CN113119562A - High-barrier plastic sheet and production process thereof - Google Patents
High-barrier plastic sheet and production process thereof Download PDFInfo
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- CN113119562A CN113119562A CN202110519792.3A CN202110519792A CN113119562A CN 113119562 A CN113119562 A CN 113119562A CN 202110519792 A CN202110519792 A CN 202110519792A CN 113119562 A CN113119562 A CN 113119562A
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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
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
- B32B27/06—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
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
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- 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
- C08J2325/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- 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
- C08J2427/00—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
- C08J2427/02—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
- C08J2427/12—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 fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
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- 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
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08J2461/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Abstract
The invention provides a high-barrier plastic sheet, which comprises a substrate layer and a barrier layer arranged on the substrate layer, wherein the barrier layer comprises the following components in parts by weight: 100 parts of polystyrene resin and 2-7 parts of polyalkylene glycol; 0.5-2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 1-4 parts of toughening agent; 0.5-3 parts of reinforcing agent and 0.3-0.6 part of antioxidant. The high-barrier plastic sheet and the production process thereof utilize the advantages of 2 parts of polyalkylene glycol and hydroquinone bis (beta-hydroxyethyl) ether to make up for deficiencies after combining the polyalkylene glycol and the hydroquinone bis (beta-hydroxyethyl) ether, thereby improving the mechanical strength, the flexibility, the water vapor barrier property and the oxygen barrier property of the plastic sheet; by introducing strontium oxide with two specifications into the barrier layer, strontium oxide particles are tightly arranged in the barrier layer, so that the internal structure is uniform, the product performance is stable, the comprehensive strength is high, and the strength and the barrier performance can be effectively improved.
Description
Technical Field
The invention relates to the technical field of plastic sheets, in particular to a high-barrier plastic sheet and a production process thereof.
Background
Various thermoformed containers such as cups, bowls and basins are used more and more widely in daily life, and with the improvement of the requirements of people on the quality of life, the market has higher and higher grade requirements on the products. Materials used for food packaging must have different high barrier properties, for example, greasy food requires high oxidation resistance and oil barrier properties, and dry food requires high moisture barrier properties; the fresh and alive fruit and vegetable foods also need to be packaged with certain oxygen, carbon dioxide and water vapor permeability, and meanwhile, the materials are required to have good mechanical properties and chemical stability so as to ensure the food packaging quality and ensure the food safety, the plastic packaging container with the barrier property has wide market demand and great development potential, and the existing packaging plastic sheet still has the defect of poor barrier property.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-barrier plastic sheet and a production process thereof, which can improve the barrier property and the mechanical property of the plastic sheet. The technical scheme adopted by the invention is as follows:
a high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 2-7 parts of polyalkylene glycol; 0.5-2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 1-4 parts of toughening agent; 0.5-3 parts of reinforcing agent and 0.3-0.6 part of antioxidant.
Preferably, the high-barrier plastic sheet is one in which: the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, and the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 2-4: 1.
Preferably, the high-barrier plastic sheet is one in which: the reinforcing agent is polylactide fiber yarns and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber yarns to the tetrafluoroethylene-butadiene copolymer is 1-3: 1.
Preferably, the high-barrier plastic sheet is one in which: the antioxidant is one or a mixture of more of tris (2, 4-di-tert-butyl basic) phosphite ester, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and bisdodecyl alcohol ester.
Preferably, the high-barrier plastic sheet is one in which: the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass:
50-80 wt% of 10-40 μm strontium oxide;
20-50 wt% of 0.1-2 μm strontium oxide.
Preferably, the high-barrier plastic sheet is one in which: the number average molecular weight Mn of the polystyrene resin is 6000 g/mol-10000 g/mol.
Preferably, the production process of the high-barrier plastic sheet comprises the following steps: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blending machine, and stirring for 15-30min at the temperature of 100-110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 130-140 ℃ through an extruder to obtain colloidal particles;
and S4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 180-220 ℃, then extruding the raw materials of each layer into the same distributor, extruding through a die head, then blowing up, cooling and shaping, cutting edges and rolling to obtain the high-barrier plastic sheet.
Preferably, the production process of the high-barrier plastic sheet comprises the following steps: the die head temperature of the step S4 is 190-240 ℃.
The invention has the advantages that: the high-barrier plastic sheet and the production process thereof utilize the advantages of 2 parts of polyalkylene glycol and hydroquinone bis (beta-hydroxyethyl) ether to make up for deficiencies after combining the polyalkylene glycol and the hydroquinone bis (beta-hydroxyethyl) ether, thereby improving the mechanical strength, the flexibility, the water vapor barrier property and the oxygen barrier property of the plastic sheet; by introducing strontium oxide with two specifications into the barrier layer, strontium oxide particles are tightly arranged in the barrier layer, so that the internal structure is uniform, the product performance is stable, the comprehensive strength is high, and the strength and the barrier performance can be effectively improved.
Detailed Description
The present invention will be further described with reference to the following specific examples.
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 2-7 parts of polyalkylene glycol; 0.5-2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 1-4 parts of toughening agent; 0.5-3 parts of reinforcing agent and 0.3-0.6 part of antioxidant. The material of the substrate layer is high impact polystyrene.
The polystyrene resin has the advantages of hard quality, transparency, electric insulation, low hygroscopicity and excellent processability, the polyalkylene glycol has excellent mechanical properties including high strength, high stability and heat resistance, and the polyalkylene glycol and the polystyrene resin generate synergistic effect with the polystyrene resin, so that the hardness, toughness and toughness resistance of the material can be obviously improved, and the comprehensive performance of the prepared plastic sheet can be improved; the introduction of the hydroquinone bis (beta-hydroxyethyl) ether can enable the plastic sheet to have a buffering effect, and the hydroquinone bis (beta-hydroxyethyl) ether is used for buffering the impact of high humidity and high temperature underwater on the plastic sheet so as to ensure the permeation resistance and the strength performance of the plastic sheet and improve the barrier property and the service life of the plastic sheet.
Wherein: the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, and the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 2-4: 1.
According to the scheme, the lignin urea-formaldehyde resin and the polyether triol with the toughening performance and the anti-aging performance are introduced into the main material, wherein the lignin urea-formaldehyde resin has outstanding corrosion resistance and weather resistance, the titanium dioxide has excellent characteristics of high strength, tear resistance, abrasion resistance and the like, the titanium dioxide is radiation-resistant, does not turn yellow, does not harden and does not shrink after being irradiated by sunlight and ultraviolet rays, and the polyether triol and the lignin urea-formaldehyde resin synergistically act to effectively improve the weather resistance of the plastic sheet at high temperature and the crack resistance of the plastic sheet at low temperature.
Wherein: the reinforcing agent is polylactide fiber yarns and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber yarns to the tetrafluoroethylene-butadiene copolymer is 1-3: 1. The introduced polylactide fiber yarns have ultrahigh mechanical strength and structural toughness, can effectively inhibit the water resistance and oxygen resistance of the barrier sheet layer, can be used in combination with tetrafluoroethylene-butadiene copolymer to further improve the barrier capability of the polylactide fiber yarns, can obviously improve the strength and toughness of the plastic sheet, and can improve the barrier performance of the plastic sheet on oxygen and water vapor, thereby improving the long-term stability of the plastic sheet.
Wherein: the antioxidant is one or a mixture of more of tris (2, 4-di-tert-butyl basic) phosphite ester, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and bisdodecyl alcohol ester.
Wherein: the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass:
50-80 wt% of 10-40 μm strontium oxide;
20-50 wt% of 0.1-2 μm strontium oxide.
The strontium oxide with two specifications is added into the barrier layer, so that strontium oxide particles are tightly arranged in the barrier layer, the internal structure is uniform, the product performance is stable, the comprehensive strength is high, and the strength and the barrier property of the barrier layer can be effectively improved.
Wherein: the number average molecular weight Mn of the polystyrene resin is 6000 g/mol-10000 g/mol. It was found that when the number average molecular weight of the polystyrene resin is defined, more excellent barrier properties can be obtained. Therefore, the number average molecular weight thereof should be limited.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blending machine, and stirring for 15-30min at the temperature of 100-110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 130-140 ℃ through an extruder to obtain colloidal particles;
and S4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 180-220 ℃, then extruding the raw materials of each layer into the same distributor, extruding through a die head, then blowing up, cooling and shaping, cutting edges and rolling to obtain the high-barrier plastic sheet.
Wherein: the die head temperature of the step S4 is 190-240 ℃.
Specific examples and comparative examples are listed below
Example 1
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 2 parts of polyalkylene glycol; 0.5 part of hydroquinone bis (beta-hydroxyethyl) ether and 1 part of flexibilizer; 0.5 part of reinforcing agent and 0.3 part of antioxidant.
The toughening agent comprises lignin urea-formaldehyde resin and polyether triol, wherein the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 2: 1; the reinforcing agent is polylactide fiber yarn and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber yarn to the tetrafluoroethylene-butadiene copolymer is 1: 1; the antioxidant is tris (2, 4-di-tert-butyl) phosphite ester; the barrier layer also comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass: 50 wt% of strontium oxide with the particle size of 10-40 mu m; 50 wt% of 0.1-2 μm strontium oxide; the polystyrene resin had a number average molecular weight Mn of 6000 g/mol.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 15min at the temperature of 100 ℃;
s3, plasticizing the stirred raw materials at 130 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting at 180 ℃, conveying, extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 190 ℃, and thus the high-barrier plastic sheet is obtained.
Example 2
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 4 parts of polyalkylene glycol; 1 part of hydroquinone bis (beta-hydroxyethyl) ether and 2 parts of a toughening agent; 1 part of reinforcing agent and 0.4 part of antioxidant.
The toughening agent comprises lignin urea-formaldehyde resin and polyether triol, wherein the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 3: 1; the reinforcing agent is polylactide fiber yarn and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber yarn to the tetrafluoroethylene-butadiene copolymer is 2: 1; the antioxidant is a mixture of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and docosanol ester, the mass ratio is 1:1:1, the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass: 60 wt% of 10-40 μm strontium oxide, 40 wt% of 0.1-2 μm strontium oxide, and 8000g/mol of polystyrene resin number average molecular weight Mn.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 20min at the temperature of 105 ℃;
s3, plasticizing the stirred raw materials at 135 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 200 ℃, then extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 220 ℃, and thus the high-barrier plastic sheet is obtained.
Example 3
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 7 parts of polyalkylene glycol; 2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 4 parts of a toughening agent; 3 parts of reinforcing agent and 0.6 part of antioxidant, wherein the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 4:1, the reinforcing agent comprises polylactide fiber filaments and a tetrafluoroethylene-butadiene copolymer, the mass ratio of the polylactide fiber filaments to the tetrafluoroethylene-butadiene copolymer is 3:1, the antioxidant is a mixture of tris (2, 4-di-tert-butyl-based) phosphite, tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and didodecanol ester, the mass ratio is 1:3:2:1, the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass: 80 wt% of strontium oxide with the particle size of 10-40 mu m, 20 wt% of strontium oxide with the particle size of 0.1-2 mu m, and the number average molecular weight Mn of the polystyrene resin is 10000 g/mol.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 30min at the temperature of 110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 140 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 220 ℃, then extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 240 ℃, and thus the high-barrier plastic sheet is obtained.
Comparative example 1
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin, 2 parts of polyalkylene glycol and 1 part of toughening agent; 0.5 part of reinforcing agent and 0.3 part of antioxidant.
The toughening agent comprises lignin urea-formaldehyde resin and polyether triol, wherein the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 2: 1; the reinforcing agent is polylactide fiber yarn and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber yarn to the tetrafluoroethylene-butadiene copolymer is 1: 1; the antioxidant is tris (2, 4-di-tert-butyl) phosphite ester; the barrier layer also comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass: 50 wt% of strontium oxide with the particle size of 10-40 mu m; 50 wt% of 0.1-2 μm strontium oxide; the polystyrene resin had a number average molecular weight Mn of 6000 g/mol.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 15min at the temperature of 100 ℃;
s3, plasticizing the stirred raw materials at 130 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting at 180 ℃, conveying, extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 190 ℃, and thus the high-barrier plastic sheet is obtained.
Comparative example 2
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 4 parts of polyalkylene glycol; 1 part of hydroquinone bis (beta-hydroxyethyl) ether and 2 parts of a toughening agent; 1 part of reinforcing agent and 0.4 part of antioxidant.
The toughening agent comprises lignin urea-formaldehyde resin, the reinforcing agent comprises polylactide fiber filaments and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber filaments to the tetrafluoroethylene-butadiene copolymer is 2: 1; the antioxidant is a mixture of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and docosanol ester, the mass ratio is 1:1:1, the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass: 60 wt% of 10-40 μm strontium oxide, 40 wt% of 0.1-2 μm strontium oxide, and 8000g/mol of polystyrene resin number average molecular weight Mn.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 20min at the temperature of 105 ℃;
s3, plasticizing the stirred raw materials at 135 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 200 ℃, then extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 220 ℃, and thus the high-barrier plastic sheet is obtained.
Comparative example 3
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 7 parts of polyalkylene glycol; 2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 4 parts of a toughening agent; 3 parts of reinforcing agent and 0.6 part of antioxidant, wherein the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 4:1, the reinforcing agent is tetrafluoroethylene-butadiene copolymer, the antioxidant is a mixture of tris (2, 4-di-tert-butyl-based) phosphite ester, tetra [ beta- (3, 5-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tert-butyl-4-methylphenol and didodecanol ester, the mass ratio is 1:3:2:1, and the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass: 80 wt% of strontium oxide with the particle size of 10-40 mu m, 20 wt% of strontium oxide with the particle size of 0.1-2 mu m, and the number average molecular weight Mn of the polystyrene resin is 10000 g/mol.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 30min at the temperature of 110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 140 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 220 ℃, then extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 240 ℃, and thus the high-barrier plastic sheet is obtained.
Comparative example 4
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 7 parts of polyalkylene glycol; 2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 4 parts of a toughening agent; 3 parts of reinforcing agent and 0.6 part of antioxidant, wherein the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 4:1, the reinforcing agent is polylactide fiber filaments and tetrafluoroethylene-butadiene copolymer, the mass ratio of the polylactide fiber yarns to the tetrafluoroethylene-butadiene copolymer is 3:1, the antioxidant is a mixture of tris (2, 4-di-tert-butyl-based) phosphite ester, tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and didodecyl alcohol ester, the mass ratio is 1:3:2:1, the barrier layer further comprises strontium oxide, the particle size of the strontium oxide is 10-40 mu m, and the number average molecular weight Mn of the polystyrene resin is 10000 g/mol.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 30min at the temperature of 110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 140 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 220 ℃, then extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 240 ℃, and thus the high-barrier plastic sheet is obtained.
Comparative example 5
A high barrier plastic sheet wherein: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 7 parts of polyalkylene glycol; 2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 4 parts of a toughening agent; 3 parts of reinforcing agent and 0.6 part of antioxidant, wherein the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 4:1, the reinforcing agent is polylactide fiber and tetrafluoroethylene-butadiene copolymer, the mass ratio of the polylactide fiber and the tetrafluoroethylene-butadiene copolymer is 3:1, the antioxidant is a mixture of tris (2, 4-di-tert-butyl-based) phosphite ester, tetrakis [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and didodecyl alcohol ester, the mass ratio is 1:3:2:1, and the number-average molecular weight Mn of the polystyrene resin is 10000 g/mol.
A process for producing a high barrier plastic sheet, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blender, and stirring for 30min at the temperature of 110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 140 ℃ through an extruder to obtain colloidal particles;
s4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 220 ℃, then extruding the raw materials of all layers into the same distributor, extruding through a die head, blowing, cooling, shaping, trimming and winding, wherein the die head temperature is 240 ℃, and thus the high-barrier plastic sheet is obtained.
The results of the performance tests of examples 1-3 and comparative examples 1-5 are listed below:
as can be seen from Table 1, comparative example 1, in which hydroquinone bis (. beta. -hydroxyethyl) ether was not added, the strength of the plastic sheet was low; comparative example 2 no polyether triol was added, which had an effect on both the strength and barrier properties of the plastic sheet; comparative example 3 no polylactide filament was added, which had an effect on both strength and barrier properties; the invention can effectively improve the mechanical strength, the water resistance and the oxygen barrier property of the plastic sheet by combining various materials by utilizing the advantages of the materials.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A high barrier plastic sheet characterized by: high separation plastic sheet includes the substrate layer and sets up the barrier layer on the substrate layer, by weight, the barrier layer includes following component: 100 parts of polystyrene resin and 2-7 parts of polyalkylene glycol; 0.5-2 parts of hydroquinone bis (beta-hydroxyethyl) ether and 1-4 parts of toughening agent; 0.5-3 parts of reinforcing agent and 0.3-0.6 part of antioxidant.
2. The high barrier plastic sheet according to claim 1, wherein: the toughening agent comprises lignin urea-formaldehyde resin and polyether triol, and the mass ratio of the lignin urea-formaldehyde resin to the polyether triol is 2-4: 1.
3. The high barrier plastic sheet according to claim 1, wherein: the reinforcing agent is polylactide fiber yarns and tetrafluoroethylene-butadiene copolymer, and the mass ratio of the polylactide fiber yarns to the tetrafluoroethylene-butadiene copolymer is 1-3: 1.
4. The high barrier plastic sheet according to claim 1, wherein: the antioxidant is one or a mixture of more of tris (2, 4-di-tert-butyl basic) phosphite ester, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-tertiary butyl-4-methylphenol and bisdodecyl alcohol ester.
5. The high barrier plastic sheet according to claim 1, wherein: the barrier layer further comprises strontium oxide, and the strontium oxide comprises the following components in parts by mass:
50-80 wt% of 10-40 μm strontium oxide;
20-50 wt% of 0.1-2 μm strontium oxide.
6. The high barrier plastic sheet according to claim 1, wherein: the number average molecular weight Mn of the polystyrene resin is 6000 g/mol-10000 g/mol.
7. The process for producing a high barrier plastic sheet according to claim 1, wherein: the method comprises the following steps:
s1, weighing and mixing the raw materials according to the composition of the raw materials;
s2, placing the mixed raw materials into a high-speed blending machine, and stirring for 15-30min at the temperature of 100-110 ℃;
s3, plasticizing the stirred raw materials at the temperature of 130-140 ℃ through an extruder to obtain colloidal particles;
and S4, respectively putting the colloidal particles and the base material layer material into an extruder, melting and conveying at 180-220 ℃, then extruding the raw materials of each layer into the same distributor, extruding through a die head, then blowing up, cooling and shaping, cutting edges and rolling to obtain the high-barrier plastic sheet.
8. The process for producing a high barrier plastic sheet according to claim 7, wherein: the die head temperature of the step S4 is 190-240 ℃.
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