CN115534470A - High-barrier medicinal packaging film and preparation method thereof - Google Patents
High-barrier medicinal packaging film and preparation method thereof Download PDFInfo
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- CN115534470A CN115534470A CN202211228673.3A CN202211228673A CN115534470A CN 115534470 A CN115534470 A CN 115534470A CN 202211228673 A CN202211228673 A CN 202211228673A CN 115534470 A CN115534470 A CN 115534470A
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- titanium dioxide
- stirring
- polyhydroxybutyrate
- packaging film
- film
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- 229920006280 packaging film Polymers 0.000 title claims abstract description 48
- 239000012785 packaging film Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 78
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 78
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 150000003608 titanium Chemical class 0.000 claims abstract description 62
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 51
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 44
- 229940070710 valerate Drugs 0.000 claims abstract description 35
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 32
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000004888 barrier function Effects 0.000 claims abstract description 12
- 229960003638 dopamine Drugs 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 42
- 239000000853 adhesive Substances 0.000 claims description 38
- 230000001070 adhesive effect Effects 0.000 claims description 38
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920001634 Copolyester Polymers 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000013329 compounding Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229920002647 polyamide Polymers 0.000 claims description 16
- 238000005096 rolling process Methods 0.000 claims description 16
- 150000003751 zinc Chemical class 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 claims description 12
- SZORMCBRRGPWKG-UHFFFAOYSA-N butanoic acid;pentanoic acid Chemical compound CCCC(O)=O.CCCCC(O)=O SZORMCBRRGPWKG-UHFFFAOYSA-N 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- 238000010345 tape casting Methods 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229940005605 valeric acid Drugs 0.000 claims description 4
- 238000009512 pharmaceutical packaging Methods 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- 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
- B32B15/09—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 polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
-
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a high-barrier medicinal packaging film and a preparation method thereof. The environment-friendly polyhydroxybutyrate-valerate is used as a raw material of a polyhydroxybutyrate-valerate film, and a modified titanium dioxide-carboxymethylcellulose compound is added. The preparation method comprises the following steps of carrying out hydrophobic modification on titanium dioxide, and simultaneously loading dopamine on graphene oxide. The mass ratio of the carboxymethyl cellulose, the acetic anhydride and the modified titanium dioxide-graphene compound is controlled, the interfacial compatibility of the carboxymethyl cellulose and the polyhydroxybutyrate-hydroxyvalerate is improved, the mechanical property of the packaging film is enhanced, and meanwhile, the packaging film is endowed with excellent barrier property.
Description
Technical Field
The invention relates to the technical field of packaging films, in particular to a high-barrier medicinal packaging film and a preparation method thereof.
Background
The medicine is a special article, and is easily affected by gas and water vapor due to environmental change, so that the medicine is affected by dampness and the properties of the medicine are affected. In order to make the medicine be stored for a longer time and safely under special conditions, a packaging film with barrier property is developed for packaging the medicine. However, the common packaging film with barrier property has no additional mechanical property and poor barrier property, so that the application of the medical packaging film in the direction is limited.
In order to solve the problems, improve the barrier property and mechanical property of the medicinal packaging film and prolong the service life of the medicinal packaging film, the invention provides the high-barrier medicinal packaging film and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a high-barrier medicinal packaging film and a preparation method thereof, and aims to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a high-barrier medicinal packaging film comprises the following steps:
the method comprises the following steps: stirring carboxymethylcellulose and deionized water at 50-60 ℃ for 40-60min, adding acetic anhydride, stirring at 70-80 ℃ for 1.5-2h, stopping stirring, adding the modified titanium dioxide-graphene oxide compound, performing ultrasonic dispersion for 3-5h, centrifuging, washing, and drying to obtain a modified titanium dioxide-carboxymethylcellulose compound;
step two: uniformly stirring polyhydroxybutyrate-valerate and chloroform at 66-72 ℃ to obtain polyhydroxybutyrate-valerate solution, uniformly stirring modified titanium dioxide-carboxymethylcellulose compound and chloroform at 30-40 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, adding the modified zinc oxide-carboxymethylcellulose compound solution into polyhydroxybutyrate-valerate solution, and performing tape casting to form a film to obtain polyhydroxybutyrate-valerate film;
step three: coating an epoxy resin adhesive on one surface of an aluminum foil, compounding a polyhydroxybutyrate-valerate film with the surface coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film, compounding the polyhydroxy butyric acid and valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medical packaging film.
Preferably, in the step one, the mass ratio of the carboxymethyl cellulose, the acetic anhydride and the modified titanium dioxide-graphene oxide compound is 1: (15-25): (0.5-0.7).
Preferably, in the second step, the mass ratio of the polyhydroxybutyrate-valerate to the modified titanium dioxide-carboxymethyl cellulose compound is 100: (3-5).
Preferably, in the step one, the preparation method of the modified titanium dioxide-graphene oxide compound comprises the following steps: taking hydrophobic titanium dioxide and deionized water, performing ultrasonic dispersion for 30-40min, adding dopamine, stirring for 20-30min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value, continuing to stir for 18-20h, adding graphene oxide, stirring for 18-20h at 25-28 ℃, filtering, washing and drying to obtain the modified titanium dioxide-graphene oxide compound.
Preferably, the preparation method of the hydrophobic titanium dioxide comprises the following steps: taking titanium dioxide and ethanol, carrying out ultrasonic dispersion for 50-70min, adding 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxy silane, stirring for 50-60min, adding 3mL1H,1H,2H and 1H-perfluorodecyl triethoxysilane, and stirring for 4-5min to obtain the hydrophobic titanium dioxide.
Preferably, the mass ratio of the hydrophobic titanium dioxide to the graphene oxide is (4-7): 0.1.
preferably, the Tris buffer solution is added with hydrochloric acid, and the pH value is adjusted to 8.0-8.5.
Compared with the prior art, the invention has the following beneficial effects:
(1) The packaging film is prepared from the polyhydroxybutyrate-hydroxyvalerate, the polyhydroxybutyrate-hydroxyvalerate can be biodegraded, and meanwhile, the biocompatibility is good, so that the packaging film is used for preparing a medicinal packaging film, and the packaging film is green and environment-friendly.
(2) Long-chain hydrophobic 1H,2H and 1H-perfluorodecyl triethoxysilane is grafted on titanium dioxide, so that the hydrophobicity of the titanium dioxide is enhanced, and meanwhile, the long chain interferes the diffusion of moisture, so that the barrier property of the membrane is enhanced.
Titanium dioxide is loaded on graphene oxide, dopamine is added, so that amino groups on the dopamine can react with carboxyl groups and hydroxyl groups on the graphene oxide, the loading capacity of the titanium dioxide is increased, and the mechanical property and the barrier property of the medicinal packaging film are enhanced due to the addition of the graphene oxide.
(3) The modified zinc oxide with gas barrier property is grafted on the carboxymethyl cellulose, so that the gas diffusion path can be prolonged, and the water vapor barrier effect can be improved. In order to further enhance the mechanical property of the packaging film, acetic anhydride is added into the carboxymethyl cellulose, and the mass ratio of the carboxymethyl cellulose to the acetic anhydride to the modified titanium dioxide-graphene composite is controlled to be 1: (20-32): (1-2). The acetyl and the ester bond of the polyhydroxybutyrate-hydroxyvalerate copolyester have certain affinity, so that the acetylated carboxymethyl cellulose improves the interface compatibility of the carboxymethyl cellulose and the polyhydroxybutyrate-hydroxyvalerate copolyester, the acetylated carboxymethyl cellulose is uniformly dispersed in the polyhydroxybutyrate-hydroxyvalerate copolyester, the mechanical property of the packaging film is improved, and the service life of the medicinal packaging film is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method comprises the following steps: preparation of hydrophobic titanium dioxide: 5g of titanium dioxide and 80mL of ethanol were ultrasonically dispersed for 60min, 3mL of 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane (3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane obtained from Allantin reagent (Shanghai)) was added, stirring was carried out for 55min, 3mL1H,1H,2H, 1H-perfluorodecyltriethoxysilane (1H, 2H, 1H-perfluorodecyltriethoxysilane obtained from Allantin reagent (Shanghai)) was added, and stirring was carried out for 4.5min, whereby hydrophobic titanium dioxide was obtained.
Step two: preparing a modified titanium dioxide-graphene oxide compound: taking 5g of hydrophobic titanium dioxide and 300mL of deionized water, performing ultrasonic dispersion for 35min, adding 4g of dopamine, stirring for 25min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, continuing stirring for 19h, adding 0.1g of graphene oxide, stirring for 19h at 27 ℃, filtering, washing and drying to obtain the modified titanium dioxide-graphene oxide compound.
Controlling the mass ratio of hydrophobic titanium dioxide to graphene oxide to be 5:0.1.
step three: preparing a modified titanium dioxide-carboxymethyl cellulose compound:
taking 1g of carboxymethyl cellulose (the carboxymethyl cellulose is purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.) and 300mL of deionized water, stirring for 50min at 55 ℃, adding 20g of acetic anhydride, stirring for 1.7h at 75 ℃, stopping stirring, adding 0.6g of modified titanium dioxide-graphene oxide compound, ultrasonically dispersing for 4h, centrifuging, washing and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound.
Controlling the mass ratio of the carboxymethyl cellulose to the acetic anhydride to the modified titanium dioxide-graphene oxide compound to be 1:20:0.6.
step four: 100g of polyhydroxybutyrate-valerate (polyhydroxybutyrate-hydroxyvalerate is purchased from Ningbo Tianan biomaterial Co., ltd.) and 900g of chloroform are uniformly stirred at 68 ℃ to obtain polyhydroxybutyrate-valerate solution, 4g of modified titanium dioxide-carboxymethylcellulose compound and 30g of chloroform are uniformly stirred at 35 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, the modified zinc oxide-carboxymethylcellulose compound solution is added into the polyhydroxybutyrate-hydroxyvalerate solution, and a film is formed by tape casting to obtain a polyhydroxybutyrate-hydroxyvalerate film with the thickness of 20 mu m.
Controlling the mass ratio of the polyhydroxy butanoic acid valeric acid copolyester to the modified titanium dioxide-carboxymethyl cellulose composite to be 100:4.
coating an epoxy resin adhesive (epoxy resin adhesive 506 purchased from Zhengzhou alpha chemical Co., ltd.) on one side of an aluminum foil with a thickness of 50 μm, compounding a polyhydroxybutyrate-valerate film with the side coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film with the thickness of 25 mu m, compounding the polyhydroxy butanoic acid valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier property medicinal packaging film.
Example 2
The method comprises the following steps: preparation of hydrophobic titanium dioxide: 5g of titanium dioxide and 80mL of ethanol were ultrasonically dispersed for 50min, 3mL of 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane (3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane from Alantin reagent (Shanghai) Co., ltd.) was added, and the mixture was stirred for 50min, and 3mL1H,1H,2H, 1H-perfluorodecyltriethoxysilane (1H, 2H, 1H-perfluorodecyltriethoxysilane from Alantin reagent (Shanghai) Co., ltd.) was added and stirred for 4min to obtain hydrophobic titanium dioxide.
Step two: preparing a modified titanium dioxide-graphene oxide compound: taking 4g of hydrophobic titanium dioxide and 300mL of deionized water, performing ultrasonic dispersion for 30min, adding dopamine, stirring for 20min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value to 8.0, continuing stirring for 18h, adding 0.1g of graphene oxide, stirring for 18h at 25 ℃, filtering, washing and drying to obtain the modified titanium dioxide-graphene oxide compound.
Controlling the mass ratio of hydrophobic titanium dioxide to graphene oxide to be 4:0.1.
step three: preparing a modified titanium dioxide-carboxymethyl cellulose compound:
taking 1g of carboxymethyl cellulose (the carboxymethyl cellulose is purchased from Sichuan Huayuan Shengtai Biotechnology Co., ltd.) and 300mL of deionized water, stirring at 50 ℃ for 40min, adding 15g of acetic anhydride, stirring at 70 ℃ for 1.5h, stopping stirring, adding 0.5g of modified titanium dioxide-graphene oxide compound, performing ultrasonic dispersion for 3h, centrifuging, washing and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound.
Controlling the mass ratio of the carboxymethyl cellulose to the acetic anhydride to the modified titanium dioxide-graphene oxide compound to be 1:15:0.5.
step four: 100g of polyhydroxybutyrate-valerate (polyhydroxybutyrate-hydroxyvalerate is purchased from Ningbo Tianan biomaterial Co., ltd.) and 900g of chloroform are uniformly stirred at 66 ℃ to obtain polyhydroxybutyrate-valerate solution, 3g of modified titanium dioxide-carboxymethylcellulose compound and 30g of chloroform are uniformly stirred at 30 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, the modified zinc oxide-carboxymethylcellulose compound solution is added into the polyhydroxybutyrate-hydroxyvalerate solution, and a film is formed by tape casting to obtain a polyhydroxybutyrate-hydroxyvalerate film with the thickness of 20 mu m.
Controlling the mass ratio of the polyhydroxy butyric acid valeric acid copolyester to the modified titanium dioxide-carboxymethyl cellulose compound to be 100:3.
coating an epoxy resin adhesive (epoxy resin adhesive 506 available from Zhengzhou alpha chemical Co., ltd.) on one side of an aluminum foil with a thickness of 50 μm, compounding a polyhydroxybutyrate-valerate film with the side coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film with the thickness of 25 mu m, compounding the polyhydroxy butanoic acid valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier property medicinal packaging film.
Example 3
The method comprises the following steps: preparation of hydrophobic titanium dioxide: 5g of titanium dioxide and 80mL of ethanol were ultrasonically dispersed for 70min, 3mL of 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane (3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane from Alantin reagent (Shanghai) Co., ltd.) was added, stirring was carried out for 60min, 3mL1H,1H,2H, 1H-perfluorodecyltriethoxysilane (1H, 2H, 1H-perfluorodecyltriethoxysilane from Alantin reagent (Shanghai) Co., ltd.) was added, and stirring was carried out for 5min, thereby obtaining hydrophobic titanium dioxide.
Step two: preparing a modified titanium dioxide-graphene oxide compound: and (2) taking 7g of hydrophobic titanium dioxide and 300mL of deionized water, performing ultrasonic dispersion for 40min, adding dopamine, stirring for 30min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value to 8.5, continuing stirring for 20h, adding 0.1g of graphene oxide, stirring for 20h at 28 ℃, filtering, washing and drying to obtain the modified titanium dioxide-graphene oxide compound.
Controlling the mass ratio of hydrophobic titanium dioxide to graphene oxide to be 7:0.1.
step three: preparing a modified titanium dioxide-carboxymethyl cellulose compound:
taking 1g of carboxymethyl cellulose (the carboxymethyl cellulose is purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.) and 300mL of deionized water, stirring for 60min at 60 ℃, adding 25g of acetic anhydride, stirring for 2h at 80 ℃, stopping stirring, adding 0.7g of modified titanium dioxide-graphene oxide compound, ultrasonically dispersing for 5h, centrifuging, washing and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound.
Controlling the mass ratio of the carboxymethyl cellulose to the acetic anhydride to the modified titanium dioxide-graphene oxide composite to be 1:25:0.7.
step four: 100g of polyhydroxybutyrate-valerate (polyhydroxybutyrate-hydroxyvalerate is purchased from Ningbo Tianan biomaterial Co., ltd.) and 900g of chloroform are uniformly stirred at 72 ℃ to obtain polyhydroxybutyrate-valerate solution, 5g of modified titanium dioxide-carboxymethylcellulose compound and 30g of chloroform are uniformly stirred at 40 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, the modified zinc oxide-carboxymethylcellulose compound solution is added into the polyhydroxybutyrate-hydroxyvalerate solution, and a film is formed by tape casting to obtain a polyhydroxybutyrate-hydroxyvalerate film with the thickness of 20 mu m.
Controlling the mass ratio of the polyhydroxy butanoic acid valeric acid copolyester to the modified titanium dioxide-carboxymethyl cellulose composite to be 100:5.
coating an epoxy resin adhesive (epoxy resin adhesive 506 available from Zhengzhou alpha chemical Co., ltd.) on one side of an aluminum foil with a thickness of 50 μm, compounding a polyhydroxybutyrate-valerate film with the side coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film with the thickness of 25 mu m, compounding the polyhydroxy butyric acid and valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medical packaging film.
Example 4: the same procedure as in example 1 was repeated except that acetic anhydride was not added.
The method comprises the following steps: preparation of hydrophobic titanium dioxide: 5g of titanium dioxide and 80mL of ethanol were ultrasonically dispersed for 60min, 3mL of 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane (3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane obtained from Allantin reagent (Shanghai)) was added, stirring was carried out for 55min, 3mL1H,1H,2H, 1H-perfluorodecyltriethoxysilane (1H, 2H, 1H-perfluorodecyltriethoxysilane obtained from Allantin reagent (Shanghai)) was added, and stirring was carried out for 4.5min, whereby hydrophobic titanium dioxide was obtained.
Step two: preparing a modified titanium dioxide-graphene oxide compound: taking 5g of hydrophobic titanium dioxide and 300mL of deionized water, performing ultrasonic dispersion for 35min, adding dopamine, stirring for 25min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, continuing stirring for 19h, adding 0.1g of graphene oxide, stirring for 19h at 27 ℃, filtering, washing, and drying to obtain the modified titanium dioxide-graphene oxide compound.
Controlling the mass ratio of hydrophobic titanium dioxide to graphene oxide to be 5:0.1.
step three: preparing a modified titanium dioxide-carboxymethyl cellulose compound:
taking 1g of carboxymethyl cellulose (the carboxymethyl cellulose is purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.) and 300mL of deionized water, stirring for 50min at 55 ℃, stopping stirring, adding 0.6g of modified titanium dioxide-graphene oxide compound, performing ultrasonic dispersion for 4h, centrifuging, washing, and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound.
Controlling the mass ratio of the carboxymethyl cellulose to the modified titanium dioxide-graphene oxide compound to be 1:0.6.
step four: 100g of polyhydroxybutyrate-valerate (polyhydroxybutyrate-hydroxyvalerate is purchased from Ningbo Tianan biomaterial Co., ltd.) and 900g of chloroform are uniformly stirred at 68 ℃ to obtain polyhydroxybutyrate-valerate solution, 4g of modified titanium dioxide-carboxymethylcellulose compound and 30g of chloroform are uniformly stirred at 35 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, the modified zinc oxide-carboxymethylcellulose compound solution is added into the polyhydroxybutyrate-hydroxyvalerate solution, and a film is formed by tape casting to obtain a polyhydroxybutyrate-hydroxyvalerate film with the thickness of 20 mu m.
Controlling the mass ratio of the polyhydroxy butyric acid valeric acid copolyester to the modified titanium dioxide-carboxymethyl cellulose compound to be 100:4.
coating an epoxy resin adhesive (epoxy resin adhesive 506 available from Zhengzhou alpha chemical Co., ltd.) on one side of an aluminum foil with a thickness of 50 μm, compounding a polyhydroxybutyrate-valerate film with the side coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film with the thickness of 25 mu m, compounding the polyhydroxy butyric acid and valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medical packaging film.
Example 5: the procedure of example 1 was repeated except that no graphene oxide was added.
The method comprises the following steps: preparation of hydrophobic titanium dioxide: 5g of titanium dioxide and 80mL of ethanol were ultrasonically dispersed for 60min, 3mL of 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane (3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane obtained from Allantin reagent (Shanghai)) was added, stirring was carried out for 55min, 3mL1H,1H,2H, 1H-perfluorodecyltriethoxysilane (1H, 2H, 1H-perfluorodecyltriethoxysilane obtained from Allantin reagent (Shanghai)) was added, and stirring was carried out for 4.5min, whereby hydrophobic titanium dioxide was obtained.
Step two: preparing a modified titanium dioxide-carboxymethyl cellulose compound:
taking 1g of carboxymethyl cellulose (the carboxymethyl cellulose is purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.) and 300mL of deionized water, stirring for 50min at 55 ℃, adding 20g of acetic anhydride, stirring for 1.7h at 75 ℃, stopping stirring, adding 0.6g of hydrophobic titanium dioxide, ultrasonically dispersing for 4h, centrifuging, washing and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound.
Controlling the mass ratio of the carboxymethyl cellulose to the acetic anhydride to the hydrophobic titanium dioxide to be 1:20:0.6.
step three: 100g of polyhydroxybutyrate-valerate (polyhydroxybutyrate-valerate is purchased from Ningbo Tianan biomaterial Co., ltd.) and 900g of chloroform are uniformly stirred at 68 ℃ to obtain polyhydroxybutyrate-valerate solution, 4g of modified titanium dioxide-carboxymethyl cellulose compound and 30g of chloroform are uniformly stirred at 35 ℃ to obtain modified zinc oxide-carboxymethyl cellulose compound solution, the modified zinc oxide-carboxymethyl cellulose compound solution is added into the polyhydroxybutyrate-valerate solution, and a film is formed by tape casting to obtain a polyhydroxybutyrate-valerate film with the thickness of 20 micrometers.
Controlling the mass ratio of the polyhydroxy butyric acid valeric acid copolyester to the modified titanium dioxide-carboxymethyl cellulose compound to be 100:4.
coating an epoxy resin adhesive (epoxy resin adhesive 506 available from Zhengzhou alpha chemical Co., ltd.) on one side of an aluminum foil with a thickness of 50 μm, compounding a polyhydroxybutyrate-valerate film with the side coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film with the thickness of 25 mu m, compounding the polyhydroxy butanoic acid valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier property medicinal packaging film.
Example 6: the hydrophobic titanium dioxide was not prepared, and the rest was the same as in example 1.
The method comprises the following steps: preparing a modified titanium dioxide-graphene oxide compound: taking 5g of titanium dioxide and 300mL of deionized water, performing ultrasonic dispersion for 35min, adding dopamine, stirring for 25min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, continuing stirring for 19h, adding 0.1g of graphene oxide, stirring for 19h at 27 ℃, filtering, washing, and drying to obtain the modified titanium dioxide-graphene oxide compound.
Controlling the mass ratio of titanium dioxide to graphene oxide to be 5:0.1.
step three: preparing a modified titanium dioxide-carboxymethyl cellulose compound:
taking 1g of carboxymethyl cellulose (the carboxymethyl cellulose is purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.) and 300mL of deionized water, stirring for 50min at 55 ℃, adding 20g of acetic anhydride, stirring for 1.7h at 75 ℃, stopping stirring, adding 0.6g of modified titanium dioxide-graphene oxide compound, ultrasonically dispersing for 4h, centrifuging, washing and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound.
Controlling the mass ratio of the carboxymethyl cellulose to the acetic anhydride to the modified titanium dioxide-graphene oxide compound to be 1:20:0.6.
step four: 100g of polyhydroxybutyrate-valerate (polyhydroxybutyrate-hydroxyvalerate is purchased from Ningbo Tianan biomaterial Co., ltd.) and 900g of chloroform are uniformly stirred at 68 ℃ to obtain polyhydroxybutyrate-valerate solution, 4g of modified titanium dioxide-carboxymethylcellulose compound and 30g of chloroform are uniformly stirred at 35 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, the modified zinc oxide-carboxymethylcellulose compound solution is added into the polyhydroxybutyrate-hydroxyvalerate solution, and a film is formed by tape casting to obtain a polyhydroxybutyrate-hydroxyvalerate film with the thickness of 20 mu m.
Controlling the mass ratio of the polyhydroxy butyric acid valeric acid copolyester to the modified titanium dioxide-carboxymethyl cellulose compound to be 100:4.
coating an epoxy resin adhesive (epoxy resin adhesive 506 available from Zhengzhou alpha chemical Co., ltd.) on one side of an aluminum foil with a thickness of 50 μm, compounding a polyhydroxybutyrate-valerate film with the side coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film with the thickness of 25 mu m, compounding the polyhydroxy butanoic acid valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier property medicinal packaging film.
Experiment of the invention
The polyhydroxybutyrate-valerate films prepared in examples 1 to 6 were subjected to a performance test, and the packaging films were formed into a dumbbell shape having a width of 10mm and a length of 60mm using an Instron 5943 universal tester at 25 ℃ and 1 mm. Min -1 The mechanical property of the medical packaging film is tested at the stretching rate of (2). Preparing the packaging film into a sample of 10cm multiplied by 10cm, packaging the sample in a sample bottle of 10mL, placing the sample bottle in a pot with the temperature of 110 ℃ and the kPa for standing for 15min, and testing the water vapor transmission rate of the packaging film. The water absorption of the packaging film was measured by preparing a 10cm x 10cm sample, drying at a relative humidity of 0% until constant weight, continuing to absorb water at a relative humidity of 100% until constant weight, and obtaining the data shown in the following table:
and (4) conclusion: as can be seen from the comparison of the data in the table, in example 4, no acetic anhydride is added, the modified titanium dioxide-graphene composite and the carboxymethyl cellulose are not soluble, and the tensile strength of the packaging film is reduced; in the embodiment 5, the graphene oxide is not added, so that the tensile strength of the packaging film is influenced, and the barrier property of the packaging film is also influenced; example 6 no hydrophobic titanium dioxide was added and the barrier properties of the packaging film were the worst.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-barrier property medicinal packaging film is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: stirring carboxymethyl cellulose and deionized water at 50-60 ℃ for 40-60min, adding acetic anhydride, stirring at 70-80 ℃ for 1.5-2h, stopping stirring, adding the modified titanium dioxide-graphene oxide compound, performing ultrasonic dispersion for 3-5h, centrifuging, washing, and drying to obtain the modified titanium dioxide-carboxymethyl cellulose compound;
step two: uniformly stirring polyhydroxybutyrate-valerate and chloroform at 66-72 ℃ to obtain polyhydroxybutyrate-valerate solution, uniformly stirring modified titanium dioxide-carboxymethylcellulose compound and chloroform at 30-40 ℃ to obtain modified zinc oxide-carboxymethylcellulose compound solution, adding the modified zinc oxide-carboxymethylcellulose compound solution into polyhydroxybutyrate-valerate solution, and performing tape casting to form a film to obtain polyhydroxybutyrate-valerate film;
step three: coating an epoxy resin adhesive on one surface of an aluminum foil, compounding a polyhydroxybutyrate-valerate film with the surface coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on one surface of a polyamide film, compounding the polyhydroxy butyric acid and valeric acid copolyester surface of the film A with one surface of the polyamide film coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medical packaging film.
2. The method for preparing the high-barrier property medicinal packaging film according to claim 1, characterized in that: in the first step, the mass ratio of the carboxymethyl cellulose, the acetic anhydride and the modified titanium dioxide-graphene oxide compound is 1: (15-25): (0.5-0.7).
3. The method for preparing the high-barrier property medicinal packaging film according to claim 1, characterized in that: in the second step, the mass ratio of the polyhydroxy butanoic acid valeric acid copolyesters to the modified titanium dioxide-carboxymethyl cellulose compound is 100: (3-5).
4. The method for preparing the high-barrier property medicinal packaging film according to claim 1, wherein the method comprises the following steps: in the first step, the preparation method of the modified titanium dioxide-graphene oxide compound comprises the following steps: taking hydrophobic titanium dioxide and deionized water, performing ultrasonic dispersion for 30-40min, adding dopamine, stirring for 20-30min, adding Tris buffer solution, adding hydrochloric acid, adjusting the pH value, continuing to stir for 18-20h, adding graphene oxide, stirring for 18-20h at 25-28 ℃, filtering, washing and drying to obtain the modified titanium dioxide-graphene oxide compound.
5. The method for preparing the high-barrier property medicinal packaging film according to claim 1, wherein the method comprises the following steps: the preparation method of the hydrophobic titanium dioxide comprises the following steps: taking titanium dioxide and ethanol, carrying out ultrasonic dispersion for 50-70min, adding 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxy silane, stirring for 50-60min, adding 3mL1H,1H,2H and 1H-perfluorodecyl triethoxysilane, and stirring for 4-5min to obtain the hydrophobic titanium dioxide.
6. The method for preparing the high-barrier property medicinal packaging film according to claim 4, wherein the method comprises the following steps: the mass ratio of the hydrophobic titanium dioxide to the graphene oxide is (4-7): 0.1.
7. the method for preparing the high-barrier property medicinal packaging film according to claim 4, is characterized by comprising the following steps of: and adding hydrochloric acid into the Tris buffer solution, and adjusting the pH value to 8.0-8.5.
8. A high barrier pharmaceutical packaging film prepared by the method of any one of claims 1-7.
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