CN116080191A - High-barrier packaging material and preparation method thereof - Google Patents
High-barrier packaging material and preparation method thereof Download PDFInfo
- Publication number
- CN116080191A CN116080191A CN202310117221.6A CN202310117221A CN116080191A CN 116080191 A CN116080191 A CN 116080191A CN 202310117221 A CN202310117221 A CN 202310117221A CN 116080191 A CN116080191 A CN 116080191A
- Authority
- CN
- China
- Prior art keywords
- packaging material
- parts
- barrier
- layer
- bonding layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005022 packaging material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004698 Polyethylene Substances 0.000 claims abstract description 65
- 230000004888 barrier function Effects 0.000 claims abstract description 60
- 229920001661 Chitosan Polymers 0.000 claims abstract description 33
- 239000002121 nanofiber Substances 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 13
- 239000004744 fabric Substances 0.000 claims abstract description 13
- -1 polyethylene Polymers 0.000 claims abstract description 13
- 239000002086 nanomaterial Substances 0.000 claims abstract description 12
- 229920000573 polyethylene Polymers 0.000 claims abstract description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 23
- 238000005266 casting Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000006640 acetylation reaction Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000010345 tape casting Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 150000001343 alkyl silanes Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 7
- 239000005030 aluminium foil Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 229920001684 low density polyethylene Polymers 0.000 description 7
- 239000004702 low-density polyethylene Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000012790 adhesive layer Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000265 homogenisation Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/082—Layered products comprising a layer of metal comprising metal 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 comprising vinyl resins; comprising acrylic resins
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
- B32B15/085—Layered products comprising a layer of metal comprising metal 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 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
-
- 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
- B32B2307/54—Yield strength; Tensile strength
-
- 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
-
- 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
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
The application discloses high separation packaging material and preparation method thereof, this packaging material is including aluminium foil, PE adhesive linkage, barrier layer, PE adhesive linkage, substrate and PE membrane that compound in proper order, the aluminium foil passes through the adhesive linkage and weaves cloth complex, the barrier layer includes the raw materials of following parts by mass: polyethylene: 100 parts; ethylene-vinyl alcohol copolymer: 20-30 parts; lamellar nanomaterial: 10-20 parts; spherical alumina particles: 5-10 parts; dispersion modifier: 1-3 parts; acetylated chitosan nanofibers: 10-20 parts. The packaging material can effectively improve the blocking capability to oxygen and moisture on the premise of keeping good tensile property.
Description
Technical Field
The application relates to the field of packaging materials, in particular to a high-barrier packaging material and a preparation method thereof.
Background
The high-barrier packaging material is an aluminum-plastic packaging material and is formed by compounding aluminum foil and plastic. It has better mechanical properties such as stiffness, tensile strength, tear resistance, wear resistance and the like, and has good blocking effect on ultraviolet light, oxygen and moisture, so that the packaging material is commonly used for precisely packaging noble articles such as precise industrial equipment, medicines and the like.
The existing aluminum-plastic packaging material generally comprises an aluminum foil reflecting layer positioned on a surface layer, a PE film sealing layer positioned on an inner layer, and a plastic woven cloth base material positioned on an intermediate layer. The PE film and the plastic woven cloth base material are compounded by hot pressing, the aluminum foil reflecting layer and the plastic woven cloth base material are compounded by an adhesive, and the adhesive is usually made of polyethylene materials for convenient production.
However, the barrier capability of polyethylene materials to oxygen and moisture remains difficult to meet the packaging requirements of medical or precision equipment.
Disclosure of Invention
The application provides a high-barrier packaging material and a preparation method thereof, which can effectively improve the barrier property of an aluminum-plastic packaging material to oxygen and moisture and meet the packaging requirements of medicines and precision equipment.
In a first aspect, the application provides a high-barrier packaging material, it includes aluminium foil, PE adhesive linkage, barrier layer, PE adhesive linkage, substrate and PE membrane that compound in proper order, the aluminium foil passes through the adhesive linkage and weaves cloth complex, the barrier layer includes the raw materials of following parts by mass:
polyethylene: 100 parts;
ethylene-vinyl alcohol copolymer: 20-30 parts;
lamellar nanomaterial: 10-20 parts;
spherical alumina particles: 5-10 parts;
dispersion modifier: 1-3 parts;
acetylated chitosan nanofibers: 10-20 parts.
According to the technical scheme, the base material of the barrier layer adopts polyethylene and ethylene-vinyl alcohol with high barrier property, so that the gas and water barrier property of the adhesive layer can be effectively improved, and the sealing property is ensured. Further, the application adopts the two forms of nano filler of the lamellar nano material and the spherical alumina particles to be matched together, so that a more compact barrier layer can be formed, the diffusion path of moisture is effectively prolonged, and the moisture barrier capability is improved. In addition, the spherical alumina can reduce friction resistance and promote dispersion and tape casting extrusion of the bonding layer.
The acetylated chitosan nanofiber is added in the method, so that on one hand, the toughening and reinforcing effects can be achieved, and the reduction of toughness and tensile property of the barrier layer caused by the addition of the filler is compensated; on the other hand, the fiber form can be matched with the lamellar nano material and the spherical alumina particles to form a denser barrier layer, so that the barrier effect on oxygen and moisture is improved.
And as the molecular chain of the chitosan nanofiber contains more hydroxyl groups, the chitosan nanofiber has stronger hydrophilicity and is unfavorable for improving the water blocking capacity of the bonding layer, so that the chitosan nanofiber modified by the acetylation and the hydrophobicity is adopted, and the problem is effectively solved.
The above lamellar nano material refers to a carbon material or silicate material having lamellar structure, such as graphite, graphene, montmorillonite, bentonite.
Preferably, the substrate is PE woven cloth, PP woven cloth or PE and PP composite woven cloth.
Preferably, the PE bonding layer is a tape casting layer made of PE material, and the bonding effect is achieved by a tape casting (laminating) process.
Preferably, the D50 particle diameter of the spherical alumina particles is less than 500nm, more preferably the D50 particle diameter of the spherical alumina particles is 50 to 100nm.
Preferably, the average length of the chitosan nanofiber is 30 nm-50 nm.
Preferably, the acetylated chitosan nanofiber consists of the following components in percentage by mass: (4-6): and (2-4) reacting chitosan nanofiber, acetic anhydride and concentrated sulfuric acid.
In the acetylation modification, concentrated sulfuric acid can activate hydroxyl groups of chitosan nanofibers, an esterification reaction is carried out to obtain a sulfuric acid ester intermediate, and then acetic anhydride acyl is substituted to form acetic ester, so that the acetylation hydrophobic modification is completed.
Preferably, the concentration of the concentrated sulfuric acid is 98wt%.
The preparation method of the preferable acetylated chitosan nanofiber comprises the following steps: dispersing chitosan nano fibers in anhydrous acetic acid, and dropwise adding concentrated sulfuric acid under the conditions of heating and stirring to perform esterification reaction; then dripping acetic anhydride for acetylation reaction, filtering and separating out fiber after the reaction is finished, and washing with absolute ethyl alcohol.
Preferably, the heating temperature is 50-60 ℃;
and/or the esterification reaction time is 10-30 min;
and/or the time of the acetylation reaction is 1-2 h.
Preferably, the lamellar nano material is selected from one or more of montmorillonite, mica, kaolin, graphene and graphene oxide.
Preferably, the particle size of the lamellar nanomaterial is 100 to 500nm, more preferably 100 to 300nm.
Preferably, the dispersion modifier comprises one or more of a long-chain alkyl silane coupling agent, a phenyl silane coupling agent and an epoxy silane coupling agent.
The inorganic nano filler with small particle diameter and specific surface area has the tendency of agglomeration and precipitation in a system, and is difficult to disperse uniformly. Therefore, by adding a proper hydrophobic silane coupling agent, the filler can be fully dispersed on the premise of ensuring the hydrophobicity of the packaging material, and the water-moisture blocking capability of the packaging material is improved.
Preferably, the dispersion modifier contains 20 to 30wt% of trimethylmethoxysilane.
The ethylene-vinyl alcohol copolymer added in the application contains a certain polar hydroxyl group, which is not beneficial to improving the compatibility with polyethylene and affecting the exertion of barrier property; on the other hand, the permeability of moisture to the adhesive layer is increased. For this purpose, a small amount of trimethylmethoxysilane is incorporated, and its monomethoxy group can be hydrolyzed into a silylhydroxyl group in the raw material blending step before the casting extrusion, thereby being capable of reacting with the hydroxyl group of the ethylene-vinyl alcohol copolymer to reduce the polarity thereof. More importantly, compared with the silane coupling agent, the adhesive has small molecular weight and high permeability, can infiltrate into ethylene-vinyl alcohol copolymer molecules to fully consume hydroxyl, and promotes the improvement of the moisture barrier property of the adhesive layer. Of course, the steric hindrance and dispersion effect of trimethylmethoxysilane are poor, and the use amount of the silane coupling agent needs to be ensured to promote uniform distribution of the nanofiller.
In a second aspect, the present application provides a method for preparing a high barrier packaging material, which is characterized by the following steps: extruding to obtain a barrier layer through a casting process, obtaining a PE bonding layer through the casting process, and distributing the PE bonding layer on a substrate in parallel, then compositing the barrier layer and the substrate, and compositing a PE film on one side of the substrate far away from the barrier layer through the casting process to obtain a composite sheet; and (3) obtaining a PE bonding layer through a tape casting process, and spreading the PE bonding layer on the surface of the barrier layer of the first composite sheet material in parallel, and compositing the aluminum foil with the composite sheet material to obtain the high-barrier packaging material.
Preferably, in the casting process of the barrier layer, the temperature of the heating section is 180+/-5 ℃; the temperature of the plasticizing section is 220+/-5 ℃; the homogenization section temperature was 230.+ -. 5 ℃.
The packaging material sequentially comprises an aluminum foil, a PE bonding layer, a barrier layer, a PE bonding layer, a PE woven cloth and a PE film from outside to inside, wherein the PE woven cloth and the PE film are the same in material, the aluminum foil layer plays a role in reflection and barrier, and the PE film plays a role in sealing.
In summary, the application has the following beneficial effects:
1. the polyethylene and ethylene-vinyl alcohol copolymer are used as base materials, the lamellar nano material, the spherical alumina particles and the acetylated chitosan nano fibers are used as fillers, and the blocking capacity of the adhesive layer and the packaging material to oxygen and moisture can be improved on the premise of guaranteeing the tensile property and tensile strength of the adhesive layer.
2. The silane coupling agent and the trimethylmethoxysilane are used as the dispersion modifier, so that the water blocking capability of the adhesive layer can be improved while the filler dispersion is promoted.
Detailed Description
Examples of preparation of starting materials and/or intermediates
Preparation example 1, acetylated chitosan nanofiber, was prepared according to the following steps:
dispersing 1 kg of chitosan nanofiber (average length of 30 nm) in 5 kg of anhydrous acetic acid, dropwise adding 0.3 kg of concentrated sulfuric acid under stirring under the heating of a water bath at 50 ℃, and continuously stirring for 20min after the dropwise adding is finished to perform esterification reaction; then 0.5 kg of acetic anhydride is dripped, stirred for 1h, acetylation reaction is carried out, fiber is separated by filtration after the reaction is finished, and the fiber is obtained after 3 times of washing with absolute ethyl alcohol.
Preparation example 2, acetylated chitosan nanofibers, were prepared according to the following steps:
dispersing 1 kg of chitosan nanofiber (average length of 30 nm) in 5 kg of anhydrous acetic acid, dropwise adding 0.4 kg of concentrated sulfuric acid under stirring under the heating of a water bath at 50 ℃, and continuously stirring for 10min after the dropwise adding is finished to perform esterification reaction; then 0.6 kg of acetic anhydride is dripped, stirred for 1h, acetylation reaction is carried out, fiber is separated by filtration after the reaction is finished, and the fiber is obtained after 3 times of washing with absolute ethyl alcohol.
Preparation example 3 acetylated chitosan nanofibers were prepared according to the following steps:
dispersing 1 kg of chitosan nanofiber (average length of 30 nm) in 5 kg of anhydrous acetic acid, dropwise adding 0.2 kg of concentrated sulfuric acid under stirring under the heating of a water bath at 50 ℃, and continuously stirring for 20min after the dropwise adding is finished to perform esterification reaction; then 0.4 kg of acetic anhydride is dripped, stirred for 1h, acetylation reaction is carried out, fiber is separated by filtration after the reaction is finished, and the fiber is obtained after 3 times of washing with absolute ethyl alcohol.
Examples
Example 1, a high barrier packaging material, was prepared as follows:
step 1: 10 kg of polyethylene (LDPE, brand 2426H), 2 kg of ethylene-vinyl alcohol copolymer (the molar content of ethylene is 30%), 1.5 kg of nano montmorillonite (the granularity of D50 is 200 nm), 0.5 kg of spherical alumina particles (the granularity of D50 is 100 nm), 0.3 kg of dispersion modifier (comprising 0.06 kg of trimethylmethoxysilane and 0.14 kg of hexadecyltrimethoxysilane), 1 kg of acetylated chitosan nanofiber obtained in preparation example 1 are taken, added into a mixer, stirred and mixed, and after 1H, the uniformly mixed raw materials are added into a casting machine for plasticizing and melting. Wherein the temperature of the heating section is 180+/-5 ℃; the temperature of the plasticizing section is 215+/-5 ℃; the temperature of the homogenization section is 225+/-5 ℃; and casting to obtain the barrier layer after plasticizing.
LDPE (brand 1C7A, coating grade) is used as a raw material, the raw material is added into a casting machine, two layers of films are obtained through casting at 330+/-5 ℃, one layer is a PE film, the other layer is a PE bonding layer, the PE film and the PE bonding layer are respectively arranged on two sides of a PE woven cloth (substrate), then the obtained barrier layer is compounded on the PE bonding layer, and the composite sheet is obtained through cooling.
Step 2: LDPE (brand 1C 7A) is taken as a raw material, the raw material is added into a casting machine, another PE bonding layer is obtained through casting at 330+/-5 ℃, the PE bonding layer is spread on a barrier layer of a composite sheet, and aluminum foil is compositely fixed on the composite sheet through the PE bonding layer, so that the high-barrier packaging material is obtained.
In the high-barrier packaging material, the thickness of the aluminum foil is 6 mu m, the thickness of the PE bonding layer is 10 mu m, the thickness of the barrier layer is 20 mu m, the thickness of the substrate is 1mm, and the thickness of the PE film is 10 mu m.
Example 2, a high barrier packaging material, was prepared as follows:
step 1: 10 kg of polyethylene (LDPE, brand 2426H), 2 kg of ethylene-vinyl alcohol copolymer (the molar content of ethylene is 30%), 1 kg of nano mica powder (the granularity of D50 is 200 nm), 1 kg of spherical alumina particles (the granularity of D50 is 100 nm), 0.4 kg of dispersion modifier (comprising 0.12 kg of trimethylmethoxysilane and 0.28 kg of hexadecyltrimethoxysilane) and 1 kg of acetylated chitosan nanofiber obtained in preparation example 2 are taken, added into a mixer, stirred and mixed, and after 1H, the uniformly mixed raw materials are added into a casting machine for plasticizing and melting. Wherein the temperature of the heating section is 190+/-5 ℃; the temperature of the plasticizing section is 210+/-5 ℃; the temperature of the homogenization section is 225+/-5 ℃; and casting to obtain the barrier layer after plasticizing.
LDPE (brand 1C7A, coating grade) is used as a raw material, the raw material is added into a casting machine, two layers of films are obtained through casting at 330+/-5 ℃, one layer is a PE film, the other layer is a PE bonding layer, the PE film and the PE bonding layer are respectively arranged on two sides of a PE woven cloth (substrate), then the obtained barrier layer is compounded on the PE bonding layer, and the composite sheet is obtained through cooling.
Step 2: LDPE (brand 1C 7A) is taken as a raw material, the raw material is added into a casting machine, another PE bonding layer is obtained through casting at 330+/-5 ℃, the PE bonding layer is spread on a barrier layer of a composite sheet, and aluminum foil is compositely fixed on the composite sheet through the PE bonding layer, so that the high-barrier packaging material is obtained.
In the high-barrier packaging material, the thickness of the aluminum foil is 6 mu m, the thickness of the PE bonding layer is 10 mu m, the thickness of the barrier layer is 20 mu m, the thickness of the substrate is 1mm, and the thickness of the PE film is 10 mu m.
Example 3, a high barrier packaging material, differs from example 1 in the raw materials of the barrier layer, specifically as follows:
step 1: 10 kg of polyethylene (LDPE, brand 2426H), 3 kg of ethylene-vinyl alcohol copolymer (the molar content of ethylene is 30%), 1.5 kg of nano montmorillonite (the granularity of D50 is 200 nm), 0.5 kg of spherical alumina particles (the granularity of D50 is 100 nm), 0.2 kg of dispersion modifier (comprising 0.05 kg of trimethylmethoxysilane and 0.15 kg of hexadecyltrimethoxysilane) and 2 kg of acetylated chitosan nanofiber obtained in preparation example 3 are taken, added into a mixer, stirred and mixed, and after 1H, the uniformly mixed raw materials are added into a casting machine for plasticizing and melting. Wherein the temperature of the heating section is 180+/-5 ℃; the temperature of the plasticizing section is 215+/-5 ℃; the temperature of the homogenization section is 225+/-5 ℃; and casting to obtain the barrier layer after plasticizing.
Example 4, a high barrier packaging material, differs from example 1 in that in the dispersion modifier, an equivalent amount of long chain silane coupling agent is used instead of trimethylmethoxysilane.
Example 5, a high barrier packaging material, differs from example 1 in that in the dispersion modifier, an equivalent amount of trimethylmethoxysilane is used instead of the long chain silane coupling agent.
Comparative example
Comparative example 1, a high barrier packaging material, differs from example 1 in that an equivalent amount of unmodified chitosan nanofibers was used instead of acetylated chitosan nanofibers.
Comparative example 2, a high barrier packaging material, differs from example 1 in that an equivalent amount of nano montmorillonite was used instead of acetylated chitosan nanofibers.
Comparative example 3, a high barrier packaging material, differs from example 1 in that an equivalent amount of nano montmorillonite was used instead of spherical alumina particles.
Comparative example 4, a high barrier packaging material, differs from example 1 in that an equivalent amount of spherical alumina particles was used instead of nano montmorillonite.
Comparative example 5, a high barrier packaging material, differs from example 1 in that the raw material of the barrier layer was not added with platelet nanomaterial, spherical alumina particles, and acetylated chitosan nanofibers.
Performance test
1. Barrier properties: the high barrier packaging material was tested for its barrier ability to oxygen and water vapour at 23 ℃ and 50RH% according to the specifications in GB/T1038-2000.
2. Tensile property test: the barrier layer was tested for tensile strength (MPa) and elongation at break (%) as specified in GB/T13022-1991.
TABLE 1 Experimental results
Analysis of results:
(1) It can be seen from the combination of examples 1 to 5 and comparative examples 1 to 5 and table 1 that the present application can improve the barrier ability of the packaging material of the present application to oxygen and moisture by using the platelet nanomaterial, the spherical alumina particles, and the acetylated chitosan nanofibers, and effectively compensate for the loss of tensile properties by the acetylated chitosan nanofibers.
(2) As can be seen from the combination of examples 1 and examples 4 to 5 and table 1, the present application uses a complex of a hydrophobic coupling agent such as trimethylmethoxysilane and a long-chain alkyl coupling agent as a dispersion modifier, which can effectively reduce the oxygen and water vapor transmission rate of the packaging material. The reason for this may be that the long-chain alkyl coupling agent may be attached to the nano-sized surface, and the long-chain alkyl plays a role in steric hindrance, inhibits aggregation, makes the nano-filler uniformly dispersed, and fully exerts the barrier effect. The trimethyl methoxy silane has the advantages of steric hindrance, no obvious dispersion effect and good permeability, and the hydrolyzed silicon hydroxyl can react with the hydroxyl of the ethylene-vinyl alcohol copolymer, so that the polarity of the ethylene-vinyl alcohol copolymer is reduced, and the compatibility and the blocking effect on moisture are improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The high-barrier packaging material is characterized by comprising an aluminum foil, a PE bonding layer, a barrier layer, a PE bonding layer, a substrate and a PE film which are sequentially compounded, wherein the aluminum foil is compounded with woven cloth through the bonding layer, and the barrier layer comprises the following raw materials in parts by mass:
polyethylene: 100 parts;
ethylene-vinyl alcohol copolymer: 20-30 parts;
lamellar nanomaterial: 10-20 parts;
spherical alumina particles: 5-10 parts;
dispersion modifier: 1-5 parts;
acetylated chitosan nanofibers: 10-20 parts.
2. The high-barrier packaging material according to claim 1, wherein the acetylated chitosan nanofibers are formed from a blend of 10: (4-6): and (2-4) reacting chitosan nanofiber, acetic anhydride and concentrated sulfuric acid.
3. The high-barrier packaging material according to claim 2, wherein the preparation method of the acetylated chitosan nanofiber comprises the following steps: dispersing chitosan nano fibers in anhydrous acetic acid, and dropwise adding concentrated sulfuric acid under the conditions of heating and stirring to perform esterification reaction; then dripping acetic anhydride for acetylation reaction, filtering and separating out fiber after the reaction is finished, and washing with absolute ethyl alcohol.
4. A high barrier packaging material according to claim 3, wherein the heating temperature is 50-60 ℃;
and/or the esterification reaction time is 10-30 min;
and/or the time of the acetylation reaction is 1-2 h.
5. The high-barrier packaging material according to claim 1, wherein the lamellar nano material is one or more selected from montmorillonite, mica, kaolin, graphene and graphene oxide.
6. The high-barrier packaging material according to claim 1, wherein the dispersion modifier comprises one or more of a long-chain alkyl silane coupling agent, a phenyl silane coupling agent and an epoxy silane coupling agent.
7. The high barrier packaging material of claim 6, wherein the dispersion modifier comprises 20 to 30wt% of trimethylmethoxysilane.
8. The method of producing a high barrier packaging material according to any one of claims 1 to 7, characterized by the steps of:
extruding to obtain a barrier layer through a casting process, obtaining a PE bonding layer through the casting process, and distributing the PE bonding layer on a substrate in parallel, then compositing the barrier layer and the substrate, and compositing a PE film on one side of the substrate far away from the barrier layer through the casting process to obtain a composite sheet;
and (3) obtaining a PE bonding layer through a tape casting process, and spreading the PE bonding layer on the surface of the barrier layer of the first composite sheet material in parallel, and compositing the aluminum foil with the composite sheet material to obtain the high-barrier packaging material.
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