CN111634093A - High-barrier polyvinyl chloride-polyethylene composite sheet and preparation method and application thereof - Google Patents

High-barrier polyvinyl chloride-polyethylene composite sheet and preparation method and application thereof Download PDF

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Publication number
CN111634093A
CN111634093A CN202010529124.4A CN202010529124A CN111634093A CN 111634093 A CN111634093 A CN 111634093A CN 202010529124 A CN202010529124 A CN 202010529124A CN 111634093 A CN111634093 A CN 111634093A
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polyvinyl chloride
polyethylene
composite sheet
layer
barrier
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张强
姜瑞
朱纯伟
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Grand Pharmaceutical Huangshi Feiyun Pharmaceutical Co ltd
Changchun Institute of Applied Chemistry of CAS
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Grand Pharmaceutical Huangshi Feiyun Pharmaceutical Co ltd
Changchun Institute of Applied Chemistry of CAS
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Priority to CN202010529124.4A priority Critical patent/CN111634093A/en
Publication of CN111634093A publication Critical patent/CN111634093A/en
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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
    • B32B27/30—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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/162—Cleaning
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a high-barrier polyvinyl chloride-polyethylene composite sheet and a preparation method and application thereof, belonging to the technical field of composite sheets. Solves the technical problem that the polyethylene-polyvinyl chloride plastic bottle for containing the antiviral oral medicine in the prior art has short shelf life. The high-barrier polyvinyl chloride-polyethylene composite sheet material disclosed by the invention is composed of a polyethylene layer, a first polyacrylamide layer, a polyurethane glue layer, a second polyacrylamide layer and a polyvinyl chloride layer which are sequentially arranged from inside to outside. The composite sheet has good barrier property, can be used as a medical packaging material, ensures the long-term stability of the contained medicine, and can greatly prolong the shelf life of the antiviral oral liquid by detecting the plastic bottle prepared by using the composite sheet.

Description

High-barrier polyvinyl chloride-polyethylene composite sheet and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite sheets, particularly relates to a high-barrier polyvinyl chloride-polyethylene composite sheet, and a preparation method and application thereof, and particularly relates to application of the high-barrier polyvinyl chloride-polyethylene composite sheet in a medicine packaging material.
Background
Polyvinyl chloride (pvc), abbreviated as pvc (polyvinyl chloride), is an initiator for Vinyl Chloride Monomer (VCM), such as peroxide and azo compound; or a polymer polymerized by a free radical polymerization mechanism under the action of light and heat.
PVC has the advantages of flame retardancy (flame retardancy of 40 or more), high chemical resistance (resistance to concentrated hydrochloric acid, 90% sulfuric acid, 60% nitric acid, and 20% sodium hydroxide), and good mechanical strength and electrical insulation, has been a common plastic with the largest output in the world, and is widely used in the fields of building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leathers, pipes, electric wires and cables, packaging films, bottles, foaming materials, sealing materials, fibers, and the like. However, PVC molecules have strong polarity, the activity of molecular chain segments is poor, the glass transition temperature is up to more than 80 ℃, and the PVC molecules have the characteristics of brittleness, hardness and poor flexibility. In addition, PVC has a small amount of crystals, so that the melting point of the PVC is higher, the liquid viscosity of the PVC is also higher due to a polar structure, and the processability is poor. These drawbacks have led to the fact that PVC cannot be used alone and is generally mixed with plasticizers, which make up 50% of the total weight, to achieve its excellent properties.
The PVC products commonly used contain dihexyl phthalate (DEHP) plasticizers. It has the functions of making PVC soft and easy to bend, and increasing the elasticity of PVC products. However, the results of many animal experiments show that DEHP has various toxicities such as reproductive development toxicity, immunotoxicity, embryotoxicity, hepatotoxicity and carcinogenicity, and has estrogen-like activity causing the metabolic change of thyroxine. Due to the high toxicity of DEHP and the high content in PVC (40-60%), PVC does not allow contact with drugs or food and cannot be used as packaging material for medical instruments or food.
In the prior art, in order to solve the problem of high toxicity of the PVC material caused by DEHP, researchers at home and abroad adopt a method of coating a layer of Polyethylene (PE) film on the surface of a PVC plate to prepare a PVC-PE composite plate, and the preparation process is shown in figure 1. The PE film is in direct contact with the drug or food, acting as an insulating layer, cutting off the contact of DEHP with the drug or food. The PE material is not added or only added with little plasticizer in the process of making the film, and the monomer ethylene is a substance widely existing in natural plants, so that the PE material is much safer as a food packaging material than a PVC material, and meanwhile, animal experiments also prove that the PE material is low in toxicity. However, the technical personnel find that when the plastic bottle prepared by taking the PVC-PE composite board as the material is used for containing the antiviral oral medicine, the concentration of the effective component (R, S) -goitrin of the antiviral oral medicine is gradually reduced along with the prolonging of time, and after half a year, the content of the (R, S) -goitrin is reduced to be lower than the effective concentration, but the antiviral oral medicine contained in the glass bottle hardly changes obviously. This result is caused by the fact that the inner wall of the plastic bottle, i.e. the surface of the PE film, has numerous micro-cracks during early processing and transport, resulting in (R, S) -goitrin penetrating the PE film through these cracks, being absorbed by DEHP in PVC, which tends to grow larger with time and therefore to decrease in concentration more rapidly.
The super-crosslinked PAM film has very high barrier effect, for example, tetracycline, sulfamethazine, estriol and the like can not permeate the crosslinked PAM film, but in the prior art, the PAM film is not applied to the PVC-PE composite board, because of the following technical difficulties: how to ensure the adhesion capability of the PAM film with the PVC plate and the PE film without influencing the physical and mechanical properties of the PVC plate and the PE film; secondly, how to control the thickness of the PAM film to be uniform and keep better light transmittance; and (III) how to maintain the higher barrier performance of the PAM film.
Disclosure of Invention
The invention aims to solve the technical problem that a polyethylene-polyvinyl chloride plastic bottle for containing antiviral oral drugs in the prior art is short in shelf life, and provides a high-barrier polyvinyl chloride-polyethylene composite sheet and a preparation method and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The high-barrier polyvinyl chloride-polyethylene composite sheet disclosed by the invention is composed of a Polyethylene (PE) layer, a first Polyacrylamide (PAM) layer, a polyurethane glue layer, a second polyacrylamide layer and a polyvinyl chloride layer which are sequentially arranged from inside to outside.
Preferably, the thickness of the polyethylene layer is 3-5 μm, the thickness of the first polyacrylamide layer is 1-4 μm, the thickness of the polyurethane glue layer is 3-5 μm, the thickness of the second polyacrylamide layer is 1-4 μm, and the thickness of the polyvinyl chloride layer is 1 mm.
The preparation method of the high-barrier polyvinyl chloride-polyethylene composite sheet comprises the following steps:
step one, respectively soaking a polyvinyl chloride plate and a polyethylene film into a solvent containing 30 wt% of Benzophenone (BP) to obtain a primary soaked polyvinyl chloride plate and a primary soaked polyethylene film;
the solvent is water or alcohols;
step two, respectively soaking the primary soaked polyvinyl chloride plate and the primary soaked polyethylene film into a solvent containing the raw material and a cross-linking agent to obtain a secondary soaked polyvinyl chloride plate and a secondary soaked polyethylene film;
the raw material is one or a mixture of N-isopropyl acrylamide and acrylamide according to any proportion, and the cross-linking agent is one or a mixture of N, N-methylene bisacrylamide and ethylene diacrylate according to any proportion; the mass ratio of the raw material to the cross-linking agent is less than 1:1 and greater than 1:3, and the solvent is water or alcohol;
respectively irradiating the upper surface of the secondary soaking polyvinyl chloride plate and the lower surface of the secondary soaking polyethylene film by using ultraviolet light, and cleaning by using water or alcohols to obtain a polyvinyl chloride-polyacrylamide plate and a polyethylene-polyacrylamide film;
and step four, bonding the upper surface of the polyvinyl chloride-polyacrylamide plate and the lower surface of the polyethylene-polyacrylamide film through polyurethane glue, hot pressing and drying to obtain the high-barrier polyvinyl chloride-polyethylene composite sheet.
Preferably, in the first step, the soaking time is 0.5 h.
Preferably, in the second step, in the solvent containing the raw material and the cross-linking agent, the concentration of the raw material is 0.2 wt% to 0.5 wt%, and the concentration of the cross-linking agent is 0.5 wt% to 1 wt%.
Preferably, in the second step, the mass ratio of the raw material to the cross-linking agent is 3: 7.
Preferably, in the second step, the soaking time is 5-10 min.
Preferably, in the third step, the wavelength of the ultraviolet light is 365nm, and the irradiation time is 1-5 min.
Preferably, in the fourth step, the hot-pressing temperature is 100-.
The invention also provides application of the high-barrier composite sheet in medical packaging materials.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the high-barrier polyvinyl chloride-polyethylene composite sheet adopts a precursor casting method, and the liquid-state precursor of PAM is soaked on a PVC plate and a PE film and then solidified into the PAM film. On one hand, the PAM film is respectively combined with the PVC plate and the PE film together by covalent bonds by adopting a covalent graft polymerization method, so that the problem that the PAM film is separated from the base material (the PVC plate and the PE film) due to large polarity difference is solved, the PAM film is ensured to have good adhesion and difficult shedding, the mechanical property of the base material is not influenced, no chemical glue is used, and the cost is reduced; on the other hand, compared with the direct hot-pressing solid film, the PAM obtained by the method has more uniform thickness and smoother surface, and can keep better light transmittance.
According to the preparation method of the high-barrier polyvinyl chloride-polyethylene composite sheet, the content of the cross-linking agent is increased, the gaps among PAM molecular weights are reduced, the density is increased, and the barrier capability of the composite sheet is improved.
The high-barrier polyvinyl chloride-polyethylene composite sheet material disclosed by the invention is good in barrier property, can be used as a medical packaging material, ensures the long-term stability of contained medicines, and can be used for greatly prolonging the quality guarantee period of antiviral oral liquid through detection.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram for preparing a PVC-PE composite board in the prior art;
FIG. 2 is a process flow diagram of the present invention for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet;
FIG. 3 is an SEM scanning electron micrograph of the upper surface of a PVC-PAM sheet according to example 1 of the present invention.
FIG. 4 is an SEM scanning electron micrograph of a cross section of a PVC-PAM plate of example 1 of the present invention.
In FIG. 5, (a) is a change rule of the content of (R, S) -goivochen in a PVC-PE plastic bottle and a PVC-PAM-PE plastic bottle stored at a low temperature of 10 ℃ for 6 months with time; (b) the change rule of the content of (R, S) -goitrin in a PVC-PE plastic bottle and a PVC-PAM-PE plastic bottle which are stored for 6 months at normal temperature and 20 ℃ along with time; (c) the change rule of the content of (R, S) -goitrin in PVC-PE plastic bottles and PVC-PAM-PE plastic bottles which are stored for 40 hours at a high temperature of 50 ℃ along with the time; (d) the change rule of the content of (R, S) -goivochen in PVC-PE plastic bottles and PVC-PAM-PE plastic bottles which are stored for 80 hours at a high temperature of 50 ℃ along with the time.
In the figure, the adhesive comprises a polyvinyl chloride layer 1, a polyurethane glue layer 2, a polyethylene layer 3, a first polyacrylamide layer 4, a second polyacrylamide layer 5 and a third polyacrylamide layer.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and not to limit the claims to the invention.
The high-barrier polyvinyl chloride-polyethylene composite sheet disclosed by the invention is composed of a polyethylene layer 3, a first polyacrylamide layer 4, a polyurethane glue layer 2, a second polyacrylamide layer 5 and a polyvinyl chloride layer 1 which are sequentially arranged from inside to outside.
In the above technical solution, the thicknesses of the polyethylene layer 3, the first polyacrylamide layer 4, the polyurethane glue layer 2, the second polyacrylamide layer 5 and the polyvinyl chloride layer 1 are not particularly limited, preferably, the thickness of the polyethylene layer 3 is 3 to 5 μm, the thickness of the first polyacrylamide layer 4 is 1 to 4 μm, the thickness of the polyurethane glue layer 3 is 3 to 5 μm, the thickness of the second polyacrylamide layer 5 is 1 to 4 μm, and the thickness of the polyvinyl chloride layer 1 is 1 mm.
The preparation method of the high-barrier polyvinyl chloride-polyethylene composite sheet comprises the following steps:
respectively soaking a polyvinyl chloride plate and a polyethylene film into ethanol containing 30 wt% of benzophenone, wherein benzophenone molecules are adsorbed on the surfaces of the polyvinyl chloride plate and the polyethylene film, so as to obtain a primary soaked polyvinyl chloride plate and a primary soaked polyethylene film;
step two, respectively soaking the primary soaked polyvinyl chloride plate and the primary soaked polyethylene film into a solvent containing the raw material and a cross-linking agent to obtain a secondary soaked polyvinyl chloride plate and a secondary soaked polyethylene film;
respectively irradiating the upper surface of the secondarily-soaked polyvinyl chloride plate and the lower surface of the secondarily-soaked polyethylene film by using ultraviolet light, wherein in the process, benzophenone molecules absorb photons to generate free radicals to initiate polymerization of raw materials and a cross-linking agent to form a PAM film, in the PAM polymerization process, a small amount of C-H bonds on the surface of the PVC plate or the PE film absorb the free radicals to generate carbon free radicals, and the carbon free radicals can also participate in polymerization reaction, so that the PAM film is combined with the PVC plate or the PE film in a covalent bond form, and then cleaning and removing unreacted monomers to obtain the polyvinyl chloride-polyacrylamide plate and the polyethylene-polyacrylamide film;
and step four, bonding the upper surface of the polyvinyl chloride-polyacrylamide plate and the lower surface of the polyethylene-polyacrylamide film through polyurethane glue, hot pressing and drying to obtain the high-barrier polyvinyl chloride-polyethylene composite sheet.
In the above technical scheme, in the step one, the soaking time is preferably more than 0.5 h.
In the above technical scheme, in the second step, the soaking time is preferably 5-10 min.
In the technical scheme, in the third step, the wavelength of the ultraviolet light is 365nm, and the irradiation time is preferably 1-5 min.
In the fourth step, the hot pressing temperature is preferably 100-150 ℃, and the pressure is preferably 5-10 atm.
The invention also provides application of the high-barrier composite sheet in medical packaging materials.
In the second step, the raw material is one or more of N-isopropyl acrylamide and acrylamide mixed according to any proportion, and the cross-linking agent is one or more of N, N-methylene bisacrylamide and ethylene diacrylate mixed according to any proportion; the mass ratio of the raw material to the cross-linking agent is less than 1:1 and more than 1: 3; the mass ratio of the raw material to the crosslinking agent is preferably 3: 7. According to the preparation method of the high-barrier polyvinyl chloride-polyethylene composite sheet, the content of the cross-linking agent is increased, gaps among PAM molecular weights are reduced, the density is increased, the barrier capability of the composite sheet is improved, and the surfaces of the prepared first polyacrylamide layer 4 and the second polyacrylamide layer 5 are crack-free. Preferably, the solvent contains raw material and cross-linking agent, the concentration of raw material is 0.2 wt% -0.5 wt%, and the concentration of cross-linking agent is 0.5 wt% -1 wt%.
In the technical scheme, the solvent and the cleaning agent are both alcohols or water, and preferably ethanol.
The invention also provides application of the high-barrier composite sheet in medical packaging materials. A common method is to blow mold a high barrier pvc-pe composite sheet into a bottle for containing an anti-viral oral drug (the pe layer 3 contacts the drug), but is not so limited.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following embodiments and the accompanying drawings.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
The most important step in the process of manufacturing the PVC-PAM-PE film is to prepare the PAM film, wherein the doping ratio of the raw material to the cross-linking agent is particularly important, and in order to discuss the optimal ratio of the raw material to the cross-linking agent, scientific researchers can manufacture more than 200 samples, and 3 representative examples of the samples are shown.
Example 1
Step one, respectively soaking a PVC plate (1mm) and a PE film (3-5 microns) into ethanol containing 30 wt% of benzophenone for 0.5h to obtain a primary soaked PVC plate and a primary soaked PE film;
step two, respectively immersing the primary immersed PVC plate and the primary immersed PE film into ethanol containing a raw material (N-isopropylacrylamide, the concentration of which is 0.507 wt%) and a cross-linking agent (N, N-methylenebisacrylamide, the concentration of which is 1.181 wt%) for 5-10min to obtain a secondary immersed PVC plate and a secondary immersed PE film;
wherein the mass ratio of the raw materials to the cross-linking agent is 3: 7;
respectively irradiating the upper surface of the secondary soaking PVC plate and the lower surface of the secondary soaking PE film by using ultraviolet light (365nm) for 1-5min, and cleaning by using ethanol to obtain a PVC-PAM plate and a PE-PAM film;
and step four, bonding the upper surface of the PVC-PAM plate and the lower surface of the PE-PAM film through polyurethane glue, hot-pressing (the hot-pressing temperature is 100-150 ℃ and the pressure is 5-10 atmospheric pressures), and drying to obtain the high-barrier polyvinyl chloride-polyethylene composite sheet.
Through inspection, the PAM film is tightly combined with the lower surface of the PVC plate and the upper surface of the PE film, the formed film is smooth, the components are uniform, the surface has no cracks, and SEM scanning electron micrographs of the upper surface and the cross section of the PVC-PAM plate are respectively shown in FIG. 3 and FIG. 4. The raw material is replaced by acrylamide, and the cross-linking agent is replaced by ethylene diacrylate to achieve the same effect.
Comparative example 1
The ratio of N-isopropylacrylamide to N, N-methylenebisacrylamide in step two of example 1 was changed to 1:1, and the procedure was otherwise the same as in example 1.
The tests show that a solidified PAM film cannot be formed on the lower surface of the PVC plate and the upper surface of the PE film, the PAM film still presents an unsolidified gel state after being irradiated by an ultraviolet lamp, and researches show that part of raw materials do not participate in polymerization reaction due to insufficient dosage of the cross-linking agent.
Comparative example 2
The ratio of N-isopropylacrylamide to N, N-methylenebisacrylamide in step two of example 1 was changed to 1:3, and the procedure was otherwise the same as in example 1.
Through inspection, after the ultraviolet lamp irradiates, the PAM film falls off from the upper surface of the PVC plate and the lower surface of the PE film, and is not tightly combined with the PVC plate and the PE film according to the original surface grafting technology.
Comparative example 3
The upper surface of a PVC plate (same as that in example 1) and the lower surface of a PE film (same as that in example 1) are bonded by polyurethane glue, hot pressed (the hot pressing temperature is 100-150 ℃ and the pressure is 5-10 atmospheric pressures), and dried to obtain the PVC-PE composite sheet.
The composite sheets of example 1 and comparative example 3 were tested for their performance.
And (3) blow-molding the two plates into 10ml antiviral oral liquid-filled plastic bottles which are respectively marked as PVC-PAM-PE plastic bottles and PVC-PE plastic bottles, packaging 10ml antiviral oral liquid, and carrying out simulation time test. Each set of tests used 180 bottles each of two plastic bottles. The test process is as follows: the content of (R, S) -goitrin in PVC-PE plastic bottles and PVC-PAM-PE plastic bottles under different storage conditions was measured by high performance liquid chromatography with respect to the change with time after 6 months storage at a low temperature of 10 ℃, 6 months storage at a normal temperature of 20 ℃, 40 hours storage at a high temperature of 50 ℃ (simulated storage for 6 months), and 80 hours storage at a high temperature of 50 ℃ (simulated storage for 12 months), and the results are shown in FIGS. 5 (a) - (d), respectively. The low temperature test is to simulate the storage condition of the refrigerator, the medium and high temperature test is an accelerated test, and the stability of long-time storage can be calculated according to the simulation result. As can be seen from FIG. 5, the PVC-PAM-PE plastic bottle can significantly improve the prevention of the absorption of the active ingredients of the antiviral oral liquid, and can greatly prolong the shelf life of the antiviral oral liquid contained in the plastic bottle.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (10)

1. The high-barrier polyvinyl chloride-polyethylene composite sheet comprises a polyethylene layer, a first polyacrylamide layer, a polyurethane glue layer, a second polyacrylamide layer and a polyvinyl chloride layer which are sequentially arranged from inside to outside.
2. The high barrier pvc-polyethylene composite sheet according to claim 1, wherein the thickness of the polyethylene layer is 3 to 5 μm, the thickness of the first polyacrylamide layer is 1 to 4 μm, the thickness of the polyurethane glue layer is 3 to 5 μm, the thickness of the second polyacrylamide layer is 1 to 4 μm, and the thickness of the pvc layer is 1 mm.
3. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 1 or 2, comprising the steps of:
step one, respectively soaking a polyvinyl chloride plate and a polyethylene film into a solvent containing 30 wt% of benzophenone to obtain a primary soaked polyvinyl chloride plate and a primary soaked polyethylene film;
the solvent is water or alcohols;
step two, respectively soaking the primary soaked polyvinyl chloride plate and the primary soaked polyethylene film into a solvent containing the raw material and a cross-linking agent to obtain a secondary soaked polyvinyl chloride plate and a secondary soaked polyethylene film;
the raw material is one or a mixture of N-isopropyl acrylamide and acrylamide according to any proportion, and the cross-linking agent is one or a mixture of N, N-methylene bisacrylamide and ethylene diacrylate according to any proportion; the mass ratio of the raw material to the cross-linking agent is less than 1:1 and greater than 1:3, and the solvent is water or alcohol;
respectively irradiating the upper surface of the secondarily soaked polyvinyl chloride plate and the lower surface of the secondarily soaked polyethylene film by using ultraviolet light, and cleaning by using ethanol or water to obtain a polyvinyl chloride-polyacrylamide plate and a polyethylene-polyacrylamide film;
and step four, bonding the upper surface of the polyvinyl chloride-polyacrylamide plate and the lower surface of the polyethylene-polyacrylamide film through polyurethane glue, hot pressing and drying to obtain the high-barrier polyvinyl chloride-polyethylene composite sheet.
4. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 3, wherein in the step one, the soaking time is 0.5 h.
5. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 3, wherein in the second step, the concentration of the raw material is 0.2 wt% to 0.5 wt% and the concentration of the cross-linking agent is 0.5 wt% to 1 wt% in the solvent containing the raw material and the cross-linking agent.
6. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 3, wherein in the second step, the mass ratio of the raw material to the cross-linking agent is 3: 7.
7. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 3, wherein in the second step, the soaking time is 5-10 min.
8. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 3, wherein in the third step, the wavelength of the ultraviolet light is 365nm, and the irradiation time is 1-5 min.
9. The method for preparing a high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 3, wherein in the fourth step, the hot pressing temperature is 100-150 ℃ and the pressure is 5-10 atm.
10. Use of the high-barrier polyvinyl chloride-polyethylene composite sheet according to claim 1 or 2 in a medical packaging material.
CN202010529124.4A 2020-06-11 2020-06-11 High-barrier polyvinyl chloride-polyethylene composite sheet and preparation method and application thereof Pending CN111634093A (en)

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CN106397822A (en) * 2015-08-03 2017-02-15 住友橡胶工业株式会社 Surface modification method and surface-modified body
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Application publication date: 20200908