CN104859237A - Degradable three-layer co-extrusion plastic composite film with oxygen separation performance - Google Patents
Degradable three-layer co-extrusion plastic composite film with oxygen separation performance Download PDFInfo
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Abstract
The invention discloses a degradable three-layer co-extrusion plastic composite film with an oxygen separation performance. 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
Technical field
The invention belongs to plastic film material field, be specially a kind of there is excellent mechanical performances there is the three-layer co-extruded composite plastic film of barrier degradable.
Background technology
It is excellent barrier that food, medicine preservation require packaging 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 packing film material has a strong impact on the quality of packaging because of the gas permeability 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, material recovery difficulty, contaminated 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 package material uses, discarded packaging material problem of environmental pollution has caused the great attention of countries in the world, and the environment friendly realizing packaging material has become one of packaging material scientific research most attraction and challenging direction.
Biodegradable plastic is one of effective way of administering plastic refuse environmental pollution, from the packaging 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 prospects are very wide.
Starch is a kind of abundance, cheap natural macromolecular material, and be also a kind of inexhaustible renewable resource, it can be biodegradable in a variety of environmental conditions, final catabolite CO
2and H
2o can be recycled by the photosynthesis of plant, can not cause any pollution to environment.Therefore, starch is widely used in research and the product development of degradation plastic, and has achieved great progress.Current, PBM masterbatch on sale on market is exactly take starch as a kind of degradation plastic masterbatch of raw material, is a kind of biodegradation material utilizing agro-ecology resource to be main material production.PBM adopts starch, vegetable fat etc. for primary raw material synthesis fully-degradable natural macromolecular material, then after specially treated, 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 hot strength and fracture strength, 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 maltotriose repetitive that α-Isosorbide-5-Nitrae-glycosidic bond connects into is polymerized with α-1,6-glycosidic bond, and mean molecule quantity 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 packaging material use with biodegradability and strong oxygen barrier.But Pullulan polysaccharide packaging 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 plastic sheeting degradability and barrier good combination, inventor discloses a kind of oxygen barrier and degredation plastic film (CN103160012A) early stage, and its raw material components is respectively low density polyethylene (LDPE) (LDPE), PBM masterbatch, Pullulan polysaccharide, antioxidant, ultra-violet 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 similitude structurally, to improve the compatibility 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 plastic sheeting, 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:
A kind of have the three-layer co-extruded composite plastic film of barrier degradable, comprise three-layer thin-film raw material, wherein the raw material components of modification Pullulan polysaccharide comprises Pullulan polysaccharide and tannic acid solution, and Pullulan polysaccharide and tannic acid solution weight ratio are 1:2 ~ 3;
Internal layer in three-layer thin-film raw material is identical with outer raw material and consumption thereof, and its component and parts by weight are:
LDPE 100 parts;
PBM masterbatch 50 ~ 70 parts;
Tannic acid modified Pullulan polysaccharide 20 ~ 40 parts;
2 ~ 4 parts, antioxidant;
Ultra-violet absorber 0.5 ~ 1 part,
Component and the respective parts by weight of middle level raw material are:
By PBM masterbatch 100 parts;
Tannic acid modified Pullulan polysaccharide 50 ~ 80 parts;
2 ~ 4 parts, antioxidant,
Wherein, wherein the raw material components of modification Pullulan polysaccharide comprises Pullulan polysaccharide and tannic acid solution, and Pullulan polysaccharide and tannic acid solution weight ratio are 1000:2 ~ 3.
And described internal layer and skin are LDPE/PBM/Pullulan layer, intermediate layer is PBM/Pullulan layer.
And described LDPE is general thin level low density polyethylene (LDPE).
And described PBM masterbatch is commercial goods.
And described antioxidant is general antioxidant is antioxidant 1010 or irgasfos 168.
And described ultra-violet absorber is general ultra-violet absorber is phenyl salicytate or ultraviolet absorbent UV-531.
The above-mentioned preparation method with the three-layer co-extruded composite plastic film of barrier degradable, comprises the following steps:
(1) the preparation of modification Pullulan polysaccharide: take Pullulan polysaccharide, adding density is be uniformly dissolved in the tannic acid solution of 2 ~ 3g/L, and pelletizing is dried in air blast, obtains tannic acid modified Pullulan polysaccharide;
(2) the preparation of three-layer thin-film raw material: internal layer and outer raw material, by formula, LDPE, PBM masterbatch, modification Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed 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, controls at 220 ~ 240 DEG C respectively;
Middle level raw material mixes 25-35 minute by formula 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, 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, hauling speed 10 ~ 50m/min.
Advantage of the present invention and good effect are:
1, a kind of preparation method with barrier degradation plastic 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, intermediate layer is PBM/Pullulan component.The present invention selects modified starch degradation plastic 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 similitude structurally, to improve the compatibility of PBM and Pullulan polysaccharide material entirety.
2, the present invention adopts tannic acid to carry out modification to Pullulan polysaccharide, and described tannic acid, 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 tannic acid is polysaccharide-modified to Pullulan, the compatibility 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, tannic acid 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 degradation plastic laminated film, internal layer ensures with outer the mechanical property that film is good, barrier and the degradability of intermediate 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 technology is simple, and production efficiency is high, industrializing implementation is easy.
4, a kind of preparation method with barrier degradation plastic 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 carbon dioxide 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.
Detailed description of the invention
The present invention is described below by concrete embodiment.Unless stated otherwise, technological 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 degradation plastic 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 2.5g/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 antioxidant, ultra-violet 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, antioxidant 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, hauling speed 30m/min.
Embodiment 2:
There is a preparation method for barrier degradation plastic 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 2g/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 antioxidant, ultra-violet 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, antioxidant 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, hauling speed 10m/min.
Embodiment 3:
There is a preparation method for barrier degradation plastic 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 3g/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 antioxidant, ultra-violet 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, antioxidant 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, hauling speed 50m/min.
Embodiment 4:
There is a preparation method for barrier degradation plastic 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 2.7g/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 antioxidant, ultra-violet 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, antioxidant 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, hauling speed 15m/min.
Embodiment 5:
There is a preparation method for barrier degradation plastic 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 2.9g/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 antioxidant, ultra-violet 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, antioxidant 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, hauling speed 40m/min.
Embodiment 6:
There is a preparation method for barrier degradation plastic 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 2.9g/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 antioxidant, ultra-violet 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, antioxidant 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, hauling speed 50m/min.
Claims (8)
1. one kind has the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: comprise three-layer thin-film raw material, wherein the raw material components of modification Pullulan polysaccharide comprises Pullulan polysaccharide and tannic acid solution, and Pullulan polysaccharide and tannic acid solution weight ratio are 1:2 ~ 3;
Internal layer in three-layer thin-film raw material is identical with outer raw material and consumption thereof, and its component and parts by weight are:
LDPE 100 parts;
PBM masterbatch 50 ~ 70 parts;
Tannic acid modified Pullulan polysaccharide 20 ~ 40 parts;
2 ~ 4 parts, antioxidant;
Ultra-violet absorber 0.5 ~ 1 part,
Component and the respective parts by weight of middle level raw material are:
By PBM masterbatch 100 parts;
Tannic acid modified Pullulan polysaccharide 50 ~ 80 parts;
2 ~ 4 parts, antioxidant,
Wherein, wherein the raw material components of modification Pullulan polysaccharide comprises Pullulan polysaccharide and tannic acid solution, and Pullulan polysaccharide and tannic acid solution weight ratio are 1000:2 ~ 3.
2. according to claim 1 have the three-layer co-extruded composite plastic film of barrier degradable, and it is characterized in that: described internal layer and skin are LDPE/PBM/Pullulan layer, intermediate layer is PBM/Pullulan layer.
3. according to claim 1 have the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: described LDPE is general thin level low density polyethylene (LDPE).
4. according to claim 1 have the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: described PBM masterbatch is commercial goods.
5. according to claim 1 have the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: described antioxidant is general antioxidant is antioxidant 1010 or irgasfos 168.
6. according to claim 1 have the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: described ultra-violet absorber is general ultra-violet absorber is phenyl salicytate or ultraviolet absorbent UV-531.
7. according to claim 1 have the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: described tannic acid solution density is 2 ~ 3g/L.
8. prepare a method as claimed in claim 1 with the three-layer co-extruded composite plastic film of barrier degradable, it is characterized in that: comprise the following steps:
(1) the preparation of modification Pullulan polysaccharide: take Pullulan polysaccharide, add in tannic acid solution 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 and outer raw material, by formula, LDPE, PBM masterbatch, modification Pullulan polysaccharide and antioxidant, ultra-violet absorber are mixed 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, controls at 220 ~ 240 DEG C respectively;
Middle level raw material mixes 25-35 minute by formula 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, 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, hauling speed 10 ~ 50m/min.
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| 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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| US20100175842A1 (en) * | 2005-03-22 | 2010-07-15 | Arrow Coated Products Ltd. | High strength paper and process of manufacture |
| 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 |
| CN103467825A (en) * | 2013-09-22 | 2013-12-25 | 苏州市湘园特种精细化工有限公司 | Degradable flame-retardant plastic nano-film |
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| US20100175842A1 (en) * | 2005-03-22 | 2010-07-15 | Arrow Coated Products Ltd. | High strength paper and process of manufacture |
| 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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| 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 |
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