CN115320201B - Multilayer high-barrier high-strength biodegradable film and preparation method thereof - Google Patents

Multilayer high-barrier high-strength biodegradable film and preparation method thereof Download PDF

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CN115320201B
CN115320201B CN202210710208.7A CN202210710208A CN115320201B CN 115320201 B CN115320201 B CN 115320201B CN 202210710208 A CN202210710208 A CN 202210710208A CN 115320201 B CN115320201 B CN 115320201B
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antioxidant
parts
gas barrier
surface layer
pbat
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CN115320201A (en
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沈斌
杨晋涛
刘应红
李育飞
何艳娜
黄其寅
戈志明
杨志明
曹正强
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Pinghu Huada Plastic Products Co ltd
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Pinghu Huada Plastic Products Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

The invention relates to the field of composite materials, and discloses a multilayer high-barrier high-strength biodegradable film and a preparation method thereof. The biodegradable film comprises an upper surface layer, a central layer and a lower surface layer which are sequentially overlapped, wherein the upper surface layer and the lower surface layer comprise the following components: PBAT pellets, PDLA pellets, modified gas barrier, chain extender, antioxidant and compatibilizer; the center layer comprises the following components: PBAT pellets, PLLA pellets, chain extender, antioxidant, compatibilizer. The three-layer material is formed by melt coextrusion at one time, and compared with the traditional processing mode, the method has the advantages of simple process, short flow, low cost and capability of effectively improving the production efficiency.

Description

Multilayer high-barrier high-strength biodegradable film and preparation method thereof
Technical Field
The invention relates to the field of composite materials, in particular to a multilayer high-barrier high-strength biodegradable film and a preparation method thereof.
Background
After the traditional plastic film is used, the plastic film is not easy to recycle and can pollute the natural environment in the treatment process. The biodegradable film material is easy to degrade in natural environment after being used, and cannot pollute the environment, and the biodegradable film material gradually becomes a current research and development hot spot due to the characteristics of innocuity, wide sources and the like.
However, biodegradable plastics themselves also have some drawbacks, such as: poor processing heat stability, incompatibility among most biodegradable plastics, low heat distortion temperature and the like. And the single biodegradable plastic is used as a film material, and has certain defects such as too high permeability of oxygen, carbon dioxide and water vapor. Therefore, the composite material can be used as a substitute of the traditional plastic film by utilizing the respective gas transmittance, mechanical properties and the like of different biodegradable materials and compounding the biodegradable materials to obtain a multi-layer material. However, most biodegradable materials are incompatible, so that poor compatibility and cohesiveness exist between the polymers of the layers of the multilayer composite material and between the layers, and the physical properties of the multilayer material are unstable and delamination is easy.
CN103640290a discloses a high-barrier completely biodegradable composite membrane, which has a three-layer structure and a PBAT outer layer; the middle layer is PPC; the inner layer is PLA. In order to improve the compatibility of the inner layer and the outer layer with the middle layer, two block copolymers of PBA-co-PC and PLA-co-PC are respectively adopted as a compatibilizer. The compatibilization of block copolymers is achieved by entanglement between the physical molecular chains, which is less effective than reactive compatibilizers. And the PBA-co-PC and PLA-co-PC copolymer is polymerized by using isocyanate as a chain extender and a conventional technology, so that the synthesis process is relatively complex, and the byproducts are more.
In CN107471511A, a layer-by-layer casting method of a dichloromethane solution in which PBAT and PLA are dissolved is adopted to obtain a PBAT/PLA multilayer composite film, but the PBAT and the PLA are incompatible, and under the condition that no compatilizer is added, the layers are mutually independent, and the compatibility is poor.
Disclosure of Invention
In order to solve the technical problems, the invention provides the multilayer high-barrier high-strength biodegradable film and the preparation method thereof. In addition, the three-layer material is formed by melt coextrusion at one time, so that compared with the traditional processing mode, the method has the advantages of simple process, short flow, low cost and capability of effectively improving the production efficiency.
The technical scheme of the invention is as follows:
a multilayer high-barrier high-strength biodegradable film comprises an upper surface layer, a central layer and a lower surface layer which are sequentially overlapped,
the upper surface layer and the lower surface layer comprise the following components: PBAT pellets, PDLA pellets, modified gas barrier, chain extender, antioxidant and compatibilizer;
the center layer comprises the following components: PBAT pellets, PLLA pellets, chain extender, antioxidant, compatibilizer.
Further, the upper surface layer and the lower surface layer are composed of the following components in parts by weight:
100 parts of PBAT granules;
1-5 parts of PDLA granules;
1-5 parts of modified gas barrier agent;
0.5-3 parts of chain extender;
0.01-0.5 part of antioxidant;
0.5-3 parts of compatilizer.
Further, the center layer package is composed of the following components in parts by weight:
0-100 parts of PBAT granules;
0-100 parts of PLLA granules;
0.5-5 parts of chain extender;
0.01-0.5 part of antioxidant;
0.5-5 parts of compatilizer;
wherein the total parts of the PBAT granules and the PLLA granules are less than or equal to 100 parts.
Further, the modified gas barrier agent is obtained after the modified gas barrier agent is modified by an epoxy silane coupling agent and a gas barrier agent.
Further, the epoxy silane coupling agent is one or a mixture of more than one of gamma-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane and 3- (2, 3-glycidoxypropyl) propyl methyl diethoxy silane.
Further, the gas barrier agent is one or a mixture of more of montmorillonite and graphene.
Further, the antioxidant is composed of a hindered phenol antioxidant and a thio-lipid antioxidant or a phosphite antioxidant, wherein the hindered phenol antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,2' -thio-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Further, the compatilizer is one or more of polyethylene glycol 2000, tributyl citrate, maleic anhydride or epoxidized soybean oil.
A preparation method of a multilayer high-barrier high-strength biodegradable film comprises the following steps:
(1) Placing an epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 5-6 hours, taking out precipitate, and drying at 100-110 ℃ to obtain the modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent in a solution of PDLA granules and dimethyl sulfoxide, reacting at a high temperature by using N, N-dimethylbenzylamine as a catalyst, and centrifugally cleaning by using dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of the upper surface layer and the lower surface layer;
(5) And uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of the central layer.
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 160-190 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film.
Further, the concentration of the epoxy silane coupling agent in the mixed solution is 2-5wt%.
Compared with the prior art, the invention has the advantages that:
(1) The multilayer high-barrier high-strength biodegradable film has a three-layer structure, and the central layer is a PBAT/PLLA composite layer, so that the multilayer high-barrier high-strength biodegradable film has better ductility and elongation at break.
(2) The method comprises the steps of modifying a gas barrier agent, successfully grafting epoxy groups on the surface of the gas barrier agent, controlling the mass ratio of the modified gas barrier agent to the PDLA during the reaction, ultrasonically dispersing the modified gas barrier agent in a dimethyl sulfoxide solution of the PDLA, using N, N-dimethylbenzylamine as a catalyst, reacting for 25 hours at the temperature of 140 ℃, controlling the mass ratio of the modified gas barrier agent to the PDLA, and enabling the epoxy groups on the surface of the modified gas barrier agent to react with carboxyl groups at the end of the PDLA in a ring-opening way, wherein a part of epoxy groups remain. The modified gas barrier agent with the PDLA grafted on the surface still has reactivity, on one hand, the residual epoxy groups on the surface of the modified gas barrier agent can react with PBAT in situ, so that the compatibility between polymers PBAT and PDLA in the layer is effectively improved, on the other hand, PDLA on the surface of the modified gas barrier agent and PLLA in the central layer can form a stereocomplex crystal due to strong intermolecular interaction force, and most of stereocomplex crystals are positioned on the interface between the upper layer/lower layer and the central layer under the intermolecular force at the two ends, so that the compatibility between the layers is greatly improved and more stable. Meanwhile, the modified flaky gas barrier agent is more hydrophobic, so that the barrier property of the flaky gas barrier agent is further improved. The existence of the interfacial stereocomplex crystal further improves the mechanical properties of the film.
(3) In multilayer blending, the interaction force between the PBAT chain segment on the surface of the modified gas barrier agent and the PBAT in the layer and the hydrogen bond action between the PDLA chain segment on the surface and the PLLA in the central layer enable most of the modified gas barrier agent to be positioned between the layers under the interaction of the two types, so that the compatibility between the layers is more stable.
(4) The three-dimensional composite crystal (the essence is hydrogen bonding between PDLA and PLLA) is introduced between the layers, so that the oxygen barrier property of the composite film is further improved, and the surface of the modified gas barrier agent is more hydrophobic.
(5) The three-layer material is formed by melt coextrusion at one time, and compared with the traditional processing mode (lamination bonding or sheet extrusion-lamination and the like), the method has the advantages of simple process, short flow, low cost and capability of effectively improving the production efficiency.
Drawings
FIG. 1 is a schematic view of the layered structure of a multilayer high barrier, high strength biodegradable film of the present invention.
Detailed Description
The invention is further described below with reference to examples.
Example 1
As shown in FIG. 1, a multilayer high barrier, high strength biodegradable film comprises an upper skin layer, a central layer and a lower skin layer laminated in sequence. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 3 parts of PDLA granules, 2 parts of modified gas barrier agent, 0.5 part of chain extender, 1 part of antioxidant and 0.5 part of compatilizer, wherein the chain extender is ADR-4370S, the compatilizer is polyethylene glycol 2000, and the antioxidant adopts 0.5 part of antioxidant 168 and 0.5 part of antioxidant 1010;
the central layer consists of the following components in parts by weight: 50 parts of PBAT granules, 50 parts of PLLA granules, 3.5 parts of chain extender, 0.02 part of antioxidant and 2 parts of compatilizer, wherein the chain extender is ADR-4370S, the compatilizer is polyethylene glycol 2000, and the antioxidant adopts 0.01 part of antioxidant 168 and 0.01 part of antioxidant 1010.
The modified gas barrier agent is obtained after modification of an epoxy silane coupling agent and a gas barrier agent, wherein the epoxy silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, and the gas barrier agent is montmorillonite.
The antioxidant comprises hindered phenol antioxidant and thio-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A preparation method of a multilayer high-barrier high-strength biodegradable film comprises the following steps of;
(1) Placing an epoxy silane coupling agent into a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 2wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 5 hours, taking out precipitate, and drying at the temperature of 100 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent with the mass ratio of 2:3.125 in a solution of PDLA granules and dimethyl sulfoxide, using N, N-dimethylbenzylamine as a catalyst, reacting at 140 ℃ for 25 hours, and centrifuging and cleaning with dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) And uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of the central layer.
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film. A step of
Example 2
As shown in FIG. 1, a multilayer high barrier, high strength biodegradable film comprises an upper skin layer, a central layer and a lower skin layer laminated in sequence. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 2 parts of PDLA granules, 3 parts of modified gas barrier agent, 0.7 part of chain extender, 0.8 part of antioxidant and 1.1 part of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.5 part of antioxidant 168 and 0.4 part of antioxidant 1010;
the central layer consists of the following components in parts by weight: 55 parts of PBAT granules, 45 parts of PLLA granules, 4.2 parts of chain extender, 0.2 part of antioxidant and 2.3 parts of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.1 part of antioxidant 168 and 0.1 part of antioxidant 1010.
The modified gas barrier agent is obtained after the modification of the epoxy silane coupling agent and the gas barrier agent, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl triethoxy silane, and the gas barrier agent is montmorillonite.
The antioxidant comprises hindered phenol antioxidant and thio-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester.
A preparation method of a multilayer high-barrier high-strength biodegradable film comprises the following steps of;
(1) Placing an epoxy silane coupling agent into a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 4wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 6 hours, taking out precipitate, and drying at 110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent with the mass ratio of 2:3.125 in a solution of PDLA granules and dimethyl sulfoxide, using N, N-dimethylbenzylamine as a catalyst, reacting at 140 ℃ for 25 hours, and centrifuging and cleaning with dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) And uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of the central layer.
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film.
Example 3
As shown in FIG. 1, a multilayer high barrier, high strength biodegradable film comprises an upper skin layer, a central layer and a lower skin layer laminated in sequence. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 4 parts of PDLA granules, 1 part of modified gas barrier agent, 0.8 part of chain extender, 1 part of antioxidant and 1.3 parts of compatilizer, wherein the chain extender is EGM, the compatilizer is tributyl citrate, and the antioxidant adopts 0.55 part of antioxidant 168 and 0.45 part of antioxidant 1010;
the central layer consists of the following components in parts by weight: 45 parts of PBAT granules, 55 parts of PLLA granules, 3.8 parts of chain extender, 0.1 part of antioxidant and 2.1 parts of compatilizer, wherein the chain extender is EGM, the compatilizer is tributyl citrate, and the antioxidant adopts 0.05 part of antioxidant 168 and 0.05 part of antioxidant 1010.
The modified gas barrier agent is obtained after modification of an epoxy silane coupling agent and a gas barrier agent, wherein the epoxy silane coupling agent is mixed 3-glycidoxypropyl triethoxysilane and 3- (2, 3-glycidoxypropyl) propyl methyl diethoxysilane, and the gas barrier agent is montmorillonite.
The antioxidant comprises hindered phenol antioxidant and thio-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester and 2,2' -thio-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester ].
A preparation method of a multilayer high-barrier high-strength biodegradable film comprises the following steps of;
(1) Placing an epoxy silane coupling agent into a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 3wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 5.5 hours, taking out precipitate, and drying at 105 ℃ to obtain the modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent with the mass ratio of 2:3.125 in a solution of PDLA granules and dimethyl sulfoxide, using N, N-dimethylbenzylamine as a catalyst, reacting at 140 ℃ for 25 hours, and centrifuging and cleaning with dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) And uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of the central layer.
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film.
Example 4
As shown in FIG. 1, a multilayer high barrier, high strength biodegradable film comprises an upper skin layer, a central layer and a lower skin layer laminated in sequence. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 2 parts of PDLA granules, 1 part of modified gas barrier agent, 0.9 part of chain extender, 0.66 part of antioxidant and 0.9 part of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.33 part of antioxidant 168 and 0.33 part of antioxidant 1010;
the central layer consists of the following components in parts by weight: 55 parts of PBAT granules, 45 parts of PLLA granules, 3.8 parts of chain extender, 0.6 part of antioxidant and 2.3 parts of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed maleic anhydride and epoxidized soybean oil, and the antioxidant adopts 0.3 part of antioxidant 168 and 0.3 part of antioxidant 1010.
The modified gas barrier agent is obtained after the modification of the epoxy silane coupling agent and the gas barrier agent, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl triethoxy silane, and the gas barrier agent is montmorillonite.
The antioxidant comprises hindered phenol antioxidant and thio-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester.
A preparation method of a multilayer high-barrier high-strength biodegradable film comprises the following steps of;
(1) Placing an epoxy silane coupling agent into a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 4wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 6 hours, taking out precipitate, and drying at 110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent with the mass ratio of 2:3.125 in a solution of PDLA granules and dimethyl sulfoxide, using N, N-dimethylbenzylamine as a catalyst, reacting at 140 ℃ for 25 hours, and centrifuging and cleaning with dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) And uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of the central layer.
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film.
Example 5
As shown in FIG. 1, a multilayer high barrier, high strength biodegradable film comprises an upper skin layer, a central layer and a lower skin layer laminated in sequence. The upper surface layer and the lower surface layer are composed of the following components in parts by weight: 100 parts of PBAT granules, 0.5 part of PDLA granules, 0.5 part of modified gas barrier agent, 1.5 parts of chain extender, 0.88 part of antioxidant and 1.4 parts of compatilizer, wherein the chain extender is SAG, the compatilizer is epoxidized soybean oil, and the antioxidant adopts 0.33 part of antioxidant 168 and 0.33 part of antioxidant 1010;
the central layer consists of the following components in parts by weight: 55 parts of PBAT granules, 45 parts of PLLA granules, 3.8 parts of chain extender, 0.6 part of antioxidant and 2.3 parts of compatilizer, wherein the chain extender is SAG, the compatilizer is mixed tributyl citrate and epoxidized soybean oil, and the antioxidant adopts 0.42 part of antioxidant 168 and 0.46 part of antioxidant 1010.
The modified gas barrier agent is obtained after modification of an epoxy silane coupling agent and a gas barrier agent, wherein the epoxy silane coupling agent is 3- (2, 3-glycidoxy) propyl methyl diethoxy silane, and the gas barrier agent is montmorillonite.
The antioxidant comprises hindered phenol antioxidant and thio-lipid antioxidant or phosphite antioxidant, wherein the hindered phenol antioxidant is 2,2' -thio-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
A preparation method of a multilayer high-barrier high-strength biodegradable film comprises the following steps of;
(1) Placing an epoxy silane coupling agent into a mixed solvent of ethanol and water to prepare a mixed solution, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 5wt%;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 6 hours, taking out precipitate, and drying at 110 ℃ to obtain a modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent with the mass ratio of 2:3.125 in a solution of PDLA granules and dimethyl sulfoxide, using N, N-dimethylbenzylamine as a catalyst, reacting at 140 ℃ for 25 hours, and centrifuging and cleaning with dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of an upper surface layer and a lower surface layer;
(5) And uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of the central layer.
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 180 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film.
Comparative example 1
The PDLA in example 1 was changed to PLLA, and the other proportions and preparation methods were unchanged
Comparative example 2
The modified gas barrier agent in the example 1 is not reacted with PDLA granules, and the other proportions and the preparation method are unchanged;
comparative example 3
The modified gas barrier agent in example 1 was replaced with a gas barrier agent, and the other proportions and the preparation method were unchanged.
Examples 1 to 5 and comparative examples 1 to 3 were tested for tensile strength, elongation at break, impact resilience according to GB/T528-1998 determination of tensile stress strain properties of vulcanized rubber or thermoplastic rubber, and examples 1 to 5 and comparative examples 1 to 3 were tested for oxygen transmission according to GB/T1038-2000, and the specific test results are shown in Table 1.
Table 1: material test results for examples 1-5 and comparative examples 1-3;
from the above test data, it can be seen that the multilayer high barrier, high strength biodegradable film of the present invention has excellent tensile strength, elongation at break, impact resilience, and low oxygen transmission rate.
Example 4 differs from comparative example 1 in that the PDLA filler of the upper and lower surface layers is replaced with PLLA, and the intermolecular strong force of the upper and lower surface layer PDLA and the central layer PLLA is changed into the molecular chain physical entanglement between the upper and lower surface layer PLLA and the central layer PLLA, on one hand, the acting force is weakened, the compatibility between layers is reduced, and the mechanical property is lowered; on the other hand, the disappearance of the stereocomplex crystal causes an increase in the oxygen transmission rate.
The difference between comparative example 2 and example 1 is that the modified gas barrier agent does not react with the PDLA pellets, and is directly melt-blended with PDLA and PBAT, and because the reactivity of the epoxy group and the carboxyl at the end of PBAT is greater than that of PDLA, more modified epoxy montmorillonite becomes smaller in the phase of PBAT on the layer-to-layer interface, and the mechanical property of the composite film is reduced.
Comparative example 3 differs from example 4 in that the gas barrier agent is not modified and thus cannot react with PDLA, PBAT in situ, and cannot play a role in compatibilization, resulting in poor mechanical properties and barrier properties.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (6)

1. The utility model provides a multilayer high separation, high strength's biodegradable film, includes superimposed top layer, central layer and lower top layer in proper order, its characterized in that:
the upper surface layer and the lower surface layer comprise the following components: PBAT pellets, PDLA pellets, modified gas barrier, chain extender, antioxidant and compatibilizer;
the center layer comprises the following components: PBAT pellets, PLLA pellets, chain extender, antioxidant, compatibilizer;
the modified gas barrier agent is obtained after modification by an epoxy silane coupling agent and a gas barrier agent;
the epoxy silane coupling agent is one or a mixture of more of gamma-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl triethoxy silane and 3- (2, 3-glycidoxypropyl) propyl methyl diethoxy silane;
the gas barrier agent is one or more of montmorillonite and graphene;
the preparation method of the multilayer high-barrier high-strength biodegradable film comprises the following steps:
(1) Placing an epoxy silane coupling agent in a mixed solvent of ethanol and water to prepare a mixed solution;
(2) Dispersing the gas barrier agent in the mixed solution, stirring and reacting for 5-6 hours, taking out precipitate, and drying at 100-110 ℃ to obtain the modified gas barrier agent;
(3) Ultrasonically dispersing a modified gas barrier agent in a solution of PDLA granules and dimethyl sulfoxide, reacting at a high temperature by using N, N-dimethylbenzylamine as a catalyst, and centrifugally cleaning by using dichloromethane and ethanol after the reaction is finished to obtain a product;
(4) Melting and blending the product, PBAT, a chain extender, an antioxidant and a compatilizer in an extruder to prepare raw materials of the upper surface layer and the lower surface layer;
(5) Uniformly mixing PBAT, PLLA, a chain extender, an antioxidant and a compatilizer, wherein the mixture is used as a raw material of a central layer;
(6) Respectively feeding the raw materials of the upper surface layer, the central layer and the lower surface layer into two different screw extruders, plasticizing at 160-190 ℃, extruding three materials through a coextrusion molding machine, and sequentially rolling, cooling, traction and shearing to obtain the biodegradable film.
2. The multilayer high barrier, high strength biodegradable film according to claim 1, wherein: the upper surface layer and the lower surface layer are composed of the following components in parts by weight:
100 parts of PBAT granules;
1-5 parts of PDLA granules;
1-5 parts of modified gas barrier agent;
0.5-3 parts of chain extender;
0.01-0.5 part of antioxidant;
0.5-3 parts of compatilizer.
3. The multilayer high barrier, high strength biodegradable film according to claim 1, wherein: the central layer package comprises the following components in parts by weight:
0-100 parts of PBAT granules;
0-100 parts of PLLA granules;
0.5-5 parts of chain extender;
0.01-0.5 part of antioxidant;
0.5-5 parts of compatilizer;
wherein the total parts of the PBAT granules and the PLLA granules are less than or equal to 100 parts.
4. The multilayer high barrier, high strength biodegradable film according to claim 1, wherein: the antioxidant consists of a hindered phenol antioxidant and a thio-lipid antioxidant or a phosphite antioxidant, wherein the hindered phenol antioxidant is one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2,2' -thio-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
5. The multilayer high barrier, high strength biodegradable film according to claim 1, wherein: the compatilizer is one or more of polyethylene glycol 2000, tributyl citrate, maleic anhydride or epoxidized soybean oil.
6. The multilayer high barrier, high strength biodegradable film according to claim 1, wherein the concentration of the epoxy silane coupling agent in the mixed solution is 2-5wt%.
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