CN112874099A - Biodegradable multilayer composite barrier film and preparation method thereof - Google Patents

Biodegradable multilayer composite barrier film and preparation method thereof Download PDF

Info

Publication number
CN112874099A
CN112874099A CN202011645101.6A CN202011645101A CN112874099A CN 112874099 A CN112874099 A CN 112874099A CN 202011645101 A CN202011645101 A CN 202011645101A CN 112874099 A CN112874099 A CN 112874099A
Authority
CN
China
Prior art keywords
layer
polylactic acid
biodegradable
barrier film
pva
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011645101.6A
Other languages
Chinese (zh)
Inventor
覃碧勋
李卫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Puca Plastic Technology Co ltd
Original Assignee
Puca Plastic Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Puca Plastic Technology Co ltd filed Critical Puca Plastic Technology Co ltd
Priority to CN202011645101.6A priority Critical patent/CN112874099A/en
Publication of CN112874099A publication Critical patent/CN112874099A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • 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
    • B32B2250/05—5 or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a biodegradable multilayer composite barrier film and a preparation method thereof, wherein the biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, the substrate layer comprises biodegradable resin, the bonding layers comprise polylactic acid modified by active groups, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers. The barrier layer is formed by drying polyvinyl alcohol solution, and can form a continuous compact PVA layer, so that the barrier layer has better gas barrier property. And active groups in the modified polylactic acid can perform chemical reaction with hydroxyl on a PVA molecular chain so as to improve the adhesive force of the barrier layer on the substrate layer, ensure that the interlayer bonding force reaches inseparable degree, and further improve the barrier property. The number of hydroxyl groups on the molecular chain of the PVA is reduced due to chemical reaction, so that the original water resistance of the PVA is improved, and the corresponding water vapor barrier property is also improved.

Description

Biodegradable multilayer composite barrier film and preparation method thereof
Technical Field
The invention relates to the technical field of plastics, in particular to a multilayer composite film, and more particularly relates to a biodegradable multilayer composite barrier film and a preparation method thereof.
Background
Since the advent of the world, plastics have been widely used in various fields of national economy, bringing great convenience to the production and life of human beings. However, its enormous usage and waste volume results in increasingly serious environmental pollution, i.e., white pollution, including river pollution, farmland mulch pollution, and marine plastic pollution. Therefore, in recent years, products capable of replacing conventional plastics have been sought.
The problem is well solved by the appearance of biodegradable plastics. Biodegradable plastics, also called biodegradable plastics, refer to plastics which are degraded by the action of microorganisms present in nature under conditions of nature such as soil and/or sandy soil, and/or under specific conditions such as composting conditions or anaerobic digestion conditions or in aqueous culture solutions, and finally completely degraded into carbon dioxide (CO) or/and methane (CH), water (H O) and mineralized inorganic salts of the elements contained therein, as well as new biomass.
Along with the restriction of plastic use in various countries in the world and the issue of plastic restriction orders in China, the research and development of biodegradable plastics become an important direction for the sustainable development of the plastic industry. Currently produced biodegradable plastics are mainly classified into four major categories: PLA (polylactic acid), PBS (polyester), PBAT (polyester), and PHA (polyhydroxyalkanoate). The biodegradable plastics can reach or exceed the performance of the traditional plastics in certain characteristics, and have similar application in practicability. However, these biodegradable plastics generally exhibit barrier properties, such as gas barrier properties, which limits their application to high barrier packaging materials.
The high-barrier plastic mainly comprises PVDC, EVOH, MXD6, PEN, PVA and the like, wherein the PVDC, EVOH, MXD6 and PEN are non-degradable plastics, and the PVA is biodegradable plastic. PVA (polyvinyl alcohol) is a water-soluble polymer obtained by hydrolyzing polyvinyl acetate without polymerizing monomers, and the PVA film is non-toxic and harmless, has high transparency, good mechanical strength, excellent barrier property to gases such as hydrogen, oxygen and the like, good solvent resistance and plays an important role in film materials.
However, the melting temperature of PVA is close to the decomposition temperature, and PVA is largely decomposed and carbonized during melting, so that a pure PVA material cannot be directly melt-extruded to form a film. In recent years, blend alloys such as PLA/PVA alloy and PBAT/PVA alloy are prepared by PVA and other degradable plastics, and then the alloys are used for preparing films, but because a large amount of low-barrier plastics are mixed in the PVA, the original excellent barrier property of the PVA is inevitably reduced, and meanwhile, the blend materials are used for preparing the films, the PVA in the obtained films can be distributed in the films in the form of particles, and compact PVA layers are not formed, so the barrier property of the films is very common.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a novel multilayer composite barrier film and a method for preparing the same, which can combine excellent biodegradability and barrier property.
In order to achieve the above purpose, the invention provides a biodegradable multilayer composite barrier film, which includes a substrate layer, adhesive layers located on two sides of the substrate layer, and a barrier layer located on one side of the adhesive layers away from the substrate layer, wherein the substrate layer is made of biodegradable resin, the adhesive layers are made of polylactic acid modified by active groups, and the barrier layer is formed by drying polyvinyl alcohol solution on the adhesive layers.
Compared with the prior art, the biodegradable multilayer composite barrier film adopts biodegradable resin, polylactic acid modified by active groups and polyvinyl alcohol solution as raw materials, and has biodegradability, so that the biodegradable multilayer composite barrier film can be prepared into biodegradable plastic. Meanwhile, the barrier layer is used as an outer layer and is formed by drying polyvinyl alcohol solution, so that a continuous and compact PVA layer can be formed, and the gas barrier layer has better gas barrier property. And the active group of the polylactic acid modified by the active group in the bonding layer can perform chemical reaction with the hydroxyl on the PVA molecular chain of the barrier layer in the drying and forming process, so that the bonding layer plays a role in bridge grafting, the adhesion of the barrier layer on the substrate layer is improved, the interlayer bonding force reaches the inseparable degree, and the barrier property is further improved. In addition, the number of the hydroxyl groups which absorb water on the molecular chain of the PVA is reduced due to the chemical reaction, so that the original water resistance of the PVA is improved, and the corresponding water vapor barrier property is also improved.
In another aspect, the present invention provides a method for preparing a biodegradable multi-layer composite barrier film, comprising:
(1) taking the biodegradable resin as a core layer material, taking the polylactic acid modified by the active groups as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and infiltrating the composite layer into the polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
In the preparation method of the biodegradable multilayer composite barrier film, the substrate layer and the bonding layer are formed by coextrusion, so that the uniform and fine thickness of each layer can be ensured, the mechanization degree is high, and continuous production can be realized. Meanwhile, the barrier layer is formed by drying a polyvinyl alcohol solution on the bonding layer to form a continuous and compact PVA layer, so that the phenomenon that PVA is distributed in a film in a particulate form in the traditional blend film making process is avoided, and the barrier property is good.
Drawings
Fig. 1 is a schematic view of a biodegradable multi-layer composite barrier film of the present invention.
Fig. 2 is a schematic view of an apparatus used in the method for preparing the biodegradable multi-layer composite barrier film of the present invention.
Detailed Description
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of biodegradable resin, the bonding layers are made of polylactic acid modified by active groups, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers. That is, the biodegradable multi-layer composite barrier film 200 of the present invention may have a 5-layer structure, as shown in fig. 1, which includes a first barrier layer 10, a first adhesive layer 20, a base layer 30, a second adhesive layer 40, and a second barrier layer 50, which are sequentially stacked. The first barrier layer 10 and the second barrier layer 50 have a symmetrical structure, and have a uniform thickness and composition, and a thickness of 2 to 10 μm. The first adhesive layer 20 and the second adhesive layer 40 have a symmetrical structure, and have a uniform thickness and composition, and a thickness of 1 to 6 μm. The thickness of the substrate layer can be 8-20 μm.
Preferably, the biodegradable resin is one or more of polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate-adipate copolymer (PBSA), polymethyl ethylene carbonate (PPC), polybutylene terephthalate-co-butylene succinate (PBST), polybutylene sebacate terephthalate (PBSeT), and Polyhydroxybutyrate (PHB).
Preferably, the polylactic acid modified by active groups is a functional monomer grafted polylactic acid, and the preparation raw materials of the functional monomer grafted polylactic acid comprise, by weight:
Figure BDA0002878609360000041
wherein, the content of the functional monomer can be but not limited to 0.3 part, 0.5 part, 0.7 part, 1.0 part, 1.5 parts, 2.0 parts, 2.5 parts, 3 parts, 4 parts and 5 parts. The functional monomer is one or more of Maleic Anhydride (MAH), Glycidyl Methacrylate (GMA), vinyl trimethoxy silane (KH-171), vinyl triethoxy silane (KH-151), vinyl tri (B-methoxyethoxy) silane (KH-172) and methacryloxypropyl triethoxy silane (KH-679).
The content of the peroxide initiator may be, but not limited to, 0.03 parts, 0.05 parts, 0.07 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.8 parts, 1 part. The peroxide initiator is one or more of dicumyl peroxide, di-tert-butyl cumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane.
The content of the first auxiliary agent may be, but not limited to, 0 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part. The first auxiliary agent is an antioxidant and/or a lubricant, the antioxidant is preferably 0.1-0.3 part, but not limited to 0.1 part, 0.15 part, 0.2 part, 0.25 part and 0.3 part, and is preferably one or more of an antioxidant 1076, an antioxidant 164, an antioxidant 168 and an antioxidant 264. The lubricant is preferably 0.1-0.3 part, but not limited to 0.1 part, 0.15 part, 0.2 part, 0.25 part and 0.3 part, and is preferably one or more of stearic acid, stearate, glyceryl stearate, oleamide and erucamide.
The preparation method of the polylactic acid modified by the active groups comprises the following steps: according to the formula, polylactic acid, functional monomer, peroxide initiator and auxiliary agent are uniformly mixed at high speed, and then are melted and extruded in an extruder, granulated and dried to obtain functional monomer grafted polylactic acid.
The polyvinyl alcohol solution is prepared from the following raw materials in parts by weight:
100 parts of deionized water;
5-30 parts of PVA resin;
0-0.2 part of a second auxiliary agent.
The content of the PVA resin can be but is not limited to 5 parts, 7 parts, 10 parts, 15 parts, 20 parts, 25 parts and 30 parts, and the alcoholysis degree of the PVA resin is 80-99%, preferably 83-95%, and more preferably 88-93%.
The content of the second auxiliary agent can be but is not limited to 0 part, 0.05 part, 0.1 part, 0.15 part and 0.2 part, and can be cosolvent and/or defoamer. The cosolvent is preferably 0.01-0.1 part, but not limited to 0.01 part, 0.05 part, 0.07 part and 0.1 part, and can be one or more of ethylene glycol, propylene glycol, glycerol, triethanolamine and polyoxyethylene ether. The defoaming agent is preferably 0.001-0.02 part, but can be limited to 0.001 part, 0.005 part, 0.01 part, 0.015 part and 0.2 part, and is preferably one or more of octanol, tributyl phosphate and silicone emulsion.
The preparation method of the polyvinyl alcohol solution comprises the following steps: firstly adding deionized water and a second auxiliary agent, slowly adding PVA resin under the stirring condition, completely soaking and swelling the PVA resin, slowly heating under the stirring condition, completely dissolving the PVA resin, and then cooling to obtain the PVA resin. Specifically, deionized water and a second auxiliary agent can be added into a dissolving kettle at room temperature, stirring is started, PVA resin is slowly added while stirring, the PVA resin is completely infiltrated and swelled, then the dissolving kettle is slowly heated to about 95 ℃ while stirring, the PVA is completely dissolved, and then the temperature is reduced to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking biodegradable resin as a core layer material and polylactic acid modified by active groups as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
The adopted device can be shown in figure 2, a core material is placed in a main cavity of a multilayer co-extruder 60, polylactic acid with a surface layer material modified by active groups is placed in a side cavity, the melting temperature of the multilayer co-extruder 60 is 150-200 ℃, the polylactic acid is extruded by a die 61 and is rolled and molded by a molding roller 70, the polylactic acid is soaked in a solution tank 80, a guide roller 81 and a liquid scraping roller 83 are arranged in the solution tank 80, and the dipped liquid enters a drying box 90 for drying and is rolled by a rolling mechanism 100. Wherein, drying cabinet 90 has the function of heating, drying and curing, and drying temperature can be 50 ~ 80 ℃. The winding mechanism 100 includes a take-up roll 110 for pulling the multilayer film and a winding roll 130 for winding up the multilayer film 200.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, the bonding layers are made of polylactic acid grafted and modified by vinyl trimethoxy silane, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 2g of vinyltrimethoxysilane and 0.1g of dicumyl peroxide are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the polylactic acid grafted and modified by the vinyltrimethoxysilane.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water into a dissolving kettle at room temperature, starting stirring, slowly adding 25g of PVA resin (alcoholysis degree is 90%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking polybutylene adipate terephthalate as a core layer material, taking polylactic acid grafted and modified by vinyl trimethoxy silane as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in a polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
Example 2
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of polylactic acid, the bonding layers are made of polylactic acid grafted and modified by vinyltrimethoxysilane, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 2g of vinyltrimethoxysilane and 0.1g of dicumyl peroxide are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the polylactic acid grafted and modified by the vinyltrimethoxysilane.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water into a dissolving kettle at room temperature, starting stirring, slowly adding 25g of PVA resin (alcoholysis degree is 90%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking polylactic acid as a core layer material, taking polylactic acid grafted and modified by vinyltrimethoxysilane as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in a polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
Example 3
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of a succinic acid butanediol ester-adipic acid butanediol ester copolymer, the bonding layers are made of polylactic acid grafted and modified by maleic anhydride, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers.
The preparation method of the maleic anhydride grafted and modified polylactic acid comprises the following steps: calculated by 100g of polylactic acid, 2g of maleic anhydride and 0.1g of dicumyl peroxide are added into the polylactic acid, and the mixture is uniformly mixed at high speed, melted, extruded and granulated in an extruder, and then dried to obtain the maleic anhydride grafted and modified polylactic acid.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water into a dissolving kettle at room temperature, starting stirring, slowly adding 25g of PVA resin (alcoholysis degree is 90%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking a succinic acid butanediol ester-adipic acid butanediol ester copolymer as a core layer material, taking polylactic acid which is grafted and modified by maleic anhydride as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in a polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
Example 4
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, the bonding layers are made of polylactic acid grafted and modified by vinyl trimethoxy silane, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 5g of vinyltrimethoxysilane and 0.5g of di-tert-butyl cumene peroxide are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the polylactic acid grafted and modified by the vinyltrimethoxysilane.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water into a dissolving kettle at room temperature, starting stirring, slowly adding 30g of PVA resin (alcoholysis degree is 95%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking polybutylene adipate terephthalate as a core layer material, taking polylactic acid grafted and modified by vinyl trimethoxy silane as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in a polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
Example 5
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, the bonding layers are made of polylactic acid grafted and modified by vinyl trimethoxy silane, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 2g of vinyltrimethoxysilane, 0.1g of dicumyl peroxide and 10760.2 g of antioxidant are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the vinyltrimethoxysilane grafted and modified polylactic acid.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water and 0.05g of cosolvent propylene glycol into a dissolving kettle at room temperature, starting stirring, slowly adding 25g of PVA resin (the alcoholysis degree is 90%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking polybutylene adipate terephthalate as a core layer material, taking polylactic acid grafted and modified by vinyl trimethoxy silane as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in a polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
Example 6
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, the bonding layers are made of polylactic acid grafted and modified by vinyl trimethoxy silane, and the barrier layer is formed by drying polyvinyl alcohol solution on the bonding layers.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 2g of vinyltrimethoxysilane, 0.1g of dicumyl peroxide, 1640.1 g of antioxidant and 0.3g of glyceryl stearate are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the vinyltrimethoxysilane grafted and modified polylactic acid.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water, 0.1g of cosolvent triethanolamine and 0.01g of defoamer octanol into a dissolving kettle at room temperature, starting stirring, slowly adding 25g of PVA resin (the alcoholysis degree is 90%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps:
(1) taking polybutylene adipate terephthalate as a core layer material, taking polylactic acid grafted and modified by vinyl trimethoxy silane as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and soaking the composite layer in a polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
Comparative example 1
The biodegradable multilayer composite barrier film comprises a substrate layer and bonding layers positioned on two sides of the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, and the bonding layers are made of polylactic acid grafted and modified by vinyl trimethoxy silane.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 2g of vinyltrimethoxysilane and 0.1g of dicumyl peroxide are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the polylactic acid grafted and modified by the vinyltrimethoxysilane.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps: taking polybutylene adipate terephthalate as a core layer material, taking polylactic acid grafted and modified by vinyl trimethoxy silane as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer.
Comparative example 2
The biodegradable multilayer composite barrier film comprises a substrate layer and barrier layers positioned on two sides of the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, and the barrier layers are formed by drying polyvinyl alcohol solution on the substrate layer.
The preparation method of the polyvinyl alcohol solution comprises the following steps: adding 100g of deionized water into a dissolving kettle at room temperature, starting stirring, slowly adding 25g of PVA resin (alcoholysis degree is 90%) while stirring to completely soak and swell the PVA resin, slowly heating the dissolving kettle to about 95 ℃ while stirring to completely dissolve the PVA, and then cooling to about 60 ℃ to obtain a PVA solution.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps: taking polybutylene adipate terephthalate as a core layer material, and performing extrusion molding to obtain a single-layer film; and soaking the film in polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a three-layer structure.
Comparative example 3
The biodegradable multilayer composite barrier film comprises a substrate layer, bonding layers positioned on two sides of the substrate layer and a barrier layer positioned on one side of the bonding layers far away from the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, the bonding layers are made of polylactic acid grafted and modified by vinyl trimethoxy silane, and the barrier layer is made of polyvinyl alcohol.
The preparation method of the polylactic acid grafted and modified by the vinyltrimethoxysilane comprises the following steps: calculated by 100g of polylactic acid, 2g of vinyltrimethoxysilane and 0.1g of dicumyl peroxide are added into the polylactic acid, and the mixture is uniformly mixed at a high speed, melted and extruded in an extruder, granulated and dried to obtain the polylactic acid grafted and modified by the vinyltrimethoxysilane.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps: polybutylene adipate terephthalate is used as a core layer material, polylactic acid grafted and modified by vinyl trimethoxy silane is used as an intermediate layer material, and a polyvinyl alcohol material is used as a surface layer material, and the five-layer composite layer is obtained through extrusion molding.
Comparative example 4
The biodegradable multilayer composite barrier film comprises a substrate layer and barrier layers positioned on two sides of the substrate layer, wherein the substrate layer is made of polybutylene adipate terephthalate, and the barrier layers are made of polylactic acid and polyvinyl alcohol.
The preparation method of the biodegradable multilayer composite barrier film comprises the following steps: the three-layer composite layer is obtained by extrusion molding of a polybutylene adipate-terephthalate core layer material and a polylactic acid-polyvinyl alcohol mixture (the weight ratio of the polybutylene adipate-terephthalate core layer material to the polylactic acid-polyvinyl alcohol mixture is 3:5) surface layer material.
The biodegradable multilayer composite barrier films of examples 1 to 6 and comparative examples 1 to 4 were subjected to barrier performance tests, and the test results are shown in table 1.
Wherein the oxygen transmission rate is less than or equal to 3cm3/(m224h 0.1MPa) shows good oxygen barrier property, 3-10 cm3/(m224h 0.1MPa) indicates good oxygen barrier property, 10 to 50cm3/(m224h 0.1MPa) indicates good oxygen barrier property, 50-100 cm3/(m224 h.0.1 MPa) indicates that the oxygen barrier property is qualified and is not less than 100cm3/(m224h 0.1MPa) indicates poor oxygen barrier properties.
The nitrogen transmission rate is less than or equal to 5cm3/(m224h 0.1MPa) represents that the nitrogen barrier property is good, 5-20 cm3/(m224h 0.1MPa) indicates good nitrogen gas barrier property, 20 to 100cm3/(m224h 0.1MPa) indicates good nitrogen gas barrier property, 100 to 200cm3/(m224 h.0.1 MPa) indicates that the nitrogen gas barrier property is qualified and is not less than 200cm3/(m224h 0.1MPa) indicates poor nitrogen gas barrier properties.
The water vapor transmission rate is less than or equal to 10g/m224h represents that the water vapor barrier property is good, and 10-20 g/m224h represents a good water vapor barrier property, 20 to 50g/m224h shows good water vapor barrier property, 50-100 g/m224h represents that the nitrogen barrier property is qualified and is not less than 100g/m224h indicates poor water vapor barrier properties.
Table 1 results of barrier property test of each example
Examples Oxygen barrier properties Barrier properties against nitrogen Water vapor barrier properties
Example 1 Is very good Is very good Good effect
Example 2 Is very good Is very good Is very good
Example 3 Is very good Is very good Good effect
Example 4 Is very good Is very good Good effect
Example 5 Is very good Is very good Good effect
Example 6 Is very good Is very good Good effect
Comparative example 1 Difference (D) Difference (D) Difference (D)
Comparative example 2 Qualified Qualified Difference (D)
Comparative example 3 Qualified Qualified Difference (D)
Comparative example 4 Qualified Qualified Difference (D)
Although the examples 1 to 6 and the comparative examples 1 to 4 all adopt degradable materials, and the prepared multilayer composite barrier film is a biodegradable plastic product, the gas barrier performance of the examples 1 to 6 is obviously better than that of the comparative examples 1 to 4, because the barrier layer is used as an outer layer and is formed by drying polyvinyl alcohol solution, a continuous and compact PVA layer can be formed, and the gas barrier property is better. And the active group of the polylactic acid modified by the active group in the bonding layer can perform chemical reaction with the hydroxyl on the PVA molecular chain of the barrier layer in the drying and forming process, so that the bonding layer plays a role in bridge grafting, the adhesion of the barrier layer on the substrate layer is improved, the interlayer bonding force reaches the inseparable degree, and the barrier property is further improved. Meanwhile, in the embodiments 1 to 6, the number of the water-absorbing hydroxyl groups on the molecular chain of the PVA is reduced due to the chemical reaction, so that the original water resistance of the PVA is improved, and the corresponding water vapor barrier property is also improved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The utility model provides a compound barrier film of biodegradable multilayer which characterized in that, includes the base member layer, is located the bond line of base member layer both sides and being located the bond line is kept away from the barrier layer of one side of base member layer, the material of base member layer includes biodegradable resin, the material of bond line includes the polylactic acid modified through active group, the barrier layer be polyvinyl alcohol solution in dry on the bond line forms.
2. The biodegradable multi-layer composite barrier film of claim 1, wherein the biodegradable resin is one or more of polylactic acid, polybutylene adipate-terephthalate, polybutylene succinate-adipate copolymer, polymethyl ethylene carbonate, polybutylene terephthalate-co-butylene succinate, polybutylene sebacate-terephthalate, and polyhydroxybutyrate.
3. The biodegradable multilayer composite barrier film according to claim 1, wherein the polylactic acid modified by active groups is a functional monomer grafted polylactic acid, and the functional monomer grafted polylactic acid is prepared from the following raw materials in parts by weight:
Figure FDA0002878609350000011
4. the biodegradable multi-layer composite barrier film of claim 3, wherein the functional monomer is one or more of maleic anhydride, glycidyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (B-methoxyethoxy) silane, and methacryloxypropyltriethoxysilane.
5. The biodegradable multilayer composite barrier film of claim 3, wherein the peroxide initiator is one or more of dicumyl peroxide, di-t-butyl cumyl peroxide and 2, 5-dimethyl-2, 5-di-t-butyl hexane peroxide.
6. The biodegradable multi-layer composite barrier film of claim 3 wherein the preparation of the polylactic acid modified with reactive groups comprises: uniformly mixing the polylactic acid, the functional monomer, the peroxide initiator and the auxiliary agent at a high speed according to the formula ratio, performing melt extrusion in an extruder, granulating, and drying to obtain the functional monomer grafted polylactic acid.
7. The biodegradable multi-layer composite barrier film of claim 1 wherein the polyvinyl alcohol solution is prepared from the following raw materials in parts by weight:
100 parts of deionized water;
5-30 parts of PVA resin;
0-0.2 part of a second auxiliary agent.
8. The biodegradable multi-layer composite barrier film of claim 7, wherein the degree of alcoholysis of the PVA resin is 80-99%.
9. The biodegradable multi-layer composite barrier film of claim 7, wherein the polyvinyl alcohol solution is prepared by a method comprising: firstly adding the deionized water and the second auxiliary agent, slowly adding the PVA resin under the stirring condition, completely soaking and swelling the PVA resin, slowly heating under the stirring condition, completely dissolving the PVA resin, and then cooling to obtain the PVA resin.
10. The method of making a biodegradable, multi-layer composite barrier film as defined in any one of claims 1 to 9 including:
(1) taking the biodegradable resin as a core layer material, taking the polylactic acid modified by the active groups as a surface layer material, and performing extrusion molding to obtain a three-layer composite layer;
(2) and infiltrating the composite layer into the polyvinyl alcohol solution, and drying to obtain the biodegradable multilayer composite barrier film with a five-layer structure.
CN202011645101.6A 2020-12-31 2020-12-31 Biodegradable multilayer composite barrier film and preparation method thereof Pending CN112874099A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011645101.6A CN112874099A (en) 2020-12-31 2020-12-31 Biodegradable multilayer composite barrier film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011645101.6A CN112874099A (en) 2020-12-31 2020-12-31 Biodegradable multilayer composite barrier film and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112874099A true CN112874099A (en) 2021-06-01

Family

ID=76046689

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011645101.6A Pending CN112874099A (en) 2020-12-31 2020-12-31 Biodegradable multilayer composite barrier film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112874099A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113752662A (en) * 2021-09-22 2021-12-07 中国热带农业科学院湛江实验站 Three-layer co-extrusion biodegradable mulching film with barrier structure
CN114015185A (en) * 2021-10-20 2022-02-08 界首市天鸿新材料股份有限公司 Biodegradable heat shrinkable film and processing technology thereof
CN114179479A (en) * 2021-12-10 2022-03-15 厦门长塑实业有限公司 Multilayer co-extrusion biaxially oriented barrier polylactic acid film and preparation method and application thereof
CN114434929A (en) * 2022-01-28 2022-05-06 上海乐纯生物技术有限公司 Degradable film of disposable bag for bio-pharmaceuticals and application thereof
CN114836013A (en) * 2022-06-22 2022-08-02 烟台大学 Full-biodegradable plastic mulching film master batch, preparation method and application thereof
CN117246015A (en) * 2023-08-24 2023-12-19 宝瑞泰(沧州)包装有限公司 Oxygen-blocking polyethylene film and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110435277A (en) * 2019-07-26 2019-11-12 广东华通新材料科技有限公司 A kind of biodegradable high-barrier vacuum evaporation film and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110435277A (en) * 2019-07-26 2019-11-12 广东华通新材料科技有限公司 A kind of biodegradable high-barrier vacuum evaporation film and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113752662A (en) * 2021-09-22 2021-12-07 中国热带农业科学院湛江实验站 Three-layer co-extrusion biodegradable mulching film with barrier structure
CN114015185A (en) * 2021-10-20 2022-02-08 界首市天鸿新材料股份有限公司 Biodegradable heat shrinkable film and processing technology thereof
CN114015185B (en) * 2021-10-20 2024-01-12 界首市天鸿新材料股份有限公司 Biodegradable heat-shrinkable film and processing technology thereof
CN114179479A (en) * 2021-12-10 2022-03-15 厦门长塑实业有限公司 Multilayer co-extrusion biaxially oriented barrier polylactic acid film and preparation method and application thereof
CN114179479B (en) * 2021-12-10 2023-05-09 福建长塑实业有限公司 Multilayer co-extrusion biaxially oriented barrier polylactic acid film and preparation method and application thereof
CN114434929A (en) * 2022-01-28 2022-05-06 上海乐纯生物技术有限公司 Degradable film of disposable bag for bio-pharmaceuticals and application thereof
CN114434929B (en) * 2022-01-28 2022-09-16 上海乐纯生物技术有限公司 Degradable film of disposable bag for bio-pharmaceuticals and application thereof
CN114836013A (en) * 2022-06-22 2022-08-02 烟台大学 Full-biodegradable plastic mulching film master batch, preparation method and application thereof
CN117246015A (en) * 2023-08-24 2023-12-19 宝瑞泰(沧州)包装有限公司 Oxygen-blocking polyethylene film and preparation method thereof
CN117246015B (en) * 2023-08-24 2024-03-12 宝瑞泰(沧州)包装有限公司 Oxygen-blocking polyethylene film and preparation method thereof

Similar Documents

Publication Publication Date Title
CN112874099A (en) Biodegradable multilayer composite barrier film and preparation method thereof
CN110791069B (en) Full-degradable high-barrier composite material for flexible package
CN113861635A (en) Starch modified PBAT/PLA biodegradable plastic film and preparation method thereof
ITMI932485A1 (en) BIODEGRADABLE COMPOSITION OF POLYETHYLENE CHEMICALLY LINKED WITH STARCH AND PROCEDURE FOR ITS PREPARATION
WO2007027163A2 (en) Degradable biodegradable polypropylene film
CN105504704B (en) Monoethanolamine activates sodium-based montmorillonite/polymer composite biodegradable blown film resin and preparation method
CN111320845B (en) Graphene reinforced and toughened biodegradable polyester compound and foam material thereof
CN115593061B (en) High-barrier biodegradable composite film and preparation process thereof
CN111454472A (en) Preparation method of high-transparency self-adhesive PBAT preservative film
CN112677598A (en) Composite film, preparation method thereof and plastic film product
CN104371296A (en) Poly-methyl ethylene carbonate composition and preparation method thereof
CN101497731B (en) Environment degrading thermoplastic glucomanan film and preparation thereof
CN102229733A (en) EVOH (ethylene vinyl alcohol) resin and preparation method thereof
CN112029171A (en) Antibacterial PE film and preparation method thereof
EP0781807B1 (en) Biodegradable composition, a process and equipment for preparing the same
CN111923546B (en) Environment-friendly degradable waterproof coating packaging paper and preparation method thereof
CN111016118B (en) Antibacterial high-oxygen barrier PE composite membrane and preparation method thereof
CN117364539A (en) Degradable full-biological-based laminated paper for food, preparation method and application
CN114921069B (en) Full-biodegradable film with high heat seal strength and preparation method and application thereof
CN114276634B (en) Environment-friendly easily-degradable gas film material and production method thereof
WO2016004870A1 (en) Polymerization method for biodegradable high-barrier thermoplastic polymer
CN115260711A (en) Hydrolysis-resistant high-barrier-property biodegradable film and preparation method thereof
CN115320201A (en) Multilayer high-barrier and high-strength biodegradable film and preparation method thereof
CN1297599C (en) Utterly biodegradable packaging film and mulch film
CN108724877B (en) Multilayer polymer film and method for producing same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210601