding pelletization in double-screw extruding pelletizing machine in conventional high-speed mixer.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C;
(3) three-layer co-extruded blown film.Adopt common three-layer co-extruded film blowing device, adopt pellet coextrusion film blowing prepared by step (2) respectively.Three extruder barrel back segment temperature all adopt four sections of controls, are respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C.Co-extruding machine head temperature divides two sections of controls, is respectively 230 DEG C, 230 DEG C.Blow-up ratio 1.5, screw speed 40r/min, pulling speed 30m/min.
Embodiment 2:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) preparation of modification Pullulan polysaccharide.Take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2000mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer raw material, and its component is LDPE 100Kg, PBM masterbatch 50Kg, tannic acid modified Pullulan polysaccharide 40Kg, and irgasfos 168 is 4Kg, and ultraviolet absorbent UV-531 is 1Kg.LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber are mixed 30 minutes in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine by formula.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C;
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50Kg, oxidation inhibitor 4Kg proportioning, mixes 35 minutes, then extruding pelletization in double-screw extruding pelletizing machine in conventional high-speed mixer.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C;
(3) three-layer co-extruded blown film.Adopt common three-layer co-extruded film blowing device, adopt pellet coextrusion film blowing prepared by step (2) respectively.Three extruder barrel back segment temperature all adopt four sections of controls, are respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C.Co-extruding machine head temperature divides two sections of controls, is respectively 230 DEG C, 230 DEG C.Blow-up ratio 2, screw speed 40r/min, pulling speed 10m/min.
Embodiment 3:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) preparation of modification Pullulan polysaccharide.Take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 3000mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer raw material, and its component is LDPE 100Kg, PBM masterbatch 60Kg, tannic acid modified Pullulan polysaccharide 30Kg, and irgasfos 168 is 3Kg, and ultraviolet absorbent UV-531 is 1Kg.LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber are mixed 35 minutes in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine by formula.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 240 DEG C;
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50Kg, oxidation inhibitor 4Kg proportioning, mixes 35 minutes, then extruding pelletization in double-screw extruding pelletizing machine in conventional high-speed mixer.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 240 DEG C;
(3) three-layer co-extruded blown film.Adopt common three-layer co-extruded film blowing device, adopt pellet coextrusion film blowing prepared by step (2) respectively.Three extruder barrel back segment temperature all adopt four sections of controls, are respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 210 DEG C, 210 DEG C, 220 DEG C, 230 DEG C.Co-extruding machine head temperature divides two sections of controls, is respectively 230 DEG C, 240 DEG C.Blow-up ratio 1.8, screw speed 30r/min, pulling speed 50m/min.
Embodiment 4:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) preparation of modification Pullulan polysaccharide.Take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2700mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer raw material, and its component is LDPE 100Kg, PBM masterbatch 50Kg, tannic acid modified Pullulan polysaccharide 40Kg, and irgasfos 168 is 4Kg, and ultraviolet absorbent UV-531 is 0.5Kg.LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber are mixed 25 minutes in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine by formula.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, and head two sections of temperature are respectively 220 DEG C, 220 DEG C;
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 80Kg, oxidation inhibitor 2Kg proportioning, mixes 35 minutes, then extruding pelletization in double-screw extruding pelletizing machine in conventional high-speed mixer.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C; .
(3) three-layer co-extruded blown film.Adopt common three-layer co-extruded film blowing device, adopt pellet coextrusion film blowing prepared by step (2) respectively.Three extruder barrel back segment temperature all adopt four sections of controls, are respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C.Co-extruding machine head temperature divides two sections of controls, is respectively 220 DEG C, 220 DEG C.Blow-up ratio 2.0, screw speed 20r/min, pulling speed 15m/min.
Embodiment 5:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) preparation of modification Pullulan polysaccharide.Take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2900mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer raw material, and its component is LDPE 100Kg, PBM masterbatch 70Kg, tannic acid modified Pullulan polysaccharide 40Kg, and irgasfos 168 is 4Kg, and ultraviolet absorbent UV-531 is 1Kg.LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber are mixed 30 minutes in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine by formula.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, and head two sections of temperature are respectively 220 DEG C, 220 DEG C;
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 75Kg, oxidation inhibitor 3Kg proportioning, mixes 35 minutes, then extruding pelletization in double-screw extruding pelletizing machine in conventional high-speed mixer.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C;
(3) three-layer co-extruded blown film.Adopt common three-layer co-extruded film blowing device, adopt pellet coextrusion film blowing prepared by step (2) respectively.Three extruder barrel back segment temperature all adopt four sections of controls, are respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C.Co-extruding machine head temperature divides two sections of controls, is respectively 230 DEG C, 230 DEG C.Blow-up ratio 1.8, screw speed 20r/min, pulling speed 40m/min.
Embodiment 6:
There is a preparation method for barrier degradable plastics laminated film, comprise the following steps:
(1) preparation of modification Pullulan polysaccharide.Take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2900mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide.
(2) preparation of three-layer thin-film raw material.Internal layer is identical with outer raw material, and its component is LDPE 100Kg, PBM masterbatch 60Kg, tannic acid modified Pullulan polysaccharide 30Kg, and irgasfos 168 is 3Kg, and ultraviolet absorbent UV-531 is 1Kg.LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber are mixed 30 minutes in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine by formula.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 200 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 220 DEG C, and head two sections of temperature are respectively 220 DEG C, 220 DEG C;
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 75Kg, oxidation inhibitor 2Kg proportioning, mixes 30 minutes, then extruding pelletization in double-screw extruding pelletizing machine in conventional high-speed mixer.Extruding granulator barrel back segment temperature divides four sections of controls, is respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 200 DEG C, 210 DEG C, 210 DEG C, 230 DEG C, and head two sections of temperature are respectively 230 DEG C, 230 DEG C;
(3) three-layer co-extruded blown film.Adopt common three-layer co-extruded film blowing device, adopt pellet coextrusion film blowing prepared by step (2) respectively.Three extruder barrel back segment temperature all adopt four sections of controls, are respectively 180 DEG C, 190 DEG C, 190 DEG C, 200 DEG C, and barrel leading portion four sections of temperature are respectively 210 DEG C, 210 DEG C, 220 DEG C, 220 DEG C.Co-extruding machine head temperature divides two sections of controls, is respectively 230 DEG C, 230 DEG C.Blow-up ratio 1.5, screw speed 30r/min, pulling speed 50m/min.

Claims (7)

1. there is a preparation method for barrier degradable plastics laminated film, it is characterized in that: the steps include:
(1) the preparation of modification Pullulan polysaccharide: take Pullulan polysaccharide 100Kg, add in the tannic acid solution of 100L concentration 2000 ~ 3000mg/L and be uniformly dissolved, pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide;
(2) the preparation of three-layer thin-film raw material: internal layer is identical with outer raw material, its component is LDPE 100Kg, PBM masterbatch 50 ~ 70Kg, tannic acid modified Pullulan polysaccharide 20 ~ 40Kg, oxidation inhibitor 2 ~ 4Kg, UV light absorber 0.5 ~ 1Kg, by formula by LDPE, PBM masterbatch, modification Pullulan polysaccharide and oxidation inhibitor, UV light absorber mixes 25-35 minute in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine, extruding granulator barrel back segment temperature divides four sections of controls, control at 180 ~ 200 DEG C respectively, barrel front-end temperature divides four sections of controls, control at 200 ~ 230 DEG C respectively, head temperature divides two sections of controls, control at 220 ~ 240 DEG C respectively,
Middle level raw material presses PBM masterbatch 100Kg, tannic acid modified Pullulan polysaccharide 50 ~ 80Kg, oxidation inhibitor 2 ~ 4Kg proportioning, 25-35 minute is mixed in conventional high-speed mixer, then extruding pelletization in double-screw extruding pelletizing machine, extruding granulator barrel back segment temperature divides four sections of controls, control at 180 ~ 200 DEG C respectively, barrel front-end temperature divides four sections of controls, controls at 200 ~ 230 DEG C respectively, head temperature divides two sections of controls, controls at 220 ~ 240 DEG C respectively;
(3) three-layer co-extruded blown film: adopt common three-layer co-extruded film blowing device, adopt the pellet coextrusion film blowing that (2) step is prepared respectively, three extruder barrel back segment temperature all adopt four sections of controls, control at 180 ~ 200 DEG C respectively, and barrel front-end temperature also all adopts four sections of controls, control at 210 ~ 230 DEG C respectively, co-extruding machine head temperature divides two sections of controls, controls at 220 ~ 240 DEG C respectively, and blow-up ratio is 1.5 ~ 2.0, screw speed 20 ~ 40r/min, pulling speed 10 ~ 50m/min.
2. the preparation method with barrier degradable plastics laminated film according to claim 1, it is characterized in that: the (1) described Pullulan polysaccharide of step is the exocellular polysaccharide that Aureobasidium pullulans fermentation produces, its basic structure is α-1, the trisaccharide maltose repeating unit that 4-glycosidic link connects into is with α-1, the straight-chain dextran that 6-glycosidic link is polymerized, molecular-weight average is 2 × 10 5.
3. the preparation method with barrier degradable plastics laminated film according to claim 1, is characterized in that: the internal layer that step is (2) described and skin are LDPE/PBM/Pullulan layer, and middle layer is PBM/Pullulan layer.
4. the preparation method with barrier degradable plastics laminated film according to claim 1, is characterized in that: the (2) described LDPE of step is general thin level Low Density Polyethylene.
5. the preparation method with barrier degradable plastics laminated film according to claim 1, is characterized in that: the (2) described PBM masterbatch of step is commercial goods.
6. the preparation method with barrier degradable plastics laminated film according to claim 1, is characterized in that: the (2) described oxidation inhibitor of step is general oxidation inhibitor is antioxidant 1010 or irgasfos 168.
7. the preparation method with barrier degradable plastics laminated film according to claim 1, is characterized in that: the (2) described UV light absorber of step is general UV light absorber is salol or ultraviolet absorbent UV-531.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107298789A (en) * 2017-08-22 2017-10-27 安徽华猫软包装有限公司 A kind of fresh-keeping use degradable plastic film and preparation method thereof
US11319566B2 (en) 2017-04-14 2022-05-03 Capsugel Belgium Nv Process for making pullulan
US11576870B2 (en) 2017-04-14 2023-02-14 Capsugel Belgium Nv Pullulan capsules

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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
CN103483664A (en) * 2013-09-22 2014-01-01 苏州市湘园特种精细化工有限公司 Degradable plastic film

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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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11319566B2 (en) 2017-04-14 2022-05-03 Capsugel Belgium Nv Process for making pullulan
US11576870B2 (en) 2017-04-14 2023-02-14 Capsugel Belgium Nv Pullulan capsules
US11878079B2 (en) 2017-04-14 2024-01-23 Capsugel Belgium Nv Pullulan capsules
CN107298789A (en) * 2017-08-22 2017-10-27 安徽华猫软包装有限公司 A kind of fresh-keeping use degradable plastic film and preparation method thereof

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