CN115366513B - Transparent high-barrier composite material and preparation method thereof - Google Patents

Transparent high-barrier composite material and preparation method thereof Download PDF

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Publication number
CN115366513B
CN115366513B CN202210954989.4A CN202210954989A CN115366513B CN 115366513 B CN115366513 B CN 115366513B CN 202210954989 A CN202210954989 A CN 202210954989A CN 115366513 B CN115366513 B CN 115366513B
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China
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layer
composite material
barrier
mass
antibacterial
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CN115366513A (en
Inventor
游国强
刘晓明
施遥
施虎林
金潮
蘧艳峰
吴尧
赵怀璞
郝杰
刘凯
马跃峰
郑建国
路文芳
杜旭红
路晶
赵凯杰
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China Institute for Radiation Protection
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China Institute for Radiation Protection
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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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • 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
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    • 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
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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    • B65D65/38—Packaging materials of special type or form
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/286—Chlorinated polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
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    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
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    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

The invention discloses a transparent high-barrier composite material and a preparation method thereof, wherein the composite material comprises a transparent protective layer, a barrier layer and an antibacterial layer, the protective layer is positioned outside the barrier layer, and plays a role in protecting the barrier layer, so that the weather resistance and chemical resistance of the composite material are improved, and the good moisture absorption resistance, corrosion resistance and the like of the composite material are effectively maintained in environments with high temperature, high humidity, high salt mist, offshore climate and high humidity and high salt concentration; the barrier layer improves the water vapor and oxygen barrier performance of the composite material, improves the moisture absorption resistance, oxidation resistance and sealing performance of the composite material package, and prolongs the environmental state in the package; the antibacterial layer improves the antibacterial performance of the composite material, reduces the propagation of bacteria in the composite material package, and ensures the performance of the composite material package under extreme conditions; the preparation method of the transparent high-barrier composite material provided by the invention is simple and convenient.

Description

Transparent high-barrier composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of packaging materials, and particularly relates to a transparent high-barrier composite material and a preparation method thereof.
Background
The package is an organic component of the weapon equipment system. The method is the general names of containers, materials and auxiliary objects adopted according to a certain technical method for protecting weapons and equipment in the circulation process and facilitating storage, transportation and supply guarantee. Packaging is one of the important technical means for realizing weapon equipment protection, and directly influences the reliability, safety and guarantee capability of weapon equipment storage.
With the wide application of new technologies and new materials in weaponry, the requirements for environmental protection are continuously increased while the performance of equipment systems is improved. Higher requirements are placed on modern military packaging.
Under the condition of severe environment or difficult storage, particularly the border defense line in China comprises severe environments such as northern cold, southern high temperature and high humidity, coastal high salt fog, offshore extreme weather and the like, and many military products such as ammunition and electronic instruments are extremely easy to cause functional failure, damp rust or mold erosion due to moisture absorption. The military packaging system is required to have good moisture-proof sealing performance, and can scientifically package and store temporary or long-term unused vehicle equipment and provide a dry airtight internal environment for the weapon equipment, so that the service life of the equipment is prolonged, the maintenance cost is reduced, the equipment investment is saved, and the equipment is ensured to be in a combat readiness usable state at any time.
In the prior art, polyvinyl chloride is adopted as the main component of the packaging material, but the polyvinyl chloride material has poor heat resistance and aging resistance, and is easy to deform and age at high temperature. The addition of lignin to polyvinyl chloride improves the anti-aging performance and strength of the polyvinyl chloride material. However, it has no antibacterial property and has a high water vapor permeability.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a transparent high-barrier composite material with antibacterial property and small water vapor transmittance and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme: a transparent high-barrier composite material comprises a transparent protective layer, a barrier layer and an antibacterial layer which are sequentially arranged from top to bottom; the protective layer is composed of chlorinated polyethylene, polyvinyl chloride and an acrylic acid impact modifier material; the barrier layer is made of one of polyvinylidene chloride or polytetrafluoroethylene and polypropylene materials; the antibacterial layer is composed of chlorinated polyethylene, polyvinyl chloride, an acrylic acid impact modifier and a nano zinc oxide material.
Further, the composite material also comprises a transition layer, wherein the transition layer is composed of ethyl acetate, vinyl acetate-ethylene copolymer and ethylene-vinyl alcohol copolymer.
The invention also provides a preparation method of the transparent high-barrier composite material, which comprises the following steps: the method comprises the following steps:
(1) Granulating the constituent materials of the protective layer, the barrier layer and the antibacterial layer by using granulating equipment;
(2) And co-extruding the granulated protective layer, barrier layer and antibacterial layer materials to form the transparent high-barrier composite material.
Further, in the step (1), a granulating device is used for preparing the transition layer material; in the step (2), the granulated transition layer, the protective layer, the barrier layer and the antibacterial layer are co-extruded to form a transparent high-barrier composite material.
The technical scheme provided by the invention has the beneficial effects that the transparent high-barrier composite material comprises a transparent protective layer, a barrier layer and an antibacterial layer, wherein the protective layer is composed of chlorinated polyethylene, polyvinyl chloride and an acrylic acid impact modifier material; the barrier layer is made of polyvinylidene chloride or polytetrafluoroethylene and polypropylene materials; the protective layer is positioned outside the barrier layer, plays a role in protecting the barrier layer, improves the weather resistance and chemical resistance of the composite material, and effectively keeps the good moisture absorption resistance, corrosion resistance and the like of the composite material in environments with high temperature, high humidity, high salt fog, offshore climates and high humidity and high salt concentration; the barrier layer improves the water vapor and oxygen barrier performance of the composite material, improves the moisture absorption resistance, oxidation resistance and sealing performance of the composite material package, and prolongs the environment state in the package; the antibacterial layer is composed of chlorinated polyethylene, polyvinyl chloride, an acrylic acid impact modifier and a nano zinc oxide material; the antibacterial layer improves the antibacterial performance of the composite material, reduces the propagation of bacteria in the composite material package, and ensures the performance of the composite material package under extreme conditions. The preparation method of the transparent high-barrier composite material provided by the invention is simple and convenient.
Drawings
FIG. 1 is a schematic view of a transparent high barrier composite structure according to an embodiment of the present invention.
Wherein, the protective layer 1, the barrier layer 2 and the antibacterial layer 3.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
Referring to fig. 1, a transparent high-barrier composite material comprises a transparent protective layer 1, a barrier layer 2 and an antibacterial layer 3 which are sequentially arranged from top to bottom; the protective layer 1 is composed of chlorinated polyethylene, polyvinyl chloride and an acrylic acid impact modifier material; the barrier layer 2 is made of one of polyvinylidene chloride or polytetrafluoroethylene and polypropylene materials; the antibacterial layer 3 is composed of chlorinated polyethylene, polyvinyl chloride, an acrylic acid impact modifier and a nano zinc oxide material.
Preferably, the protective layer 1 comprises, by mass, 2-70% of chlorinated polyethylene, 25-97% of polyvinyl chloride and 1-5% of an acrylic acid impact modifier, the barrier layer 2 comprises, by mass, 100% of polyvinylidene chloride or 1-97% of polytetrafluoroethylene and 3-99% of polypropylene, and the antibacterial layer 3 comprises, by mass, 2-85% of chlorinated polyethylene, 3-85% of polyvinyl chloride, 1-5% of an acrylic acid impact modifier and 0-10% of nano zinc oxide.
Preferably, the barrier layer 2 is provided in 2 layers.
Preferably, a transition layer is arranged among the protective layer 1, the barrier layer 2 and the antibacterial layer 3, and the transition layer is arranged between the adjacent barrier layers 2.
Preferably, the transition layer composition comprises 75-85% of vinyl acetate-ethylene copolymer, 5-15% of ethyl acetate and 10-20% of ethylene-vinyl alcohol copolymer in percentage by mass.
The performance index detection data of the transparent high-barrier composite material of the embodiment of the invention are shown in table 1.
TABLE 1 Performance index of the transparent high barrier composite of the examples of this invention
As can be seen from Table 1, the transparent high-barrier composite material of the embodiment of the invention has the advantages of good performance indexes, thin total thickness, good acid and alkali resistance, small water vapor and oxygen transmission rate and effective antibacterial property; the composite material packaging material can be used as a military material packaging material and has good moisture absorption resistance, corrosion resistance, water vapor and oxygen blocking performance in environments such as low temperature, high temperature and high humidity, high salt fog, high salt concentration and the like, and the inner environment state of the composite material packaging material can be effectively maintained.
The invention also provides a preparation method of the transparent high-barrier composite material, which comprises the following steps: the method comprises the following steps:
(1) Granulating the above constituent materials of the protective layer 1, the barrier layer 2 and the antibacterial layer 3 by using granulating equipment;
(2) And co-extruding the materials of the granulated protective layer 1, the barrier layer 2 and the antibacterial layer 3 to form a transparent high-barrier composite material.
Preferably, in the step (1), the transition layer composition material is granulated using a granulating apparatus; in the step (2), the granulated transition layer, the protective layer 1, the barrier layer 2 and the antibacterial layer 3 are co-extruded to form a transparent high-barrier composite material.
Example two
The embodiment of the invention provides a transparent high-barrier composite material, which comprises a transparent protective layer 1, a barrier layer 2 and an antibacterial layer 3 which are sequentially arranged from top to bottom; the protective layer 1 comprises, by mass, 35% of chlorinated polyethylene, 60% of polyvinyl chloride and 5% of an acrylic acid impact modifier; the barrier layer 2 comprises 100% of polyvinylidene chloride in percentage by mass; the antibacterial layer 3 comprises 32% of chlorinated polyethylene, 61% of polyvinyl chloride, 4% of acrylic acid impact modifier and 3% of nano zinc oxide in percentage by mass.
Preferably, the composite material further comprises a transition layer, wherein the composition content of the transition layer comprises 82% of vinyl acetate-ethylene copolymer, 6% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer in percentage by mass.
The performance index detection data of the transparent high-barrier composite material of the embodiment of the invention are shown in table 2.
TABLE 2 Performance index of transparent high Barrier composite according to embodiments of the invention
The rest is the same as the first embodiment.
Example III
The embodiment of the invention provides a transparent high-barrier composite material, which comprises a transparent protective layer 1, a barrier layer 2 and an antibacterial layer 3 which are sequentially arranged from top to bottom; the protective layer 1 comprises 25% of chlorinated polyethylene, 70% of polyvinyl chloride and 5% of acrylic acid impact modifier in percentage by mass; the barrier layer 2 comprises 50% of polytetrafluoroethylene and 50% of polypropylene in percentage by mass; the antibacterial layer 3 comprises 61% of chlorinated polyethylene, 31% of polyvinyl chloride, 5% of acrylic acid impact modifier and 3% of nano zinc oxide in percentage by mass.
Preferably, the composite material further comprises a transition layer, wherein the component content of the transition layer comprises 75% of vinyl acetate-ethylene copolymer, 13% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer in percentage by mass.
The performance index detection data of the transparent high-barrier composite material of the embodiment of the invention are shown in table 3.
TABLE 3 Performance index of transparent high Barrier composite according to embodiments of the invention
The rest is the same as the first embodiment.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (7)

1. A transparent high-barrier composite material is characterized in that: comprises a transparent protective layer (1), a barrier layer (2) and an antibacterial layer (3) which are arranged in sequence from top to bottom; the protective layer (1) is composed of chlorinated polyethylene, polyvinyl chloride and an acrylic acid impact modifier material; the barrier layer (2) is made of one of polyvinylidene chloride or polytetrafluoroethylene and polypropylene materials; the antibacterial layer (3) is composed of chlorinated polyethylene, polyvinyl chloride, an acrylic acid impact modifier and a nano zinc oxide material; the barrier layer (2) is provided with 2 layers; a transition layer is arranged among the protective layer (1), the barrier layer (2) and the antibacterial layer (3), and the transition layer is arranged between adjacent barrier layers (2); the transition layer comprises 75-85% of vinyl acetate-ethylene copolymer, 5-15% of ethyl acetate and 10-20% of ethylene-vinyl alcohol copolymer by mass percent.
2. A transparent high barrier composite according to claim 1, characterized in that: the protective layer (1) comprises, by mass, 2% -70% of chlorinated polyethylene, 25% -97% of polyvinyl chloride and 1% -5% of an acrylic acid impact modifier; the component content of the barrier layer (2) is calculated by mass percent and consists of 100 percent of polyvinylidene chloride or 1-97 percent of polytetrafluoroethylene and 3-99 percent of polypropylene; the antibacterial layer (3) comprises 2-85% of chlorinated polyethylene, 3-85% of polyvinyl chloride, 1-5% of acrylic acid impact modifier and 0-10% of nano zinc oxide by mass percent.
3. A transparent high barrier composite according to claim 1, characterized in that: the protective layer (1) comprises, by mass, 35% of chlorinated polyethylene, 60% of polyvinyl chloride and 5% of an acrylic acid impact modifier; the component content of the barrier layer (2) is 100% of polyvinylidene chloride in percentage by mass; the antibacterial layer (3) comprises 32% of chlorinated polyethylene, 61% of polyvinyl chloride, 4% of acrylic acid impact modifier and 3% of nano zinc oxide in percentage by mass.
4. A transparent high barrier composite according to claim 1, characterized in that: the transition layer comprises 82% of vinyl acetate-ethylene copolymer, 6% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer in percentage by mass.
5. A transparent high barrier composite according to claim 1, characterized in that: the protective layer (1) comprises 25% of chlorinated polyethylene, 70% of polyvinyl chloride and 5% of acrylic acid impact modifier in percentage by mass; the barrier layer (2) comprises 50% of polytetrafluoroethylene and 50% of polypropylene material by mass percent; the antibacterial layer (3) comprises 61% of chlorinated polyethylene, 31% of polyvinyl chloride, 5% of acrylic acid impact modifier and 3% of nano zinc oxide in percentage by mass.
6. A transparent high barrier composite according to claim 1, characterized in that: the transition layer comprises 75% of vinyl acetate-ethylene copolymer, 13% of ethyl acetate and 12% of ethylene-vinyl alcohol copolymer in percentage by mass.
7. The method for preparing a transparent high barrier composite material according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
granulating materials of the protective layer (1), the barrier layer (2) and the antibacterial layer (3) by using granulating equipment;
(2) And sequentially co-extruding the materials of the granulated protective layer (1), the barrier layer (2) and the antibacterial layer (3) into a transparent high-barrier composite material.
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