CN109225783A - A kind of production technology of packaging composite film - Google Patents

A kind of production technology of packaging composite film Download PDF

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Publication number
CN109225783A
CN109225783A CN201811020852.1A CN201811020852A CN109225783A CN 109225783 A CN109225783 A CN 109225783A CN 201811020852 A CN201811020852 A CN 201811020852A CN 109225783 A CN109225783 A CN 109225783A
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thin polymer
polymer film
hyperbranched
solution
cation
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CN109225783B (en
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柏金枝
张辉
闫斌
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Sichuan Huili Industrial Co Ltd
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Sichuan Huili Industrial Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a kind of production technologies of packaging composite film, the following steps are included: the imitative mussel polymer of hyperbranched cation is configured to binder aqueous solution by (A), the hyperbranched imitative mussel polymer of cation includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer and photoresponse monomer；(B) prepare graphene oxide solution；(C) thin polymer film is immersed in binder aqueous solution, takes out and thin polymer film is immersed in graphene oxide solution after drying；(D) thin polymer film prepared in step (C) is immersed in binder aqueous solution, takes out and thin polymer film is immersed in graphene oxide solution after drying；(E) step (D) is repeated；(F) thin polymer film prepared in step (E) is put into reducing agent aqueous solution, obtains packaging composite film after being heated to reflux condensation.Present invention eliminates corona steps, not only reduce process costs, also simplify processing step.

Description

A kind of production technology of packaging composite film
Technical field
The present invention relates to packaging material fields, and in particular to a kind of production technology of packaging composite film.
Background technique
Main packaging material of the thin polymer film packaging material as drug, has become more and more heavier in daily life It wants.However, being influenced by plastic film production process and own physical chemical characteristic, so that plastics are to oxygen, vapor, liquid The barrier property of substance and other low molecular weight substances is difficult to meet the requirement of most drugs packaging.Oxygen and vapor etc. are small Molecular gas will lead to the active constituent in drug to the infiltration of packaging material and oxidation deterioration occur, and then cause the numerous of microorganism Phenomena such as growing, direct consequence are exactly to greatly shorten the shelf-life of drug.So improving plastic film packaging material to small molecule It the gas such as barrier property of oxygen, vapor and assigns its anti-microbial property and is of great significance to its quality-improving.
Graphene is a kind of two-dimentional carbon nanomaterial, and each carbon atom is with sp2The mode and other 3 of hydridization formation covalent bond A carbon atom is connected, and is then arranged in cellular hexagonal lattice.Remaining single electron 2P track phase mutual respect on each carbon atom It closes, forms delocalization and be conjugated big pi bond.Graphene hexatomic ring pore-size is only 0.15nm, than known minimum gas molecule --- helium Gas diameter also wants small, has natural barrier properties for gases.Meanwhile single-layer graphene is up to 97% to the transmitance of visible light, It is easy to prepare the thin-film material of high light transmittance under suitable preparation condition.Also, the thickness of single-layer graphene is only 0.34nm, and width is up to several microns to several tens cm.These make graphene become ideal nanometer barrier material.
Currently, being by adhesive by graphene and polymer thin using a kind of method that graphene prepares packaging composite film Film bonding, but since the contact area of existing adhesive and graphene, thin polymer film is small, reaction site is few, so that bonding Agent and the bonding intensity of graphene, thin polymer film are weak, in turn result in the complex process of packaging composite film, packaging composite film finished product Barrier property it is poor, hardly possible meets to drug packages barrier property requirement increase increasingly the needs of.
Summary of the invention
The purpose of the present invention is to provide a kind of production technologies of packaging composite film, to solve existing packaging composite film system The problem of standby complex process, packaging composite film barrier property difficulty made from technique meets high barrier drug packages requirement.
The present invention is achieved through the following technical solutions:
A kind of production technology of packaging composite film, comprising the following steps:
(A) the imitative mussel polymer of hyperbranched cation is prepared using reversible addion-fragmentation chain transfer polymerization, then will be made The standby imitative mussel polymer of hyperbranched cation is configured to binder aqueous solution, wherein the hyperbranched imitative mussel of cation is poly- Closing object includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer and photoresponse monomer；
(B) prepare graphene oxide solution；
(C) thin polymer film is immersed in the binder aqueous solution prepared in step (A), is taken after being soaked for a period of time Out, and by thin polymer film it dries；Thin polymer film is immersed in later in the graphene oxide solution prepared in step (B), It is taken out after being soaked for a period of time, and thin polymer film is dried, obtain the thin polymer film that surface is graphene layer, later illumination Solidification adhesive；
(D) thin polymer film that the surface prepared in step (C) is graphene layer is immersed in the viscous of the middle preparation of step (A) In mixture aqueous solution, taken out after being soaked for a period of time, and thin polymer film is dried；Thin polymer film is immersed in step later (B) it in the graphene oxide solution prepared in, is taken out after being soaked for a period of time, and thin polymer film is dried, thin polymer film On graphene number of plies increase by one layer, illumination curing adhesive later；
(E) step (D) is repeated, until the graphene number of plies on thin polymer film reaches the required number of plies；
(F) thin polymer film prepared in step (E) is put into reducing agent aqueous solution, is obtained after being heated to reflux condensation Packaging composite film.
In the prior art, the Chinese patent of Publication No. CN107880305A discloses a kind of high air-liquid barrier property The preparation method of polymer composites, in the preparation method, using dipping process by graphene group functional layer dispersion liquid Coated on thin polymer film.But since the bonding intensity of its adhesive and graphene, thin polymer film that use is weak, into And cause the complex process of packaging composite film.Be embodied in, application temperature be 20~50 DEG C, coating pressure be 0.1~ 5MPa, set time are 2~96h；Simultaneously before coating, thin polymer film carries out sided corona treatment.In art production process, Complicated reaction condition and technique duration will cause high production cost, be unfavorable for large-scale industrial production.In addition, existing stone The barrier property of black alkene packaging composite film is poor, and hardly possible, which meets, requires the needs of increasing increasingly to drug packages barrier property.
To solve the above-mentioned problems, the present invention utilizes reversible addion-fragmentation chain transfer polymerization (RAFT by step (A) Polymerization) the imitative mussel polymer of hyperbranched cation is made, which includes more ortho-phenolic hydroxyls Benzophenone acrylamide monomer, cationic monomer and photoresponse monomer later gather the obtained imitative mussel of hyperbranched cation Closing object and being made into concentration is that binder aqueous solution is spare.
Commercially available graphene oxide solution can be used in step (B), oxygen can also be prepared by existing Hummers method Graphite alkene solution.
In step (C), thin polymer film is immersed in the binder aqueous solution prepared in step (A) first, impregnates one It takes out, and is cleaned using deionized water, then thin polymer film is put into baking oven and is dried after the section time；Later by thin polymer film It is immersed in the graphene oxide solution prepared in step (B), is taken out after being soaked for a period of time, and cleaned using deionized water, Thin polymer film is put into baking oven again and is dried, obtains the thin polymer film that surface is graphene layer, illumination curing bonds later Agent.The thin polymer film formed in step (C), surface is stained with one layer of graphene layer by adhesive phase.Preferably, gather Polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride can be used by closing object film (PVC), the drug packages thin polymer film such as polybutylene terephthalate (PBT) (PBT).Preferably, above-mentioned cleaning cleaning polyalcohol is thin The time of film is 30 seconds.
In step (D), it is water-soluble that the thin polymer film prepared in step (C) is immersed in the adhesive prepared in step (A) In liquid, taken out after being soaked for a period of time, and cleaned using deionized water, then thin polymer film is put into baking oven and is dried；Later Thin polymer film is immersed in the graphene oxide solution prepared in step (B), is taken out after being soaked for a period of time, and use is gone Ionized water cleaning, then thin polymer film is put into baking oven and is dried, the graphene number of plies on thin polymer film increases by one layer, later Illumination curing adhesive.Preferably, the time of above-mentioned cleaning cleaning polyalcohol film is 30 seconds.
Later, it repeats the above steps, so that the graphene layer of polymeric film surface coating reaches the required number of plies, preferably Ground, the number of plies of graphene layer are 1~30 layer.
After the completion of graphene layer coating, thin polymer film is put into reducing agent aqueous solution, is obtained after being heated to reflux condensation Packaging composite film.The reducing agent can be any one of sodium ascorbate, hydroiodic acid, hydrazine hydrate, sodium borohydride.
In the technical scheme, the imitative mussel polymer of hyperbranched cation includes more ortho-phenolic hydroxyl benzophenone alkene acyls Amine monomers and cationic monomer.Preferably, more ortho-phenolic hydroxyl benzophenone acrylamide monomers are 2,3,4- trihvdroxvbenzoyls To benzoyl-(2- amino-ethyl) acrylamide, 2,3- dihydroxybenzoyls are to benzoyl-(2- amino-ethyl) acryloyl Amine or 2, benzoyl-(2- amino-ethyl) acrylamide between 3,4- trihvdroxvbenzoyls, above-mentioned more ortho-phenolic hydroxyl benzophenone Acrylamide monomer can be synthesized by esterification commonly used in the art, or by commercially available；Cationic monomer is N- (2- Amino-ethyl) (methyl) acrylamide hydrochloride, N- (3- aminopropyl) (methyl) acrylamide hydrochloride, N- (4- amino fourth Base) (methyl) acrylamide hydrochloride, N- (6- Aminohexyl) (methyl) acrylamide hydrochloride and 2- amino-ethyl) (first Any one of base) acrylate hydrochloride.
Has a large amount of free catechol group in more ortho-phenolic hydroxyl benzophenone acrylamide monomers, catechol group is in sun Catechol group can be improved in the presence of ionic end groups by synergistic effect to the binding force of polymer film layer.In addition, big A series of intermolecular interaction such as model moral of different intensity can be passed through by measuring free catechol group and cation group Hua Li, hydrogen bond and cation-pi interaction force etc. make the imitative mussel polymer of hyperbranched cation to multiple polymers film Layer all has good adhesion property.Therefore, more ortho-phenolic hydroxyl benzophenone acrylamide monomers and cationic monomer are contained Binding strength obtained by the hyperbranched imitative mussel polymer of cation between adhesive and polymer film layer significantly improves.
The hyperbranched imitative mussel polymer of cation further includes photoresponse monomer.Preferably, the photoresponse monomer can be 4- azido -2,3,5,6- tetrafluoro benzoyls-(2- amino-ethyl) acrylamide, 4- azido -2,3,5- trifluoro-benzene formyl - (2- amino-ethyl) acrylamide, 4- azido -2,3- tetrafluoro benzoyl-(2- amino-ethyl) acrylamide, 4- azido-benzene Formyl-(2- amino-ethyl) acrylamide it is any.
The photoresponse monomer and graphene molecules are there are other than molecular separating force, and photoresponse monomer generates under illumination effect Phenyl ring free radical, phenyl ring free radical can occur chemical reaction and form covalent bond, greatly with C-H key in attack graphene molecules Ground improves the bond strength between polymer and graphene molecules.
It can be seen that adhesive prepared by the hyperbranched imitative mussel polymer of cation increases adhesive and gathers significantly Close the adhesive strength of object film layer and the bond strength of adhesive and graphene layer.Less adhesive can be used The bonding of strength is completed, adhesive phase thickness is reduced, so that under the premise of overall thickness is constant, gross mass does not dramatically increase, stone The number of plies of black alkene layer can be substantially improved, and steam penetrating capacity, the oxygen transit dose of packaging composite film produced are substantially reduced, Tensile strength dramatically increases, and can meet the needs of drug packages material well.
Moreover, in the prior art, on the polymer film before spraying binder, it usually needs to thin polymer film Carry out sided corona treatment.In the application, more ortho-phenolic hydroxyl benzophenone acrylamide monomers contain a large amount of catechol group, Ke Yiyu Polymeric film surface forms various types of intermolecular forces such as hydrogen bond, Van der Waals force, cation pi active force etc., thus Well in conjunction with polymeric film surface, even if not having corona step, binder aqueous solution can also be coated in poly- well It closes in object film layer, eliminates corona step, not only reduce process costs, also simplify processing step；Meanwhile it is of the invention Reaction condition is mild, soaking technology can be completed at normal temperatures and pressures, and soaking time is short, when the graphene number of plies is less than 10 When layer, the total duration of immersion is no more than 2 hours, is effectively shortened working hour, has extensive promotional value.
As a kind of preferred preparation process of the imitative mussel polymer of hyperbranched cation of the invention, the step (A) The following steps are included:
(A1) initiator, RAFT reagent and the first reaction mixture are added into the container equipped with DMF, it is anti-forms second Answer mixture；
(A2) the second reaction mixture is stirred to uniform, in logical argon gas removing reaction system oxygen；
(A3) it heats, the second reaction mixture of stirring is reacted；
(A4) after the product for reaching required molecular weight, in air by reaction system exposure, and fast quickly cooling in a cold water bath But to terminate reaction；
(A5) it purifies to obtain the imitative mussel polymer of hyperbranched cation；
(A6) the imitative mussel polymer of hyperbranched cation is configured to binder aqueous solution；
In above-mentioned steps, first reaction mixture includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cation Monomer, photoresponse monomer, polyethylene glycol diene acid esters and polyethylene glycol olefin(e) acid ester.
Firstly, by initiator, RAFT reagent, more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer, photoresponse Monomer, polyethylene glycol diene acid esters and polyethylene glycol olefin(e) acid ester are added to the burning of the round bottom equipped with DMF (N,N-dimethylformamide) It in bottle and stirs evenly, it is preferable that the concentration of initiator is 0.012M, is passed through argon gas later to remove the oxygen in reaction system Gas, it is preferable that the time that is passed through of argon gas is to go out for 20~25 minutes.Round-bottomed flask is put into oil bath later and heats and stirs, it is excellent Selection of land, oil bath temperature are 60~90 DEG C, and mixing speed is 600~800rpm.Reaction is until reach expected conversion ratio, and obtain After the product of required molecular weight, in air by reaction system exposure, and round-bottomed flask is put into cold bath and makes reactant It is fast cooling.The imitative mussel polymer of hyperbranched cation of light brown is obtained after purified product later, it is preferable that used in purifying Solvent be methylene chloride and ether.After purification, the imitative mussel polymer of hyperbranched cation is configured to concentration is 0.5~5mg/ The binder aqueous solution of mL.
Preferably, the polyethylene glycol diene acid esters is polyethyleneglycol diacrylate or glycol dimethacrylates Ester, polyethylene glycol diene acid esters are used to adjust the esterification degree of polymer；The polyethylene glycol olefin(e) acid ester is methoxypolyethylene glycol third Olefin(e) acid ester or methoxypolyethylene glycol methacrylate, polyethylene glycol olefin(e) acid ester are used to adjust the solubility of polymer, it is preferable that Wherein the molecular weight of polyethylene glycol is 200~6000.
Further, more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer, photoresponse monomer, poly- second The molar percentage of glycol olefin(e) acid ester and polyethylene glycol diene acid esters is successively are as follows: and 20%~40%, 30%~40%, 1%~ 5%, 20%~40%, 5%~10%.
Further, in step (A1), the molar ratio of the initiator, RAFT reagent and the first reaction mixture is 1:2: 100。
Further, the initiator be 1,1 '-azo it is bis- (cyclohexane carbonitrile, 2,2'- azo two (2- methyl propionitrile) or 4,4'- azos are bis- (4- cyanopentanoic acid), the RAFT reagent be 2- (dodecyl trithiocarbonic acid ester group) -2 Methylpropionic acid, 4- cyano -4- (phenyl formyl sulfenyl) valeric acid and 2- cyano -2- propyl -4- cyano diphenyl disulfide are for any in carbonic ester Kind.
As a kind of preferred preparation process of graphene oxide solution of the invention, the step (B) includes following step It is rapid:
(B1) graphite powder is added in the concentrated sulfuric acid, potassium permanganate is stirring evenly and then adding into ice-water bath, control water-bath temperature Degree is 10-15 DEG C, is reacted 2 hours；
(B2) reaction solution is moved into isothermal reaction 30min in 35 DEG C of water-baths, continues to stir, and distillation is added into reaction solution Water controls temperature at 80 DEG C later, reacts 15 minutes；
(B3) a certain amount of 15% hydrogen peroxide is added into reaction solution until bubble generates, filtering while hot and with hydrochloric acid and going Ion water washing filter cake is in neutrality up to filtrate, and graphene oxide water solution is made；
(B4) using before graphene oxide water solution, graphene oxide water solution is diluted with deionized water and ultrasound 1 is small When, obtain graphene oxide solution.
Above-mentioned technical proposal improves the existing Hummers method for preparing graphene oxide, on the one hand, when reacting total Between less than 3 hours, be greatly shortened the reaction total duration of Hummers method, and without standing, drying, effectively improve Production efficiency；On the other hand, entire reaction process is using water as solvent, and preparation condition is environmentally friendly, and aftertreatment technology is more Simply, production cost is reduced.
Further, before carrying out the step (C), deionized water cleaning cleaning polyalcohol film is used first, by polymer The contaminant removal of film surface adherency.Pollutant by taking out polymeric film surface adherency can further increase bonding The adhesive strength of agent, and finally improve the quality of packaging composite film product.
Further, in the step (C) and step (D), the mass fraction of binder aqueous solution is 0.01%, aoxidizes stone The mass fraction of black alkene solution is 0.01%.
Further, in the step (C) and step (D), soaking time is 4~7 minutes, it is preferable that soaking time is 5 minutes.
Further, reducing agent is hydrazine hydrate aqueous solution in the step (F), and reflux temperature is 60 °, return time 24 Hour.
As a kind of preferred structure of the imitative mussel polymer of the hyperbranched cation of the present invention, the hyperbranched cation is imitative to be made a gift of Shellfish polymer has structure shown in formula I:
In the formula I, x=1~10, y=20~80, z=30~80, w=5~20, u=20~80, K=1~5, n= 10~50, m=5~30；
In the formula I, R1Any one of group shown in the formula II,
In the formula I, R2Any one of group shown in the formula III,
Under light conditions, the covalent bond between the fluoro substituents and graphene of photoresponse group can be broken or combine, into And the bond strength between polymer and graphene can be changed according to intensity of illumination, enable the adhesive strength of adhesive It is adjusted according to specific requirements, is more suitable for graphene film packaging material.Preferably, in formula I, K=1~3, n=20~ 30, m=10~20.
Compared to traditional small molecule adhesive and common polymer adhesive, it is disclosed in this invention it is hyperbranched sun from The imitative mussel polymer of son has the excellent non-selective adhesion property of imitative mussel, good biocompatibility and adhesive strength adjustable Property.
Further, the degree of polymerization of the imitative mussel polymer of hyperbranched cation is 100~400.
Compared with prior art, the present invention having the following advantages and benefits:
1, in the present invention, more ortho-phenolic hydroxyl benzophenone acrylamide monomers contain a large amount of catechol group, can with it is poly- It closes object film surface and forms various types of intermolecular forces such as hydrogen bond, Van der Waals force, cation pi active force etc., thus very Well in conjunction with polymeric film surface, even if not having corona step, binder aqueous solution can also be coated in polymerization well In object film layer, corona step is eliminated, process costs are not only reduced, also simplifies processing step；
2, reaction condition of the present invention is mild, soaking technology can be completed at normal temperatures and pressures, and soaking time is short, when described When graphene number of plies is less than 10 layers, the total duration of immersion is no more than 2 hours, is effectively shortened working hour, has extensive promote Value；
3, the present invention by the adhesive of the imitative mussel polymer preparation of hyperbranched cation increase significantly adhesive with The adhesive strength and adhesive of polymer film layer and the bond strength of graphene layer, can be used less adhesive i.e. The bonding of achievable strength, adhesive phase thickness are reduced, so that under the premise of overall thickness is constant, gross mass does not dramatically increase, The number of plies of graphene layer can be substantially improved, and steam penetrating capacity, the oxygen transit dose of packaging composite film produced obviously drop Low, tensile strength dramatically increases, and can meet the needs of drug packages material well；
4, the present invention improves the existing Hummers method for preparing graphene oxide, on the one hand, reaction total time is not Foot 3 hours, is greatly shortened the reaction total duration of Hummers method, and without standing, drying, effectively improve life Produce efficiency；On the other hand, entire reaction process is using water as solvent, and preparation condition is environmentally friendly, and aftertreatment technology is simpler, Reduce production cost.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this The restriction of invention.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art Conventional method known to member can be prepared, such as photoresponse monomer can be synthesized by esterification, more ortho-phenolic hydroxyl benzophenone Acrylamide monomer can according to [J] Polymer Bulletin, 2012,68,441-452, Tetrahedron Letters, Mode disclosed in 2008,49,1336-1339 synthesizes.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze the preparation of pure or adhesive The purity requirement of field routine.
The expression way of the substituent group is not particularly limited in the present invention, is all made of table well known to those skilled in the art Up to mode, those skilled in the art are based on common sense, can be according to its meaning of its expression way correct understanding.
All raw materials of the present invention, the trade mark and abbreviation belong to this field routine trade mark and abbreviation, each trade mark and abbreviation In the field of its associated uses be it is explicit, those skilled in the art according to the trade mark, abbreviation and corresponding purposes, It can be commercially available or be prepared by a conventional method to obtain from city's mid-sales.
Embodiment 1:
Prepare the imitative mussel polymer P 1 of hyperbranched cation:
By benzoyl-(2- amino-ethyl) acrylamide between 2,3,4- trihvdroxvbenzoyls, N- (2- amino-ethyl) (first Base) acrylamide hydrochloride, 4- azido -2,3,5,6- phenyl tetrafluoride carboxyethyl amine (methyl) acrylamides, polyethylene glycol first Ether acrylate (PEGMEA), (PEGDEA, the ethylene glycol degree of polymerization are 22) to be added with RAFT reagent to polyethyleneglycol diacrylate Bis- (4- cyanopentanoic acid) concentration of initiator 4,4'- azo are in the N,N-dimethylformamide solution of 0.012M.Wherein, PEGMEA The middle ethylene glycol degree of polymerization is that the ethylene glycol degree of polymerization is that 22,4,4'- azos are bis- (4- cyanopentanoic acid) in 15, PEGDEA, RAFT reagent The molar ratio of the first reaction mixture constituted with all monomers for participating in polymerization is 1:2:100.2,3,4- trihydroxy benzene first Benzoyl-(2- amino-ethyl) acrylamide between acyl group: N- (2- amino-ethyl) (methyl) acrylamide hydrochloride: 4- nitrine Base -2,3,5,6- phenyl tetrafluoride carboxyethyl amine (methyl) acrylamide: the molar percentage of PEGDMEA:PEGEA is 40%: 30%:5%:15%:10%.After mixing evenly by resulting second reaction mixture, lead to 20~25min of argon gas to remove wherein Oxygen.Mixed system is placed in 70 DEG C, is stirred to react under conditions of 700rmp and divides needed for reach expected conversion ratio, obtaining The product of son amount.At the end of reaction, in air by reaction system exposure, and it is quickly cooled down in cold water and terminates reaction.With two After product is further purified in chloromethanes and ether, the imitative mussel polymer P 1 of the hyperbranched cation of light brown adhesive is obtained.Later The imitative mussel polymer P 1 of hyperbranched cation is dissolved in second alcohol and water (volume ratio 1:1), obtaining mass fraction is 0.01% Binder aqueous solution S1.
The structure of the hyperbranched imitative mussel polymer P 1 of cation are as follows:
The map testing result of the structure is 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)。
Embodiment 2:
Prepare the imitative mussel polymer P 2 of hyperbranched cation:
By 2,3,4- trihvdroxvbenzoyl paraphenylene terephthalamide ethyl (methyl) acrylamide hydrochlorides, N- (3- aminopropan Base) (methyl) acrylamide hydrochloride, 4- azido -2,3,5,6- phenyl tetrafluoride carboxyethyl amine (methyl) acrylamides, poly- second Initiator 2,2'- is added in glycol methyl ether acetate (PEGMEA), polyethyleneglycol diacrylate (PEGDEA) and RAFT reagent (the 2- methyl propionitrile) concentration of azo two is in the N,N-dimethylformamide solution of 0.012M.Wherein, ethylene glycol is poly- in PEGMEA Right is that the ethylene glycol degree of polymerization is 10,2,2'- azos two (2- methyl propionitrile), RAFT reagent and all participations in 45, PEGDEA The molar ratio for the first reaction mixture that the monomer of polymerization is constituted is 1:2:100.2,3,4- trihvdroxvbenzoyl benzoyl Amine ethyl (methyl) acrylamide hydrochloride: N- (3- aminopropyl) (methyl) acrylamide hydrochloride: azido -2,3 4-, 5,6- phenyl tetrafluoride carboxyethyl amine (methyl) acrylamide: the molar percentage of PEGDEA:PEGMEA is 20%:33%:2%: 35%:10%.After mixing evenly by the second reaction mixture of gained, lead to 20~25min of argon gas and remove oxygen therein.It will mix Zoarium system is placed in 70 DEG C, is stirred to react under conditions of 700rmp up to reaching expected conversion ratio, obtains the product of required molecular weight. At the end of reaction, in air by reaction system exposure, and it is quickly cooled down in cold water and terminates reaction.With methylene chloride and ether After product is further purified, the imitative mussel polymer P 2 of the hyperbranched cation of light brown adhesive is obtained.Later by it is hyperbranched sun from The imitative mussel polymer P 2 of son is dissolved in second alcohol and water (volume ratio 1:1), and acquisition mass fraction is 0.01% binder aqueous solution S2。
The structure of the hyperbranched imitative mussel polymer P 2 of cation are as follows:
The map testing result of the structure is 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-)；
19F NMR(188MHz,DMSO-D6) δ (ppm): -134.69~-134.88 (2F), -147.58~-147.71 (2F)。
Embodiment 3:
Prepare the imitative mussel polymer P 3 of hyperbranched cation:
By 2,3- dihydroxybenzoyl benzoates amine ethyl (methyl) acrylamide hydrochloride, N- (4- amino fourth Base) (methyl) acrylamide hydrochloride, 4- azido-benzoyl ethylamine (methyl) acrylamide, methoxypolyethylene glycol propylene Acid esters (PEGMEA), polyethyleneglycol diacrylate (PEGDEA) and RAFT reagent 2- (dodecyl trithiocarbonic acid ester group)- It is molten that the N,N-dimethylformamide that (the 2- methyl propionitrile) concentration of initiator 2,2'- azo two is 0.012M is added in 2- methylpropanoic acid In liquid.Wherein, the ethylene glycol degree of polymerization is that the ethylene glycol degree of polymerization is 8,2,2'- azo, two (2- methyl in 5, PEGDEA in PEGMEA Propionitrile), the molar ratio for the first reaction mixture that RAFT reagent and all monomers for participating in polymerization are constituted is 1:2:100.2, 3- dihydroxybenzoyl benzoates amine ethyl (methyl) acrylamide hydrochloride: N- (4- aminobutyl) (methyl) propylene Amide hydrochloride: 4- azido-benzoyl ethylamine (methyl) acrylamide: the molar percentage of PEGDEA:PEGMEA is 25%:35%:5%:30%:5%.After mixing evenly by gained mixed solution, lead to 20~25min of argon gas and remove oxygen therein Gas.Mixed system is placed in 70 DEG C, is stirred to react under conditions of 700rmp up to reaching expected conversion ratio, obtains required molecular weight Product.At the end of reaction, in air by reaction system exposure, and it is quickly cooled down in cold water and terminates reaction.Use dichloromethane After product is further purified in alkane and ether, the imitative mussel polymer P 3 of the hyperbranched cation of light brown adhesive is obtained.It will surpass later Branched cationic is imitated mussel polymer P 3 and is dissolved in second alcohol and water (volume ratio 1:1), and obtaining mass fraction is 0.01% bonding Agent aqueous solution S3.
The structure of the hyperbranched imitative mussel polymer P 3 of cation are as follows:
The map testing result of the structure is 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-)。
Embodiment 4:
Prepare Key works Drug packing film M1, M2 and M3:
Firstly, the graphene oxide solution that mass fraction is 0.01% is prepared by existing Hummers method；
Then, three pieces of PET films are cleaned, removes the pollutant on PET film surface；
Three pieces of PET films after cleaning are separately immersed in the binder aqueous solution S1 prepared in 1~embodiment of embodiment 3 It is impregnated in~S3 5 minutes, is then cleaned 30 seconds with deionized water, PET film is put into later in 40 DEG C of baking oven and is dried；Again PET film is put into graphene oxide solution and is impregnated 5 minutes, is then cleaned 30 seconds with deionized water, later by PET film It is put into 40 DEG C of baking oven and dries, form the PET film that graphene number of plies is 1 layer；Then the distance 25 under 1000W medium pressure mercury lamp Centimeters expose 10 seconds with solidification adhesive layer, improve bonding intensity；
Above-mentioned soaking technology is repeated later, until the graphene number of plies of PET film is 30 layers.
Finally PET film is put into hydrazine hydrate aqueous solution, and as a child obtains stone with reflux condensation mode 24 in 60 DEG C of heating Packaging composite film M1, M2 and the M3 that the black alkene number of plies is 30 layers.
Embodiment 5:
Comparative example 1 uses PVC solid medicinal stiff sheet, and comparative example 2 uses PVDC solid medicinal stiff sheet.
Same thickness, pharmaceutical packaging composite membrane M1, M2 of quality, M3, comparative example 1 and comparative example are detected according to national standards 2 physical parameter, obtained physical parameter are as shown in table 1:
The physical parameter of each packaging composite film of table 1
Project Unit M1 M2 M3 Comparative example 1 Comparative example 2
Steam penetrating capacity g/m2.atm.day 0.28 0.35 0.33 1.01 0.42
Oxygen transit dose cc/m2.atm.day 0.19 0.26 0.31 12.27 0.523
Tensile strength (vertical/horizontal) MPa 65.3/64.7 63.9/62.7 64.1/63.4 66.2/65.3 56.7/55.7
Heat sealing strength N/15mm 10.9 11.1 10.8 11.5 10.8
Heavy metal % <0.0001 <0.0001 <0.0001 <0.0001 <0.0001
Readily oxidizable substance ml <1.5 <1.5 <1.5 <1.5 <2
Nonvolatile matter mg <25 <30 <30 <30 <30
Total number of bacteria A/cm2 <1000 <1000 <1000 <1000 <1000
Total number of molds A/cm2 <100 <100 <100 <100 <100
Escherichia coli A/cm2 0 0 0 0 0
As it can be seen from table 1 under identical quality and thickness, compared to comparative example 1 and comparative example 2, Examples 1 to 3 Prepared Key works Drug packing is decreased obviously with the steam penetrating capacity and oxygen transit dose of film M1, M2 and M3, is effectively prevented The micro-molecular gas such as oxygen and vapor penetrate into packaging material, avoid the active constituent in drug that oxidation deterioration, containment occurs Phenomena such as microbial reproduction, to extend the shelf-life of drug.
Embodiment 6
On the basis of embodiment 4, the preparation method of redox graphene solution is improved.
The 23ml concentrated sulfuric acid is added in 1 gram of graphite powder, is placed in ice-water bath, stirs, add the Gao Meng of 2.5g Sour potassium controls 10~15 DEG C of bath temperature and reacts 2 hours, reaction solution is moved into isothermal reaction 30min in 35 DEG C of water-baths, phase later Between continue to stir, 80ml distilled water is then added into reaction solution, and controls temperature in 80 DEG C of reaction 15min, then to reaction solution For the hydrogen peroxide of middle addition a certain amount of 15% until bubble generates, filtering while hot simultaneously washs filter cake with hydrochloric acid and deionized water until filtering Liquid is in neutrality, and it is spare that graphene oxide aqueous dispersions are made.
In the technical solution, total time is reacted less than 3 hours, the reaction total duration of Hummers method, and nothing is greatly shortened Need stand, drying and etc., effectively improve production efficiency；On the other hand, entire reaction process is using water as solvent, system Standby condition environmental protection, and aftertreatment technology is simpler, reduces production cost.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include Within protection scope of the present invention.

Claims (10)

1. a kind of production technology of packaging composite film, which comprises the following steps:
(A) the imitative mussel polymer of hyperbranched cation is prepared using reversible addion-fragmentation chain transfer polymerization, then will be prepared The hyperbranched imitative mussel polymer of cation is configured to binder aqueous solution, wherein the hyperbranched imitative mussel polymer of cation Including more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer and photoresponse monomer；
(B) prepare graphene oxide solution；
(C) thin polymer film is immersed in the binder aqueous solution prepared in step (A), is taken out after being soaked for a period of time, and Thin polymer film is dried；Thin polymer film is immersed in later in the graphene oxide solution prepared in step (B), impregnates one It is taken out after the section time, and thin polymer film is dried, obtain the thin polymer film that surface is graphene layer, illumination curing is viscous later Mixture；
(D) thin polymer film that the surface prepared in step (C) is graphene layer is immersed in the adhesive prepared in step (A) In aqueous solution, taken out after being soaked for a period of time, and thin polymer film is dried；Thin polymer film is immersed in step (B) later In the graphene oxide solution of middle preparation, taken out after being soaked for a period of time, and thin polymer film is dried, on thin polymer film Graphene number of plies increases by one layer, later illumination curing adhesive；
(E) step (D) is repeated, until the graphene number of plies on thin polymer film reaches the required number of plies；
(F) thin polymer film prepared in step (E) is put into reducing agent aqueous solution, is packed after being heated to reflux condensation Composite membrane.
2. a kind of production technology of packaging composite film according to claim 1, which is characterized in that the step (A) includes Following steps:
(A1) initiator, RAFT reagent and the first reaction mixture are added into the container equipped with DMF, it is mixed forms the second reaction Close object；
(A2) the second reaction mixture is stirred to uniform, in logical argon gas removing reaction system oxygen；
(A3) it heats, the second reaction mixture of stirring is reacted；
(A4) after the product for reaching required molecular weight, by reaction system exposure in air, and be quickly cooled down in a cold water bath with Terminate reaction；
(A5) it purifies to obtain the imitative mussel polymer of hyperbranched cation；
(A6) the imitative mussel polymer of hyperbranched cation is configured to binder aqueous solution；
In above-mentioned steps, first reaction mixture include more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer, Photoresponse monomer, polyethylene glycol diene acid esters and polyethylene glycol olefin(e) acid ester.
3. a kind of production technology of packaging composite film according to claim 2, which is characterized in that more ortho-phenolic hydroxyls two Benzophenone acrylamide monomer, cationic monomer, photoresponse monomer, polyethylene glycol olefin(e) acid ester and polyethylene glycol diene acid esters mole Percentage is successively are as follows: 20%~40%, 30%~40%, 1%~5%, 20%~40%, 5%~10%.
4. a kind of production technology of packaging composite film according to claim 1, which is characterized in that the step (B) includes Following steps:
(B1) graphite powder is added in the concentrated sulfuric acid, potassium permanganate is stirring evenly and then adding into ice-water bath, control bath temperature is It 10-15 DEG C, reacts 2 hours；
(B2) reaction solution is moved into isothermal reaction 30min in 35 DEG C of water-baths, continues to stir, and distilled water is added into reaction solution, Control temperature is reacted 15 minutes at 80 DEG C later；
(B3) a certain amount of 15% hydrogen peroxide is added into reaction solution until bubble generates, filtering while hot and with hydrochloric acid and deionization Water washing filter cake is in neutrality up to filtrate, and graphene oxide water solution is made；
(B4) using before graphene oxide water solution, graphene oxide water solution deionized water is diluted into simultaneously ultrasound 1 hour, is obtained Obtain graphene oxide solution.
5. a kind of production technology of packaging composite film according to claim 1, which is characterized in that carry out the step (C) Before, deionized water cleaning cleaning polyalcohol film is used first, the contaminant removal that polymeric film surface is adhered to.
6. a kind of production technology of packaging composite film according to claim 1, which is characterized in that the step (C) and step Suddenly in (D), the mass fraction of binder aqueous solution is 0.01%, and the mass fraction of graphene oxide solution is 0.01%.
7. a kind of production technology of packaging composite film according to claim 1, which is characterized in that the step (C) and step Suddenly in (D), soaking time is 4~7 minutes.
8. a kind of production technology of packaging composite film according to claim 1, which is characterized in that in the step (F) also Former agent is hydrazine hydrate aqueous solution, and reflux temperature is 60 °, and return time is 24 hours.
9. a kind of production technology of packaging composite film described according to claim 1~any one of 8, which is characterized in that described The hyperbranched imitative mussel polymer of cation has structure shown in formula I:
In the formula I, x=1~10, y=20~80, z=30~80, w=5~20, u=20~80, K=1~5, n=10~ 50, m=5~30；
In the formula I, R1Any one of group shown in the formula II,
In the formula I, R2Any one of group shown in the formula III,
10. a kind of production technology of packaging composite film according to claim 9, which is characterized in that it is described it is hyperbranched sun from The degree of polymerization of the imitative mussel polymer of son is 100~400.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104774295A (en) * 2015-04-09 2015-07-15 清华大学 Macromolecular adhesive containing dopamine phosphate ester structure as well as preparation method and application of macromolecular adhesive
WO2017004174A1 (en) * 2015-06-30 2017-01-05 Purdue Research Foundation Adhesives and methods of making the same
CN107880305A (en) * 2017-12-19 2018-04-06 中物院成都科学技术发展中心 A kind of polymer composites of high air-liquid barrier property and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104774295A (en) * 2015-04-09 2015-07-15 清华大学 Macromolecular adhesive containing dopamine phosphate ester structure as well as preparation method and application of macromolecular adhesive
WO2017004174A1 (en) * 2015-06-30 2017-01-05 Purdue Research Foundation Adhesives and methods of making the same
CN107880305A (en) * 2017-12-19 2018-04-06 中物院成都科学技术发展中心 A kind of polymer composites of high air-liquid barrier property and preparation method thereof

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