CN109225783B

CN109225783B - Production process of packaging composite film

Info

Publication number: CN109225783B
Application number: CN201811020852.1A
Authority: CN
Inventors: 柏金枝; 张辉; 闫斌
Original assignee: Sichuan Huili Industrial Co Ltd
Current assignee: Sichuan Huili Industrial Co Ltd
Priority date: 2018-09-03
Filing date: 2018-09-03
Publication date: 2021-02-19
Anticipated expiration: 2038-09-03
Also published as: CN109225783A

Abstract

The invention discloses a production process of a packaging composite film, which comprises the following steps: (A) preparing a hyperbranched cationic mussel-like polymer into an adhesive aqueous solution, wherein the hyperbranched cationic mussel-like polymer comprises a poly-o-phenolic hydroxyl benzophenone enamide monomer, a cationic monomer and a photoresponsive monomer; (B) preparing a graphene oxide solution; (C) soaking the polymer film in an adhesive aqueous solution, taking out and drying the polymer film, and then soaking the polymer film in a graphene oxide solution; (D) soaking the polymer film prepared in the step (C) in an adhesive aqueous solution, taking out and drying the polymer film, and soaking the polymer film in a graphene oxide solution; (E) repeating step (D); (F) and (E) putting the polymer film prepared in the step (E) into a reducing agent water solution, and heating, refluxing and condensing to obtain the packaging composite film. The invention omits a corona step, thereby not only reducing the process cost, but also simplifying the process steps.

Description

Production process of packaging composite film

Technical Field

The invention relates to the field of packaging materials, in particular to a production process of a packaging composite film.

Background

Polymer film packaging materials have become increasingly important in daily life as the primary packaging material for pharmaceuticals. However, due to the influence of the production process of plastic films and the physical and chemical properties of the plastic films, the barrier properties of the plastic to oxygen, water vapor, liquid substances and other low molecular weight substances are difficult to meet the requirements of most drug packages. The permeation of oxygen, water vapor and other small molecular gases to the packaging material can cause the oxidative deterioration of active ingredients in the medicine, further cause the reproduction of microorganisms and other phenomena, and the shelf life of the medicine is greatly shortened as a direct consequence. Therefore, the improvement of the barrier property of the plastic film packaging material to small molecule gases such as oxygen and water vapor and the endowment of the plastic film packaging material with antibacterial performance have important significance for the improvement of the quality of the plastic film packaging material.

Graphene is a two-dimensional carbon nanomaterial with sp for each carbon atom²The hybridization forms covalent bonds with 3 other carbon atoms, and then the bonds are arranged into a honeycomb hexagonal lattice. Single electron 2P orbital phase remaining on each carbon atomAnd the two are superposed to form delocalized conjugated large pi-shaped bonds. The pore size of the graphene six-membered ring is only 0.15nm, the diameter of the graphene six-membered ring is smaller than that of helium which is a known minimum gas molecule, and the graphene six-membered ring has natural gas barrier property. Meanwhile, the transmittance of the single-layer graphene to visible light is as high as 97%, and a high-light-transmittance film material can be easily prepared under appropriate preparation conditions. Moreover, the thickness of the single-layer graphene is only 0.34nm, and the width of the single-layer graphene can reach several micrometers to tens of centimeters. These make graphene an ideal nano-barrier material.

At present, one method for preparing the packaging composite film by utilizing the graphene is to bond the graphene and the polymer film through an adhesive, but the existing adhesive has small contact area with the graphene and the polymer film and few reaction sites, so that the bonding fastness of the adhesive, the graphene and the polymer film is weak, the process of the packaging composite film is complex, the barrier property of a finished product of the packaging composite film is poor, and the requirement on the barrier property of the medicine packaging is difficult to meet increasing requirements.

Disclosure of Invention

The invention aims to provide a production process of a packaging composite film, which aims to solve the problems that the existing preparation process of the packaging composite film is complex, and the barrier property of the packaging composite film prepared by the process is difficult to meet the packaging requirement of high-barrier medicaments.

The invention is realized by the following technical scheme:

a process for producing a packaging composite film comprising the steps of:

(A) preparing a hyperbranched cationic mussel-like polymer by adopting a reversible addition-fragmentation chain transfer polymerization method, and preparing the prepared hyperbranched cationic mussel-like polymer into an adhesive aqueous solution, wherein the hyperbranched cationic mussel-like polymer comprises a poly-o-phenolic hydroxyl benzophenone enamide monomer, a cationic monomer and a photoresponsive monomer;

(B) preparing a graphene oxide solution;

(C) soaking the polymer film in the adhesive aqueous solution prepared in the step (A), taking out after soaking for a period of time, and drying the polymer film; soaking the polymer film in the graphene oxide solution prepared in the step (B), taking out after soaking for a period of time, drying the polymer film to obtain the polymer film with the surface being the graphene layer, and then irradiating and curing the adhesive;

(D) soaking the polymer film with the graphene layer on the surface prepared in the step (C) in the adhesive aqueous solution prepared in the step (A), taking out after soaking for a period of time, and drying the polymer film; soaking the polymer film in the graphene oxide solution prepared in the step (B), taking out after soaking for a period of time, drying the polymer film, adding one layer of graphene on the polymer film, and then irradiating and curing the adhesive;

(E) repeating the step (D) until the number of graphene layers on the polymer film reaches the required number;

(F) and (E) putting the polymer film prepared in the step (E) into a reducing agent water solution, and heating, refluxing and condensing to obtain the packaging composite film.

In the prior art, chinese patent publication No. CN107880305A discloses a method for preparing a polymer composite material with high gas and liquid barrier properties, in which a polymer film is coated with a graphene group functional layer dispersion liquid by a dip coating process. However, the adhesive used in the method has poor adhesion with graphene and polymer films, which further complicates the process of packaging the composite film. Specifically, the coating temperature is 20-50 ℃, the coating pressure is 0.1-5 MPa, and the fixing time is 2-96 h; while the polymer film is corona treated prior to coating. In the process of production, complicated reaction conditions and long process time cause high production cost, and are not beneficial to large-scale industrial production. In addition, the existing graphene packaging composite film has poor barrier property and is difficult to meet the increasing demand on the barrier property of drug packaging.

In order to solve the problems, the hyperbranched cationic mussel-like polymer is prepared by a reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) method through the step (A), and comprises a poly-o-phenolic hydroxyl benzophenone enamide monomer, a cationic monomer and a photoresponsive monomer, and then the prepared hyperbranched cationic mussel-like polymer is prepared into an adhesive aqueous solution with the concentration for later use.

In the step (B), a commercially available graphene oxide solution may be used, or a graphene oxide solution may be prepared by the conventional Hummers method.

In the step (C), firstly, soaking the polymer film in the aqueous solution of the adhesive prepared in the step (A), taking out after soaking for a period of time, cleaning with deionized water, and then putting the polymer film into an oven for drying; and (C) soaking the polymer film in the graphene oxide solution prepared in the step (B), taking out after soaking for a period of time, washing with deionized water, drying the polymer film in an oven to obtain the polymer film with the graphene layer on the surface, and then irradiating and curing the adhesive. The polymer film formed in the step (C) has a graphene layer adhered to the surface thereof via an adhesive layer. Preferably, the polymer film may be a polymer film for drug packaging such as polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polybutylene terephthalate (PBT). Preferably, the time for cleaning the polymer film is 30 seconds.

In the step (D), the polymer film prepared in the step (C) is soaked in the adhesive aqueous solution prepared in the step (A), the polymer film is taken out after being soaked for a period of time, is washed by deionized water, and is then placed into an oven to be dried; and (C) soaking the polymer film in the graphene oxide solution prepared in the step (B), taking out after soaking for a period of time, washing with deionized water, putting the polymer film into an oven for drying, adding one layer of graphene on the polymer film, and then irradiating and curing the adhesive. Preferably, the time for cleaning the polymer film is 30 seconds.

And then, repeating the steps to enable the graphene layers coated on the surface of the polymer film to reach the required number of layers, preferably, the number of the graphene layers is 1-30.

And after the graphene layer is coated, putting the polymer film into a reducing agent aqueous solution, and heating, refluxing and condensing to obtain the packaging composite film. The reducing agent may be any one of sodium ascorbate, hydroiodic acid, hydrazine hydrate, and sodium borohydride.

In the technical scheme, the hyperbranched cationic mussel-like polymer comprises a poly-o-phenolic hydroxybenzophenone enamide monomer and a cationic monomer. Preferably, the poly-o-phenol hydroxybenzophenone enamide monomer is 2,3, 4-trihydroxybenzoyl p-benzoyl- (2-aminoethyl) acrylamide, 2, 3-dihydroxybenzoyl p-benzoyl- (2-aminoethyl) acrylamide or 2,3, 4-trihydroxybenzoyl m-benzoyl- (2-aminoethyl) acrylamide, which can be synthesized by esterification reactions commonly used in the art or commercially available; the cationic monomer is any one of N- (2-aminoethyl) (meth) acrylamide hydrochloride, N- (3-aminopropyl) (meth) acrylamide hydrochloride, N- (4-aminobutyl) (meth) acrylamide hydrochloride, N- (6-aminohexyl) (meth) acrylamide hydrochloride, and 2-aminoethyl) (meth) acrylate hydrochloride.

The poly-o-phenol hydroxy benzophenone alkene amide monomer has a large number of free catechol radicals, and the catechol radicals can improve the binding force of the catechol radicals to the polymer film layer through a synergistic effect in the presence of a cationic end group. In addition, the large number of free catechol groups and cationic groups can enable the hyperbranched cationic mussel-like polymer to have good adhesion properties to a variety of polymer film layers through a series of intermolecular interactions of different strengths, such as van der waals forces, hydrogen bonds, and cation-pi interactions. Therefore, the bonding fastness between the adhesive and the polymer film layer is obviously improved by the hyperbranched cationic mussel-like polymer containing the poly-o-phenolic hydroxybenzophenone enamide monomer and the cationic monomer.

The hyperbranched cationic mussel-like polymer also comprises a photo-responsive monomer. Preferably, the photo-responsive monomer may be any one of 4-azido-2, 3,5, 6-tetrafluorobenzoyl- (2-aminoethyl) acrylamide, 4-azido-2, 3, 5-trifluorobenzoyl- (2-aminoethyl) acrylamide, 4-azido-2, 3-tetrafluorobenzoyl- (2-aminoethyl) acrylamide, and 4-azido-benzoyl- (2-aminoethyl) acrylamide.

Besides intermolecular force, the photoresponse monomer generates benzene ring free radicals under the action of illumination, and the benzene ring free radicals can attack C-H bonds on graphene molecules to generate chemical reaction to form covalent bonds, so that the bonding strength between the polymer and the graphene molecules is greatly improved.

It can be seen that the adhesive prepared from the hyperbranched cationic mussel-like polymer significantly increases the adhesive strength of the adhesive to the polymer film layer and the bonding strength of the adhesive to the graphene layer. Can use less adhesive can accomplish powerful bonding, and the adhesive layer thickness reduces for under the prerequisite that the gross thickness is unchangeable, total mass does not show the increase not, the number of piles of graphite alkene layer can promote by a wide margin, and the vapor permeability of the packaging composite membrane of producing, oxygen permeability obviously reduce, and tensile strength is showing and is increasing, can satisfy the demand of pharmaceutical packaging material well.

Furthermore, prior art techniques typically require corona treatment of the polymer film prior to spraying the adhesive thereon. In the application, the poly-o-phenolic hydroxybenzophenone enamide monomer contains a large amount of catechol groups, and can form various intermolecular acting forces such as hydrogen bonds, van der waals forces, cation pi acting forces and the like with the surface of the polymer film, so that the poly-o-phenolic hydroxybenzophenone enamide monomer can be well combined with the surface of the polymer film, and even if a corona step is not carried out, an adhesive aqueous solution can be well coated on the polymer film, so that the corona step is omitted, the process cost is reduced, and the process steps are simplified; meanwhile, the reaction conditions of the invention are mild, the soaking process can be completed at normal temperature and normal pressure, the soaking time is short, when the number of the graphene layers is less than 10, the total soaking time is not more than 2 hours, the working hours are effectively shortened, and the invention has wide popularization value.

As a preferred preparation process of the hyperbranched cationic mussel-like polymer of the invention, the step (a) comprises the steps of:

(A1) adding an initiator, a RAFT agent and the first reaction mixture to a vessel containing DMF to form a second reaction mixture;

(A2) stirring the second reaction mixture until the second reaction mixture is uniform, and introducing argon to remove oxygen in the reaction system;

(A3) heating and stirring the second reaction mixture for reaction;

(A4) after the desired molecular weight of the product was reached, the reaction was exposed to air and rapidly cooled in a cold water bath to terminate the reaction;

(A5) purifying to obtain a hyperbranched cationic mussel-like polymer;

(A6) preparing the hyperbranched cationic mussel-like polymer into an adhesive aqueous solution;

in the above step, the first reaction mixture includes a poly-o-phenolic hydroxybenzophenone enamide monomer, a cationic monomer, a photoresponsive monomer, a polyethylene glycol diacrylate and a polyethylene glycol diacrylate.

Firstly, adding an initiator, a RAFT reagent, a poly-o-phenol hydroxy benzophenone enamide monomer, a cationic monomer, a photoresponsive monomer, polyethylene glycol diacrylate and polyethylene glycol diacrylate into a round-bottom flask filled with DMF (N, N-dimethylformamide) and uniformly stirring, preferably, the concentration of the initiator is 0.012M, and then introducing argon to remove oxygen in a reaction system, preferably, the introducing time of the argon is 20-25 minutes. And then putting the round-bottom flask into an oil bath for heating and stirring, wherein the oil bath temperature is preferably 60-90 ℃, and the stirring speed is 600-800 rpm. After the reaction was carried out until the desired conversion was achieved and the desired molecular weight of the product was obtained, the reaction system was exposed to air and the round-bottom flask was placed in a cold water bath to allow the reaction system to cool rapidly. The product is then purified to give a light brown hyperbranched cationic mussel-like polymer, preferably using dichloromethane and diethyl ether as solvents. After purification, preparing the hyperbranched cationic mussel-like polymer into an adhesive aqueous solution with the concentration of 0.5-5 mg/mL.

Preferably, the polyethylene glycol dienoate is polyethylene glycol diacrylate or polyethylene glycol dimethacrylate, and the polyethylene glycol dienoate is used for adjusting the esterification degree of the polymer; the polyethylene glycol enoate is polyethylene glycol methyl ether acrylate or polyethylene glycol methyl ether methacrylate, the polyethylene glycol enoate is used for adjusting the solubility of the polymer, and preferably, the molecular weight of polyethylene glycol is 200-6000.

Further, the mol percentages of the poly-o-phenol hydroxybenzophenone enamide monomer, the cationic monomer, the photoresponsive monomer, the polyethylene glycol enoate and the polyethylene glycol enoate are as follows in sequence: 20-40%, 30-40%, 1-5%, 20-40% and 5-10%.

Further, in step (a1), the molar ratio of the initiator, the RAFT agent and the first reaction mixture is 1:2: 100.

Further, the initiator is 1,1 ' -azobis (cyclohexanecarbonitrile, 2' -azobis (2-methylpropanenitrile) or 4,4' -azobis (4-cyanopentanoic acid), and the RAFT agent is any one of 2- (dodecyltrithiocarbonate) -2-methylpropanoic acid, 4-cyano-4- (phenylthiocarbonylthio) pentanoic acid and 2-cyano-2-propyl-4-cyanobenzene dithiocarbonate.

As a preferred preparation process of the graphene oxide solution of the present invention, the step (B) includes the steps of:

(B1) adding graphite powder into concentrated sulfuric acid, uniformly stirring in an ice-water bath, adding potassium permanganate, controlling the temperature of the water bath to be 10-15 ℃, and reacting for 2 hours;

(B2) transferring the reaction solution into a 35 ℃ water bath for constant temperature reaction for 30min, continuously stirring, adding distilled water into the reaction solution, and then controlling the temperature at 80 ℃ for reaction for 15 min;

(B3) adding a certain amount of 15% hydrogen peroxide into the reaction solution until bubbles are generated, filtering while hot, and washing a filter cake with hydrochloric acid and deionized water until the filtrate is neutral to prepare a graphene oxide aqueous solution;

(B4) before using the graphene oxide aqueous solution, diluting the graphene oxide aqueous solution with deionized water and performing ultrasonic treatment for 1 hour to obtain the graphene oxide solution.

According to the technical scheme, the existing Hummers method for preparing graphene oxide is improved, on one hand, the total reaction time is less than 3 hours, the total reaction time of the Hummers method is greatly shortened, the steps of standing, drying and the like are not needed, and the production efficiency is effectively improved; on the other hand, water is used as a solvent in the whole reaction process, the preparation conditions are environment-friendly, the post-treatment process is simpler, and the production cost is reduced.

Further, before the step (C), the polymer film is first washed with deionized water to remove the contaminants adhered to the surface of the polymer film. The adhesive strength of the adhesive can be further improved by removing contaminants adhered to the surface of the polymer film, and ultimately the quality of the packaging composite film product.

Further, in the step (C) and the step (D), the mass fraction of the binder aqueous solution is 0.01%, and the mass fraction of the graphene oxide solution is 0.01%.

Further, in the step (C) and the step (D), the soaking time is 4-7 minutes, and preferably, the soaking time is 5 minutes.

Further, in the step (F), the reducing agent is hydrazine hydrate aqueous solution, the reflux temperature is 60 degrees, and the reflux time is 24 hours.

As a preferred structure of the hyperbranched cationic mussel-like polymer of the invention, the hyperbranched cationic mussel-like polymer has a structure of formula i:

in the formula I, x is 1-10, y is 20-80, z is 30-80, w is 5-20, u is 20-80, K is 1-5, n is 10-50, and m is 5-30;

in the formula I, R₁Any one selected from the group shown in formula II,

in the formula I, R₂Any one selected from the group represented by formula III,

under the illumination condition, the covalent bond between the fluorine substituent of the photoresponse group and the graphene can be broken or combined, so that the bonding strength between the polymer and the graphene can be changed according to the illumination strength, the bonding strength of the adhesive can be adjusted according to specific requirements, and the graphene film packaging material is more suitable for graphene film packaging materials. Preferably, in the formula I, K is 1-3, n is 20-30, and m is 10-20.

Compared with the traditional small-molecule adhesive and the common polymer adhesive, the hyperbranched cationic mussel-like polymer disclosed by the invention has excellent mussel-like non-selective adhesion performance, good biocompatibility and bonding strength adjustability.

Furthermore, the polymerization degree of the hyperbranched cationic mussel-like polymer is 100-400.

Compared with the prior art, the invention has the following advantages and beneficial effects:

1. in the invention, the poly-o-phenolic hydroxyl benzophenone enamide monomer contains a large amount of catechol groups, and can form various intermolecular acting forces such as hydrogen bonds, van der waals forces, cation pi acting forces and the like with the surface of the polymer film, so that the poly-o-phenolic hydroxyl benzophenone enamide monomer can be well combined with the surface of the polymer film, and even if no corona step is carried out, the adhesive aqueous solution can be well coated on the polymer film, so that the corona step is omitted, the process cost is reduced, and the process steps are simplified;

2. the method has mild reaction conditions, can finish the soaking process at normal temperature and normal pressure, has short soaking time, and effectively shortens the working hours by ensuring that the total soaking time is not more than 2 hours when the number of the graphene layers is less than 10, thereby having wide popularization value;

3. the adhesive prepared from the hyperbranched cationic mussel-like polymer remarkably increases the adhesive strength between the adhesive and the polymer film layer and the bonding strength between the adhesive and the graphene layer, can finish strong bonding by using less adhesive, has reduced thickness, greatly improves the number of layers of the graphene layer on the premise of unchanged total thickness and insignificant increase of total mass, obviously reduces the water vapor permeability and the oxygen permeability of the produced packaging composite film, remarkably increases the tensile strength, and can well meet the requirements of pharmaceutical packaging materials;

4. the method improves the existing Hummers method for preparing graphene oxide, on one hand, the total reaction time is less than 3 hours, the total reaction time of the Hummers method is greatly shortened, the steps of standing, drying and the like are not needed, and the production efficiency is effectively improved; on the other hand, water is used as a solvent in the whole reaction process, the preparation conditions are environment-friendly, the post-treatment process is simpler, and the production cost is reduced.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.

All of the starting materials of the present invention, the sources of which are not particularly limited, are commercially available or can be prepared according to conventional methods well known to those skilled in the art, for example, the photoresponsive monomer can be synthesized by esterification, and the polyphthalin hydroxybenzophenone enamide monomer can be synthesized in the manner disclosed in [ J ] Polymer Bulletin,2012,68, 441-.

All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the field of analytical purification or binder preparation.

The expression of the substituent in the present invention is not particularly limited, and the expression known to those skilled in the art is used, and the meaning of the substituent can be correctly understood by the skilled in the art based on the general knowledge.

All the raw materials, the marks and the acronyms thereof belong to the conventional marks and the acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by the conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.

Example 1:

preparing a hyperbranched cationic mussel-like polymer P1:

2,3, 4-Trihydroxybenzoyl-M-benzoyl- (2-aminoethyl) acrylamide, N- (2-aminoethyl) (meth) acrylamide hydrochloride, 4-azido-2, 3,5, 6-tetrafluorobenzoylethylamine (meth) acrylamide, polyethylene glycol methyl ether acrylate (PEGMEA), polyethylene glycol diacrylate (PEGDEA, degree of polymerization of ethylene glycol 22) and RAFT reagent were added to a 0.012M solution of initiator 4,4' -azobis (4-cyanovaleric acid) in N, N-dimethylformamide. Wherein the molar ratio of the first reaction mixture consisting of PEGMEA with a polymerization degree of ethylene glycol of 15, PEGDEA with a polymerization degree of ethylene glycol of 22, 4,4' -azobis (4-cyanovaleric acid), RAFT agent and all monomers involved in the polymerization is 1:2: 100. 2,3, 4-trihydroxybenzoyl-m-benzoyl- (2-aminoethyl) acrylamide: n- (2-aminoethyl) (meth) acrylamide hydrochloride: 4-azido-2, 3,5, 6-tetrafluorobenzoylethylamine (meth) acrylamide: PEGDMEA: mole percent of PEGEA is 40%: 30%: 5%: 15%: 10 percent. And (3) uniformly stirring the obtained second reaction mixture, and introducing argon for 20-25 min to remove oxygen in the second reaction mixture. The mixed system is placed at 70 ℃ and 700rmp and stirred for reaction until the expected conversion rate is reached, and the product with the required molecular weight is obtained. At the end of the reaction, the reaction system was exposed to air and quenched in cold water. After further purification of the product with dichloromethane and diethyl ether, a light brown adhesive hyperbranched cationic mussel-like polymer P1 was obtained. Then, the hyperbranched cationic mussel-like polymer P1 is dissolved in ethanol and water (volume ratio is 1:1), and an aqueous adhesive solution S1 with the mass fraction of 0.01% is obtained.

The hyperbranched cationic mussel-like polymer P1 has the structure:

the map detection results of the structure are as follows:

¹H NMR(400MHz,DMSO-D₆)δ(ppm)：7.90-8.2(-NHCOC₆H₄CO-)6.6-7.2(C₆H₂(OH)₃),5.35(-C₆H₃(OH)₂),4.32(CH₂OOC-),3.50-3.8(-CH₂CH₂O-,-OCNHCH₂CH₂-),3.22(CH₃O-),3.03(-OCNHCH₂CH₂NH₃Cl),2.16(-CH₂CHCO-),1.25-1.96(-CH₂CHCO-)；

¹⁹F NMR(188MHz,DMSO-D₆)δ(ppm)：-134.69～-134.88(2F),-147.58～-147.71(2F)。

example 2:

preparing a hyperbranched cationic mussel-like polymer P2:

2,3, 4-Trihydroxybenzoyl-p-benzamide ethyl (meth) acrylamide hydrochloride, N- (3-aminopropyl) (meth) acrylamide hydrochloride, 4-azido-2, 3,5, 6-tetrafluorobenzamide ethyl amine (meth) acrylamide, polyethylene glycol methyl ether acrylate (PEGMEA), polyethylene glycol diacrylate (PEGDEA) and RAFT reagent were added to a solution of 2,2' -azobis (2-methylpropionitrile) in N, N-dimethylformamide as an initiator at a concentration of 0.012M. Wherein the molar ratio of the first reaction mixture consisting of PEGMEA with a glycol polymerization degree of 45, PEGDEA with a glycol polymerization degree of 10, 2,2' -azobis (2-methylpropanenitrile), RAFT reagent and all monomers participating in polymerization is 1:2: 100. 2,3, 4-trihydroxybenzoylbenzamide ethyl (meth) acrylamide hydrochloride: n- (3-aminopropyl) (meth) acrylamide hydrochloride: 4-azido-2, 3,5, 6-tetrafluorobenzoylethylamine (meth) acrylamide: PEGDEA: the mole percentage of PEGMEA is 20%: 33%: 2%: 35%: 10 percent. And (3) uniformly stirring the obtained second reaction mixture, and introducing argon for 20-25 min to remove oxygen in the second reaction mixture. The mixed system is placed at 70 ℃ and 700rmp and stirred for reaction until the expected conversion rate is reached, and the product with the required molecular weight is obtained. At the end of the reaction, the reaction system was exposed to air and quenched in cold water. After further purification of the product with dichloromethane and diethyl ether, a light brown adhesive hyperbranched cationic mussel-like polymer P2 was obtained. Then, the hyperbranched cationic mussel-like polymer P2 is dissolved in ethanol and water (volume ratio is 1:1), and an adhesive aqueous solution S2 with the mass fraction of 0.01% is obtained.

The hyperbranched cationic mussel-like polymer P2 has the structure:

the map detection results of the structure are as follows:

¹H NMR(400MHz,DMSO-D₆)δ(ppm)：

7.90-8.2(-NHCOC₆H₄CO-)6.6-7.2(C₆H₂(OH)₃),5.35(C₆H₂(OH)₃),4.32(CH₂OOC-),3.50-3.8(-CH₂CH₂O-,-OCNHCH₂CH₂-),3.22(CH₃O-),3.03(-OCNHCH₂CH₂NH₃Cl),2.16(-CH₂CHCO-),1.25-1.96(-CH₂CHCO-)；

example 3:

preparing a hyperbranched cationic mussel-like polymer P3:

2, 3-Dihydroxybenzoylbenzoate aminoethyl (meth) acrylamide hydrochloride, N- (4-aminobutyl) (meth) acrylamide hydrochloride, 4-azido-benzoylethylamine (meth) acrylamide, polyethylene glycol methyl ether acrylate (PEGMEA), polyethylene glycol diacrylate (PEGDEA) and RAFT reagent 2- (dodecyltrithiocarbonate) -2-methylpropionic acid were added to a solution of initiator 2,2' -azobis (2-methylpropionitrile) in N, N-dimethylformamide at a concentration of 0.012M. Wherein the molar ratio of the first reaction mixture consisting of PEGMEA with a degree of polymerization of ethylene glycol of 5, PEGDEA with a degree of polymerization of ethylene glycol of 8, 2,2' -azobis (2-methylpropanenitrile), RAFT agent and all monomers involved in the polymerization is 1:2: 100. 2, 3-dihydroxybenzoylbenzoic acid ester aminoethyl (meth) acrylamide hydrochloride: n- (4-aminobutyl) (meth) acrylamide hydrochloride: 4-azido-benzoylethylamine (meth) acrylamide: PEGDEA: the mole percentage of PEGMEA is 25%: 35%: 5%: 30%: 5 percent. And (3) uniformly stirring the obtained mixed solution, and introducing argon for 20-25 min to remove oxygen in the mixed solution. The mixed system is placed at 70 ℃ and 700rmp and stirred for reaction until the expected conversion rate is reached, and the product with the required molecular weight is obtained. At the end of the reaction, the reaction system was exposed to air and quenched in cold water. After further purification of the product with dichloromethane and diethyl ether, a light brown adhesive hyperbranched cationic mussel-like polymer P3 was obtained. Then, the hyperbranched cationic mussel-like polymer P3 is dissolved in ethanol and water (volume ratio is 1:1), and an adhesive aqueous solution S3 with the mass fraction of 0.01% is obtained.

The hyperbranched cationic mussel-like polymer P3 has the structure:

the map detection results of the structure are as follows:

¹H NMR(400MHz,DMSO-D₆)δ(ppm)：7.90-8.2(-NHCOC₆H₄CO-)6.6-7.5(N₃C₆H₄CO-,-C₆H₃(OH)₂),5.35(-C₆H₃(OH)₃),4.32(CH₂OOC-),3.50-3.8(-CH₂CH₂O-,-OCNHCH₂CH₂-),3.22(CH₃O-),3.03(-OCNHCH₂CH₂NH₃Cl),2.16(-CH₂CHCO-),1.25-1.96(-CH₂CHCO-)。

example 4:

preparation of films for pharmaceutical packaging M1, M2 and M3:

firstly, preparing a graphene oxide solution with the mass fraction of 0.01% by using the conventional Hummers method;

subsequently, cleaning the three PET films to remove pollutants on the surfaces of the PET films;

soaking the three cleaned PET films in the adhesive aqueous solutions S1-S3 prepared in the embodiments 1-3 for 5 minutes, cleaning the films with deionized water for 30 seconds, and then drying the PET films in an oven at 40 ℃; then placing the PET film into the graphene oxide solution to be soaked for 5 minutes, then washing the PET film for 30 seconds by using deionized water, and then placing the PET film into a drying oven at 40 ℃ to be dried to form the PET film with 1 layer of graphene layers; then exposing for 10 seconds at a distance of 25 cm under a 1000W medium-pressure mercury lamp to cure the adhesive layer, so as to improve the adhesion fastness;

and repeating the soaking process until the number of the graphene layers of the PET film is 30.

Finally, the PET film is put into hydrazine hydrate aqueous solution, and is heated and refluxed and condensed for 24 hours at 60 ℃ to obtain packaging composite films M1, M2 and M3 with 30 layers of graphene layers.

Example 5:

the hard PVC solid medicinal tablet is adopted in comparative example 1, and the hard PVDC solid medicinal tablet is adopted in comparative example 2.

The physical parameters of the composite films for packaging medicine M1, M2, M3, comparative example 1 and comparative example 2 with the same thickness and quality are tested according to national standards, and the obtained physical parameters are shown in Table 1:

TABLE 1 physical parameters of the composite packaging films

Item

Unit of

M1

M2

M3

Comparative example 1

Comparative example 2

Water vapor transmission capacity

g/m².atm.day

0.28

0.35

0.33

1.01

0.42

Oxygen permeability

cc/m².atm.day

0.19

0.26

0.31

12.27

0.523

Tensile Strength (longitudinal/horizontal)

MPa

65.3/64.7

63.9/62.7

64.1/63.4

66.2/65.3

56.7/55.7

Heat seal strength

N/15mm

10.9

11.1

10.8

11.5

10.8

Heavy metals

％

<0.0001

Easily oxidized substance

ml

<1.5

<2

Non-volatile matter

mg

<25

<30

Total number of bacteria

Per cm²

<1000

Total number of moulds

Per cm²

<100

Escherichia coli

Per cm²

0

As can be seen from table 1, under the same quality and thickness, compared with comparative example 1 and comparative example 2, the water vapor permeability and the oxygen permeability of the films M1, M2 and M3 for packaging medicines prepared in examples 1 to 3 are significantly reduced, so that small molecule gases such as oxygen and water vapor are effectively prevented from permeating into a packaging material, the active ingredients in the medicines are prevented from being oxidized and deteriorated, the phenomena such as microbial propagation and the like are prevented, and the shelf life of the medicines is prolonged.

Example 6

On the basis of the embodiment 4, the preparation method of the reduced graphene oxide solution is improved.

Adding 1 g of graphite powder into 23ml of concentrated sulfuric acid, placing the mixture in an ice-water bath, fully and uniformly stirring, adding 2.5g of potassium permanganate, controlling the temperature of the water bath to be 10-15 ℃ for reaction for 2 hours, then moving the reaction solution into a 35 ℃ water bath for constant-temperature reaction for 30min, continuously stirring the reaction solution, then adding 80ml of distilled water into the reaction solution, controlling the temperature to be 80 ℃ for reaction for 15min, adding a certain amount of 15% hydrogen peroxide into the reaction solution until bubbles are generated, filtering while hot, and washing a filter cake with hydrochloric acid and deionized water until the filtrate is neutral to prepare the graphene oxide aqueous dispersion for later use.

In the technical scheme, the total reaction time is less than 3 hours, the total reaction time of the Hummers method is greatly shortened, the steps of standing, drying and the like are not needed, and the production efficiency is effectively improved; on the other hand, water is used as a solvent in the whole reaction process, the preparation conditions are environment-friendly, the post-treatment process is simpler, and the production cost is reduced.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims

1. A process for producing a packaging composite film, comprising the steps of:

(B) preparing a graphene oxide solution;

(F) putting the polymer film prepared in the step (E) into a reducing agent aqueous solution, heating, refluxing and condensing to obtain a packaging composite film;

the step (A) includes the steps of:

(A3) heating and stirring the second reaction mixture for reaction;

(A5) purifying to obtain a hyperbranched cationic mussel-like polymer;

in the above step, the first reaction mixture comprises a poly-o-phenol hydroxybenzophenone enamide monomer, a cationic monomer, a photoresponsive monomer, polyethylene glycol dienoate and polyethylene glycol enoate;

the hyperbranched cationic mussel-like polymer has a structure shown in a formula I:

in the formula I, R₁Any one selected from the group shown in formula II,

2. the production process of the packaging composite film according to claim 1, wherein the mol percentages of the poly-o-phenol hydroxybenzophenone enamide monomer, the cationic monomer, the photoresponsive monomer, the polyethylene glycol enoate and the polyethylene glycol enoate are as follows: 20-40%, 30-40%, 1-5%, 20-40% and 5-10%.

3. A process for the production of a packaging composite film according to claim 1 wherein step (B) comprises the steps of:

4. The process of claim 1 wherein step (C) is preceded by first rinsing the polymer film with deionized water to remove contaminants adhered to the surface of the polymer film.

5. The process for producing a packaging composite film according to claim 1, wherein in the steps (C) and (D), the mass fraction of the aqueous binder solution is 0.01%, and the mass fraction of the graphene oxide solution is 0.01%.

6. A process for producing a packaging composite film according to claim 1, wherein the soaking time in step (C) and step (D) is 4 to 7 minutes.

7. A process for the production of a packaging composite film according to claim 1, wherein the reducing agent in step (F) is an aqueous solution of hydrazine hydrate, the reflux temperature is 60 ℃ and the reflux time is 24 hours.