CN111409346A - Degradable film and preparation method thereof - Google Patents
Degradable film and preparation method thereof Download PDFInfo
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- CN111409346A CN111409346A CN202010350506.0A CN202010350506A CN111409346A CN 111409346 A CN111409346 A CN 111409346A CN 202010350506 A CN202010350506 A CN 202010350506A CN 111409346 A CN111409346 A CN 111409346A
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
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- B32B2307/00—Properties of the layers or laminate
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a degradable film, which comprises an inner layer and an outer layer, wherein the inner layer comprises the following components in parts by weight: 60-80 parts of polylactic acid-glycolic acid copolymer, 20-65 parts of polycaprolactone, 2.5-15 parts of modified compatilizer, 4-19 parts of flexibilizer and 0.2-4 parts of opening agent; the outer layer comprises the following components in parts by weight: 60-100 parts of polylactic acid-glycolic acid copolymer, 20-60 parts of polycaprolactone, 8-20 parts of diacetyl epoxy vegetable oil acid glyceride, 2-18 parts of modified compatilizer, 1.8-30 parts of filler and 4-16.4 parts of functional additive. The film has good low-temperature heat sealability, tensile mechanical strength and elongation at break, and can be applied to the aspects of agricultural mulching films, preservative films, shopping bags and the like.
Description
Technical Field
The invention relates to the technical field of degradable materials, in particular to a degradable film and a preparation method thereof.
Background
In modern life, the application of plastic products such as express packages, adhesive tapes, shopping bags, garbage bags, food packages and the like is all the same. The portable, beautiful and soft plastic product provides convenience for daily life, but the plastic product is difficult to degrade after the service life is over, and brings great negative influence on the social environment of the current generation and the future. The new plastics economics report that only 14% of the plastic packages are recovered worldwide, plus losses in processing, are ultimately effectively recovered by only 10%. The current disposal mode of the traditional non-degradable plastics mainly depends on incineration or landfill. The degradation time of the plastic piled in the soil is more than 300 years, the plastic particles enter the sea and enter the human body, the potential harm to human body organs and the threat to life safety after other animals eat the plastic by mistake remind that the dependence on the non-degradable plastic products is gradually reduced.
In 2020, the national development reform Commission issues an opinion book for further enhancing plastic pollution control, the opinion book requires that non-degradable plastic bags are prohibited to be used in places such as markets, supermarkets and the like in built areas of direct prefecture cities, provincial cities and planned single-row cities, trade market specifications and use limitation of the non-degradable plastic bags are provided, and environment-friendly cloth bags, paper bags and degradable plastic bag products are widely used under the requirements of the policies; in addition, the suggestion book clearly requires that the production and the sale of ultrathin non-degradable plastic shopping bags with the thickness of less than 0.025 mm and polyethylene agricultural mulching films with the thickness of less than 0.01 mm are forbidden, and the degradable mulching films need to be popularized in a large scale in key film covering areas. The plastic inhibition is imminent, and the development and application of degradable substitute products are further promoted.
P L GA has good biocompatibility and degradability, but has a wide application range, but is limited by factors such as too high price and degradation rate, and the like, and the application of P L GA is mostly concentrated in the biomedical field, such as surgical sutures, orthopedic fixation, tissue repair materials, drug controlled release systems and the like, and the application of the P L GA in replacing the conventional non-degradable plastic film in daily life needs to be developed.
Disclosure of Invention
One of the objects of the present invention is to provide a degradable film which is completely degradable within a certain period of time after the end of its useful life, converted into biomass, carbon dioxide and water, green and environmentally friendly, harmless to the environment and human health, and has a fast degradation rate, as well as good tensile and tear strength in all directions, high elastic modulus, high elongation at break and heat-sealable at low temperatures.
The invention discloses a degradable film, which comprises an inner layer and an outer layer, wherein the inner layer comprises the following components in parts by weight: 60-80 parts of polylactic acid-glycolic acid copolymer, 20-65 parts of polycaprolactone, 2.5-15 parts of modified compatilizer, 4-19 parts of flexibilizer and 0.2-4 parts of opening agent;
preferably, the thickness of the inner layer is 8-80 μm;
preferably, the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 4-12 ten thousand, wherein the ratio of monomer lactic acid to glycolic acid is (3-7): (7-3);
preferably, the weight average molecular weight of the polycaprolactone is 4-9 ten thousand;
preferably, the modified compatilizer is prepared from glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer or polycaprolactone, and more preferably, the modified compatilizer can be glycidyl methacrylate grafted polycaprolactone;
preferably, the toughening agent is other biodegradable polymers, including at least one of polybutylene adipate terephthalate, polymethyl ethylene carbonate, polyhydroxyalkanoate, poly- β -hydroxybutyric acid, polylactic acid-caprolactone copolymer, and polybutylene terephthalate-co-succinate;
preferably, the opening agent is added to increase the lubricating property of the inner layer of the film and prevent adhesion, and comprises at least one of flake graphite, talcum powder, diatomite, barium sulfate, titanium dioxide and opening master batch.
Wherein the outer layer comprises the following components in parts by weight: 60-100 parts of polylactic acid-glycolic acid copolymer, 20-60 parts of polycaprolactone, 8-20 parts of diacetyl epoxy vegetable oil acid glyceride, 2-18 parts of modified compatilizer, 1.8-30 parts of filler and 4-16.4 parts of functional auxiliary agent.
Preferably, the thickness of the outer layer is 12-150 μm;
preferably, the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 4-12 ten thousand, wherein the ratio of monomer lactic acid to glycolic acid is (3-7): (7-3);
preferably, the weight average molecular weight of the polycaprolactone is 4-9 ten thousand;
preferably, the diacetyl epoxy vegetable oil acid glyceride is a small molecular plasticizer, and the relative molecular mass is 300-2000;
preferably, the modified compatilizer is prepared from glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer or grafted polycaprolactone, and more preferably, the modified compatilizer can be glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer;
preferably, the filler can be at least one of heavy calcium carbonate, nano calcium carbonate, talcum powder, barium sulfate, montmorillonite, chitosan, sodium alginate, mica powder, white carbon black and cellulose nanocrystals;
preferably, the functional auxiliary agent comprises 0.2-4 parts of slipping agent, 0.5-13 parts of antistatic agent and 0.03-1 part of ultraviolet absorber.
The degradable film also comprises a core layer, wherein the core layer comprises the following components in parts by weight: 80-120 parts of polylactic acid-glycolic acid copolymer, 20-40 parts of polycaprolactone, 5-16 parts of diacetyl epoxy vegetable oil acid glyceride and 3-8 parts of modified compatilizer;
preferably, the thickness of the core layer is 20-100 μm;
preferably, the weight average molecular weight of the polylactic acid-glycolic acid copolymer is 4-12 ten thousand, wherein the ratio of monomer lactic acid to glycolic acid is (3-7): (7-3);
preferably, the weight average molecular weight of the polycaprolactone is 4-9 ten thousand;
preferably, the diacetyl epoxy vegetable oil acid glyceride is a small molecular plasticizer, and the relative molecular mass is 300-2000;
preferably, the modified compatilizer is prepared from glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer or polycaprolactone, and more preferably, the modified compatilizer can be glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer;
the invention also aims to provide a preparation method of the degradable film. The preparation steps are as follows:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Weighing all the raw materials according to the weight parts of the inner layer, the outer layer and the core layer to prepare three types:
(3) respectively mixing the three raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min;
(4) and (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melt blending, wherein the operation temperature of each temperature zone of the extruder is 110-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using an extruder, wherein the three biodegradable polyester materials are respectively and correspondingly used as raw materials of an inner layer, an outer layer and a core layer of the co-extrusion film, the operation temperature of each temperature zone of the film blowing machine is 120-200 ℃, the rotating speed is 40-200r/min, and the degradable film is obtained by sequentially melting, plasticizing, pressurizing, cooling, drawing and rolling.
Preferably, the modified compatilizer added in each layer is prepared by the following method:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part of initiator, and spraying the mixture onto the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into an extruder, melting and blending to prepare modified master batches, wherein the operating temperature of each temperature zone of the extruder is 120-.
Preferably, the initiator is at least one of benzoyl peroxide, dicumyl peroxide, N-dimethylaniline, N-dimethyl-p-toluidine, and more preferably, the initiator may be dicumyl peroxide.
The invention has the beneficial effects that:
the film prepared by the invention has stable performance when used at room temperature, is not easily influenced by moisture and humidity, has high biodegradability under the condition of simulated compost, has short degradation time, and has the degradation rate of more than 90 percent in 6 months. In addition, the film has the advantages of good all-directional tensile and tearing strength, high elastic modulus, high elongation at break and low-temperature heat sealing, and can be applied to supermarket shopping bags, disposable plastic bags, garbage bags and the like to reduce white pollution caused by the conventional disposable non-degradable plastic bags.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The degradable film of the embodiment comprises an inner layer and an outer layer, wherein the inner layer comprises the following components in parts by weight: 80 parts of polylactic acid-glycolic acid copolymer, 65 parts of polycaprolactone, 4 parts of glycidyl methacrylate grafted polycaprolactone, 10 parts of polyhydroxyalkanoate, 2 parts of polylactic acid-caprolactone copolymer and 0.2 part of flake graphite;
the outer layer comprises the following components in parts by weight: 100 parts of polylactic acid-glycolic acid copolymer, 60 parts of polycaprolactone, 20 parts of diacetyl epoxy vegetable oil acid glyceride, 10 parts of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer, 1.8 parts of nano calcium carbonate, 1.2 parts of sodium alginate, 4 parts of slipping agent, 12 parts of antistatic agent and 0.4 part of ultraviolet absorbent;
the degradable film of the embodiment further comprises a core layer, wherein the core layer comprises the following components in parts by weight: 120 parts of polylactic acid-glycolic acid copolymer, 40 parts of polycaprolactone, 5 parts of diacetyl epoxy vegetable oil acid glyceride and 3 parts of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer.
This example provides a method for preparing a degradable film as described above. The preparation steps are as follows:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Weighing all the raw materials according to the weight parts of the inner layer, the outer layer and the core layer to prepare three types:
(3) respectively mixing the three raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min;
(4) and (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melt blending, wherein the operation temperature of each temperature zone of the extruder is 120-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using an extruder, wherein the three biodegradable polyester materials are respectively and correspondingly used as raw materials of an inner layer, an outer layer and a core layer of the co-extrusion film, the operation temperature of each temperature zone of the film blowing machine is 120-160 ℃, the rotating speed of a screw is 60-120r/min, and the degradable film is obtained by sequentially melting, plasticizing, pressurizing, cooling, drawing and rolling.
The preparation method of the glycidyl methacrylate grafted polycaprolactone and glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer added in each layer is as follows:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part by weight of dicumyl peroxide, and spraying the mixture on the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into a double-screw extruder for melting and blending to prepare modified master batches, wherein the operating temperature of each temperature zone of the extruder is 120-.
The degradable film prepared in example 1 had an inner layer thickness of 25 μm, an outer layer thickness of 30 μm and a core layer thickness of 25 μm.
Example 2
The degradable film comprises an inner layer and an outer layer, wherein the inner layer comprises the following components, by weight, 60 parts of polylactic acid-glycolic acid copolymer, 20 parts of polycaprolactone, 15 parts of glycidyl methacrylate grafted polycaprolactone, 2 parts of poly- β -hydroxybutyric acid, 2 parts of polymethyl ethylene carbonate, 0.5 part of talcum powder and 1 part of diatomite;
wherein the outer layer comprises the following components in parts by weight: 70 parts of polylactic acid-glycolic acid copolymer, 50 parts of polycaprolactone, 12 parts of diacetyl epoxy vegetable oil acid glyceride, 18 parts of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer, 0.3 part of chitosan, 1.5 parts of montmorillonite and 6 parts of functional auxiliary agent;
the degradable core layer of the embodiment further comprises a core layer, wherein the core layer comprises the following components in parts by weight: 80 parts of polylactic acid-glycolic acid copolymer, 20 parts of polycaprolactone, 16 parts of diacetyl epoxy vegetable oil acid glyceride and 8 parts of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer.
This example provides a method for preparing a degradable film as described above. The preparation steps are as follows:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Weighing all the raw materials according to the weight parts of the inner layer, the outer layer and the core layer to prepare three types;
(3) respectively mixing the three raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min;
(4) and (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melting and blending, wherein the operation temperature of each temperature zone of the extruder is 120-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using a multilayer co-extrusion extruder, wherein the three biodegradable polyester materials are respectively and correspondingly used as raw materials of an inner layer, an outer layer and a core layer of the co-extrusion blown film, the operation temperature of each temperature zone of the film blowing machine is 130-180 ℃, the rotating speed is 40-60r/min, and the degradable film is obtained by sequentially melting, plasticizing, pressurizing, cooling, drawing and rolling.
The preparation method of the glycidyl methacrylate grafted polycaprolactone and glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer added in each layer is as follows:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part by weight of dicumyl peroxide, and spraying the mixture on the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into an extruder, melting and blending to prepare modified master batches, wherein the operation temperature of each temperature zone of the extruder is 140-.
The degradable film prepared in example 1 had an inner layer thickness of 25 μm, an outer layer thickness of 25 μm and a core layer thickness of 30 μm.
Example 3
The degradable film of the embodiment comprises an inner layer and an outer layer, wherein the inner layer comprises the following components in parts by weight: 70 parts of polylactic acid-glycolic acid copolymer, 45 parts of polycaprolactone, 2.5 parts of glycidyl methacrylate grafted polycaprolactone, 15 parts of polybutylene adipate terephthalate, 4 parts of polylactic acid-caprolactone copolymer and 4 parts of open master batch;
wherein the outer layer comprises the following components in parts by weight: 60 parts of polylactic acid-glycolic acid copolymer, 20 parts of polycaprolactone, 8 parts of diacetyl epoxy vegetable oil acid glyceride, 2 parts of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer, 7.5 parts of mica powder, 3 parts of cellulose nanocrystal and 4 parts of functional auxiliary agent.
This example provides a method for preparing a degradable polymeric film as described above. The preparation steps are as follows:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Weighing all the raw materials according to the weight parts of the inner layer and the outer layer to prepare 2 types;
(3) respectively mixing the two types of raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min;
(4) and (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melt blending, wherein the operation temperature of each temperature zone of the extruder is 140-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using an extruder, wherein the two biodegradable polyester materials are respectively and correspondingly used as raw materials of an inner layer and an outer layer of a co-extrusion film, the operation temperature of each temperature zone of the film blowing machine is 140-190 ℃, the rotating speed is 60-100r/min, and the degradable film is obtained by sequentially carrying out melting, plasticizing, pressurizing, cooling, traction and rolling.
The preparation method of the glycidyl methacrylate grafted polycaprolactone and glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer added in each layer is as follows:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part by weight of dicumyl peroxide, and spraying the mixture on the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into an extruder, melting and blending to prepare modified master batches, wherein the operating temperature of each temperature zone of the extruder is 120-.
The degradable film prepared in example 3 had an inner layer thickness of 15 μm, an outer layer thickness of 20 μm and a core layer thickness of 25 μm.
Comparative example 1
The degradable film of this comparative example comprises an outer layer and an inner layer, wherein the inner layer comprises the following components in parts by weight: 80 parts of polylactic acid-glycolic acid copolymer, 5 parts of polycaprolactone, 0.2 part of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer, 1 part of polyhydroxyalkanoate, 0.2 part of polylactic acid-caprolactone copolymer and 0.5 part of flake graphite;
the outer layer comprises the following components in parts by weight: 90 parts of polylactic acid-glycolic acid copolymer, 5.5 parts of polycaprolactone, 5 parts of diacetyl epoxy vegetable oil acid glyceride, 2 parts of heavy calcium carbonate and 8 parts of functional auxiliary agent.
The degradable film of the present comparative example further comprises a core layer, wherein the core layer comprises the following components in parts by weight: 95 parts of polylactic acid-glycolic acid copolymer, 3 parts of polycaprolactone, 4 parts of diacetyl epoxy vegetable oil acid glyceride and 2 parts of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer;
the embodiment provides a preparation method of a degradable film. The preparation steps are as follows:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Weighing all the raw materials according to the weight parts of the inner layer, the outer layer and the core layer to prepare three types;
(3) respectively mixing the raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min;
(4) and (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melting and blending, wherein the operation temperature of each temperature zone of the extruder is 120-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using an extruder, wherein the three biodegradable polyester materials are respectively and correspondingly used as raw materials of an inner layer, an outer layer and a core layer of the co-extrusion film, the operation temperature of each temperature zone of the film blowing machine is 120-160 ℃, the screw rotation speed is 40-120r/min, and the degradable film is obtained by sequentially melting, plasticizing, pressurizing, cooling, drawing and rolling.
The preparation method of the glycidyl methacrylate grafted polycaprolactone and glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer added in each layer is as follows:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part by weight of dicumyl peroxide, and spraying the mixture on the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into an extruder, melting and blending to prepare modified master batches, wherein the operating temperature of each temperature zone of the extruder is 120-.
The degradable film prepared in comparative example 1 had an inner layer thickness of 25 μm, an outer layer thickness of 30 μm, and a core layer thickness of 25 μm.
Comparative example 2
The degradable film of the comparative example comprises an inner layer and an outer layer, wherein the inner layer comprises the following components in parts by weight: 65 parts of polylactic acid-glycolic acid copolymer, 25 parts of polycaprolactone, 0.5 part of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer, 10 parts of polyhydroxyalkanoate, 2 parts of polylactic acid-caprolactone copolymer and 0.5 part of flake graphite;
wherein the outer layer comprises the following components in parts by weight: 70 parts of polylactic acid-glycolic acid copolymer, 25 parts of polycaprolactone, 0.1 part of diacetyl epoxy vegetable oil acid glyceride, 0.8 part of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer, 2 parts of heavy calcium carbonate and 8 parts of functional auxiliary agent.
The degradable film of the present comparative example further comprises a core layer, wherein the core layer comprises the following components in parts by weight: 90 parts of polylactic acid-glycolic acid copolymer, 30 parts of polycaprolactone, 0.15 part of diacetyl epoxy vegetable oil acid glyceride and 0.25 part of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer.
This example provides a method for preparing a degradable film as described above. The preparation steps are as follows:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Weighing all the raw materials according to the weight parts of the inner layer, the outer layer and the core layer to prepare three types;
(3) and (3) respectively mixing the three raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min.
(4) And (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melting and blending, wherein the operation temperature of each temperature zone of the extruder is 120-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using an extruder, wherein the three biodegradable polyesters are respectively and correspondingly used as raw materials of an inner layer, an outer layer and a core layer of the co-extrusion blown film, the operation temperature of each temperature zone of the film blowing machine is 120-160 ℃, the rotating speed of a screw is 60-120r/min, and the degradable film is obtained by sequentially carrying out melting, plasticizing, pressurizing, cooling, traction and rolling.
The preparation method of the glycidyl methacrylate grafted polycaprolactone and glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer added in each layer is as follows:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part by weight of dicumyl peroxide, and spraying the mixture on the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into an extruder, melting and blending to prepare modified master batches, wherein the operation temperature of each temperature zone of the extruder is 120-.
The degradable film prepared in comparative example 2 had an inner layer thickness of 25 μm, an outer layer thickness of 25 μm, and a core layer thickness of 30 μm.
Test examples
The films prepared in examples 1 to 3 were tested for tensile strength in the transverse and longitudinal directions, elongation at break in the transverse and longitudinal directions, heat seal strength, oxygen transmission rate and water vapor transmission rate, respectively, and the results are shown in Table 1. From the tensile comparison results of examples 1-3 and comparative examples 1-2, it can be seen that the tensile strength in both the transverse direction and the longitudinal direction of examples 1-3 in the present invention is higher than 25MPa, and meets the requirement that the tensile strength in the longitudinal direction is not lower than 11.76MPa according to the standard of the current standard GB13735-2017 polyethylene blow-molded agricultural ground cover film. For the films of examples 1-3, the elongation at break in the transverse direction and the longitudinal direction exceeds 230 percent, which shows that the films have better toughness and reach the standard of 'superior products' in the physical and mechanical properties of agricultural mulching films. In addition, the heat seal strength of the plastic shopping bags of examples 1-3 is between 9 and 12N/15mm, according to the standard GB/T21661-. It is worth noting that the comparative examples and the examples have reduced transverse and longitudinal tensile strength and elongation at break, and it can be known from the matching of the raw materials of the comparative experiments that the modified compatilizer, polycaprolactone, composite toughening agent and small molecule plasticizer have a synergistic effect on the mechanical properties of the multilayer composite system, and the lack of one or great reduction of one of them in parts by weight will have a certain negative effect on the system. The addition of the modified compatilizer can obviously improve the compatibility of the polylactic acid-glycolic acid copolymer and the polycaprolactone, and can regulate and control the degradation rate, the processing and forming process and the tensile property of the film. From the water vapor transmission rate of each set of data, it can be seen that the addition of polycaprolactone and composite toughening agent will result in a decrease in the water vapor transmission rate of the film, which is related to the added raw material increasing the hydrophobicity of the system. And the oxygen transmission rate of the film is increased by adding the polycaprolactone and the composite toughening agent. The film prepared by the invention has potential for being applied to wrapping fresh fruits and vegetables. The films of examples 1 to 3 had a degradation rate of more than 90% after a composting time of 180 days under simulated composting conditions, and the mass loss rates of comparative examples 1 and 2 were more than 90% within 90 days of composting, indicating that the films prepared according to the invention were degradable under composting conditions. Compared with the agricultural mulching film and the preservative film sold in the market, the film prepared by the embodiment meets the use requirements under the same conditions in the aspects of barrier property and tensile mechanical property. In addition, the invention uses degradable resin, so the prepared biodegradable film is green and environment-friendly, the post treatment has no pressure on the environment, and the film is superior to the existing film in the market in the aspect of degradability.
Table 1: test examples results of Performance test
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The degradable film is characterized by comprising an inner layer and an outer layer, wherein the inner layer comprises the following components in parts by weight:
60-80 parts of polylactic acid-glycolic acid copolymer;
20-65 parts of polycaprolactone;
2.5-15 parts of a modified compatilizer;
4-19 parts of a toughening agent;
0.2-4 parts of an opening agent;
the outer layer comprises the following components in parts by weight:
60-100 parts of polylactic acid-glycolic acid copolymer;
20-60 parts of polycaprolactone;
8-20 parts of diacetyl epoxy vegetable oil glyceride;
2-18 parts of a modified compatilizer;
1.8-30 parts of a filler;
4-16.4 parts of functional auxiliary agent.
2. The degradable film of claim 1 further comprising a core layer,
the core layer comprises the following components in parts by weight:
80-120 parts of polylactic acid-glycolic acid copolymer;
20-40 parts of polycaprolactone;
5-16 parts of diacetyl epoxy vegetable oil glyceride;
3-8 parts of a modified compatilizer.
3. The degradable film of claim 1, wherein the modifying compatibilizer is at least one of glycidyl methacrylate grafted polylactic acid-glycolic acid copolymer and glycidyl methacrylate grafted polycaprolactone.
4. The degradable film of claim 1, wherein the toughening agent is at least one of polybutylene adipate terephthalate, polymethyl ethylene carbonate, polyhydroxyalkanoate, poly- β -hydroxybutyric acid, polylactic acid-caprolactone copolymer, and polybutylene terephthalate-co-succinate.
5. The degradable film of claim 1, wherein the filler comprises at least one of ground calcium carbonate, nano calcium carbonate, talc, barium sulfate, montmorillonite, chitosan, sodium alginate, mica powder, white carbon black and cellulose nanocrystals.
6. The degradable film of claim 1, wherein the functional adjuvant comprises 0.2-4 parts of slipping agent, 0.5-20 parts of antistatic agent and 0.03-1 part of ultraviolet absorber.
7. The degradable film of claim 2 wherein said inner layer has a thickness of 8-80 μm, said outer layer has a thickness of 12-150 μm, and said core layer has a thickness of 20-100 μm.
8. A method for preparing the degradable film according to any one of claims 2 to 7, comprising the steps of:
(1) and (3) placing the polylactic acid-glycolic acid copolymer, the polycaprolactone and the flexibilizer at 40-50 ℃ for vacuum drying for 8-24 h.
(2) Preparing all the raw materials into three types according to the parts by weight of claim 2:
(3) and (3) respectively mixing the three raw materials in the step (2) in a high-speed mixer at normal temperature for 5-10 min.
(4) And (4) adding the uniformly mixed raw materials in the step (3) into an extruder in batches for melt blending, wherein the operation temperature of each temperature zone of the extruder is 110-.
(5) And (3) carrying out vacuum drying treatment on the biodegradable polyester material obtained in the step (4) at the temperature of 50-80 ℃ for 4-12 h.
(6) And (3) blowing the biodegradable polyester material dried in the step (5) as a master batch into a film by using an extruder, wherein the 3 biodegradable polyester materials are respectively used as raw materials of an inner layer, an outer layer and a core layer of the co-extrusion blown film correspondingly, the operation temperature of each temperature zone of the film blowing machine is 120-200 ℃, the rotating speed is 40-200r/min, and the biodegradable polyester film is obtained by sequentially melting, plasticizing, pressurizing, cooling, drawing and rolling.
9. The method for preparing a degradable film according to claim 8, wherein the modified compatibilizer is prepared by the following steps:
(1) uniformly mixing 2-14 parts by weight of glycidyl methacrylate and 0.2-1 part of initiator, and spraying the mixture onto the surface of 40-150 parts of polylactic acid-glycolic acid copolymer or 20-120 parts of polycaprolactone;
(2) and (2) adding the mixture obtained in the step (1) into an extruder, melting and blending to prepare modified master batches, wherein the operation temperature of each temperature zone of the extruder is 120-.
10. The method of claim 9, wherein the initiator is at least one of benzoyl peroxide, dicumyl peroxide, N-dimethylaniline and N, N-dimethyl-p-toluidine.
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