CN109096517A - A kind of drug packages film and preparation method thereof - Google Patents
A kind of drug packages film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of drug packages films and preparation method thereof, wherein drug packages film includes the graphite ene coatings of thin polymer film and coating on the polymer film, the graphite ene coatings include graphene and Photocurable adhesive, the Photocurable adhesive includes the imitative mussel polymer of hyperbranched cation, and the hyperbranched imitative mussel polymer of cation includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer and photoresponse monomer.The present invention increases the adhesive strength of Photocurable adhesive and thin polymer film by the Photocurable adhesive of the imitative mussel polymer preparation of hyperbranched cation significantly, thus, the combination of the graphite ene coatings that Photocurable adhesive and graphene are constituted on the polymer film is stronger, it is more preferable to coat effect, simultaneously, just because of coating effect significantly improves, thus the preparation process of drug packages film is simplified to a certain extent.
Description
Technical field
The present invention relates to packaging material fields, and in particular to a kind of drug packages film and preparation method thereof.
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 body substance and other low molecular weight substances is difficult to meet the requirement of most drugs packaging.Oxygen and vapor
Equal micro-molecular gas will lead to the active constituent in drug to the infiltration of packaging material and oxidation deterioration occur, and then cause micro- life
Phenomena such as breeding of object, direct consequence are exactly to greatly shorten the shelf-life of drug.So improving plastic film packaging material
To the micro-molecular gas such as barrier property of oxygen, vapor and assigns its anti-microbial property and be 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, prepare the method for graphene composite film first is that the graphene for preparing graphene solution and binder solution applies
Layer solution, and graphene coating solution is coated on polymeric film surface to form graphene composite film.But due to existing
The contact area of some adhesives and graphene, thin polymer film is small, reaction site is few, so that adhesive and thin polymer film,
The adhesive strength of graphene is low, in turn results in that coating effect is bad, and coating processes are complicated；Meanwhile existing graphene composite film
Steam penetrating capacity and oxygen transit dose it is still higher, hardly possible meet most drugs packaging requirement.
Summary of the invention
The purpose of the present invention is to provide a kind of drug packages films and preparation method thereof, to solve existing packaging film barrier
The problem that performance is poor and the coating effect of graphite ene coatings is bad, coating processes are complicated.
The present invention is achieved through the following technical solutions:
A kind of drug packages film, the graphite ene coatings including thin polymer film and coating on the polymer film are described
Graphite ene coatings include graphene and Photocurable adhesive, and the Photocurable adhesive includes that the imitative mussel of hyperbranched cation is poly-
Object is closed, the hyperbranched imitative mussel polymer of cation includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cationic monomer
And photoresponse monomer.
In the prior art, the Chinese patent of Publication No. CN108165120A discloses the high-termal conductivity for radiator
Graphite ene coatings and preparation method, adhesive and thin polymer film used in this method, graphene adhesive strength compared with
It is low, cause coating effect poor, and coating processes are complicated.Moreover, in order to make the adhesive strength in graphite ene coatings meet medicine
The demand of object packaging film, improves accounting of the adhesive in graphite ene coatings, and the adhesive of high accounting reduces final finished
Translucency；Moreover, the steam penetrating capacity of existing graphene composite film and oxygen transit dose are still higher, and hardly possible is full
The requirement of sufficient most drugs packaging.
To solve the above-mentioned problems, the present invention provides a kind of drug packages film, same as the prior art, the drugs
Packaging film includes the graphite ene coatings of thin polymer film and coating on the polymer film.Preferably, polymer film layer
Polypropylene (PP) can be used, polyethylene (PE), polyethylene terephthalate (PET), polyvinyl chloride (PVC), gathered to benzene
The drug packages thin polymer films such as dioctyl phthalate butanediol ester (PBT)；Graphite ene coatings include graphene and Photocurable adhesive.
Unlike the prior art, Photocurable adhesive used in the present invention includes that the imitative mussel of hyperbranched cation is poly-
Object is closed, the hyperbranched imitative mussel polymer of cation includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers and cation mono
Body.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) acrylamide or 2,3,4- trihydroxies
Benzoyl-(2- amino-ethyl) acrylamide between benzoyl, above-mentioned more ortho-phenolic hydroxyl benzophenone acrylamide monomers can lead to
Esterification synthesis commonly used in the art is crossed, or by commercially available；Cationic monomer is N- (2- amino-ethyl) (methyl)
Acrylamide hydrochloride, N- (3- aminopropyl) (methyl) acrylamide hydrochloride, N- (4- aminobutyl) (methyl) acryloyl
Amine hydrochlorate, N- (6- Aminohexyl) (methyl) acrylamide hydrochloride and 2- amino-ethyl) (methyl) acrylate hydrochloride
Any one of.
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
Bonding intensity obtained by the hyperbranched imitative mussel polymer of cation between adhesive and thin polymer film 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 -
Benzoyl-(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 be occurred chemical reaction and be formed covalent bond, pole with C-H key in attack graphene molecules
The earth improves the bond strength between polymer and graphene molecules.
It can be seen that Photocurable adhesive prepared by the hyperbranched imitative mussel polymer of cation increases light and consolidates significantly
Change the adhesive strength of adhesive and thin polymer film, thus, the graphite ene coatings that Photocurable adhesive and graphene are constituted are poly-
The combination closed on object film is stronger, and coating effect is more preferable, meanwhile, just because of coating effect significantly improves, thus certain
The preparation process of drug packages film is simplified in degree.In addition, since the adhesive strength of Photocurable adhesive and graphene is also shown
It writes and increases, therefore can reduce accounting of the Photocurable adhesive in graphite ene coatings, and then improve the saturating of drug packages film
Photosensitiveness.Moreover, compared to existing graphene composite film, drug packages film obtained by the present invention reduces significantly
Steam penetrating capacity and oxygen transit dose can satisfy the requirement of most drugs packaging.
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=2~10, y=10~30, z=40~100, w=1~15, u=10~40, K=0~7, n
=10~80, m=5~45；
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 fluoro substituents and graphene in photoresponse monomer can be broken or combine,
So that the bond strength between polymer and graphene can change according to intensity of illumination, so that the adhesive strength of adhesive
It can be adjusted according to specific requirements, be more suitable for graphene film packaging material.Preferably, hyperbranched cation is imitative makes a gift of
The degree of polymerization of shellfish polymer is 100~400.Preferably, in formula I, K=1~3, n=10~30, m=20~45.
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 can
Tonality.
Further, the mass ratio of graphene and Photocurable adhesive is 1:0.01~1:0.2 in the graphite ene coatings.
The present invention passes through the adhesive strength of Photocurable adhesive and graphene, can reduce Photocurable adhesive in graphite ene coatings
Accounting, and then improve drug packages film translucency.Middle graphene and adhesive 1:0.2~1:0.8 compared to the prior art
Quality accounting, the present invention in the mass ratio of graphene and Photocurable adhesive be 1:0.01~1:0.2.
Further, the graphite ene coatings with a thickness of 20~500nm, it is preferable that graphite ene coatings with a thickness of 20
~60nm.The thickness is not higher than the average value of existing graphite ene coatings, but has to steam penetrating capacity, oxygen transit dose
High barrier.
Further, the thin polymer film be polypropylene, polyethylene, polyethylene terephthalate, polyvinyl chloride,
Any one of polybutylene terephthalate (PBT).
The present invention also provides the preparation method of said medicine packaging film, the preparation method the following steps are included:
(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；
(B) redox graphene solution is prepared；
(C) it is molten that the binder aqueous solution prepared in step (A) is added to the redox graphene prepared into step (B)
It in liquid, stirs evenly, is configured to graphene coating solution；
(D) graphene coating solution is coated on thin polymer film, is dried to form graphite ene coatings.
In step (A), it is imitative that hyperbranched cation is made using reversible addion-fragmentation chain transfer polymerization (RAFT polymerization)
Mussel polymer, which includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, cation
It is spare to be made into binder aqueous solution later by monomer and photoresponse monomer for the obtained imitative mussel polymer of hyperbranched cation.
In step (B), commercially available graphene oxide can be used, it is molten graphene oxide can also to be prepared by Hummers method
Liquid restores graphene oxide using reducing agent to obtain the redox graphene solution of stably dispersing later.Preferably, also
Former agent is one of sodium ascorbate, hydroiodic acid, hydrazine hydrate, sodium borohydride.
In step (C), binder aqueous solution is added into redox graphene solution and is stirred evenly, it is preferable that
Mixing time is 5~60min, and mixing speed is 200~500rpm, and uniform and stable graphite ene coatings are formed after the completion of stirring
Solution for standby.Before carrying out step (C), clear water cleaning cleaning polyalcohol film surface can be used to remove the pollutant on surface,
Improve the adhesion strength of polymeric film surface.
In the prior art, on the polymer film before graphene coated coating solution, 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, can be with
Various types of intermolecular forces such as hydrogen bond, Van der Waals force, cation pi active force etc. are formed with polymeric film surface,
Thus well in conjunction with polymeric film surface, therefore even if there is no corona step, binder aqueous solution also can be well
Coated in corona step on polymer film layer, is eliminated, not only reduces process costs, simplifies processing step, also shorten
Working hour has extensive promotional value.
In step (D), after graphite ene coatings are coated on thin polymer film, graphene coating solution is dried at 40 DEG C
Dry-cure 8 hours, the graphite ene coatings being adhered on thin polymer film are formed after drying.
In above-mentioned technique, the graphene coating solution coated on the polymer film makes drug packages film have high-barrier
Performance；Meanwhile coating processes are simple, it is only necessary to coat a graphene coating solution；Moreover, preparation process is true
Under the premise of protecting preferable coating effect, eliminate corona step used in the prior art, not only reduce technique at
Originally, processing step is simplified, also shortens working hour, there is extensive promotional value.
Further, 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, form second
Reaction 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 the binder aqueous solution that concentration is 0.1~5mg/mL；
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.
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
To after the product of required molecular weight, in air by reaction system exposure, and round-bottomed flask is put into and makes to react in cold bath
System fast cooling.The imitative mussel polymer of hyperbranched cation of light brown is obtained after purified product later, it is preferable that purifying
Solvent used is methylene chloride and ether.After purification, the imitative mussel polymer of hyperbranched cation is configured to concentration is 0.1
The binder aqueous solution of~5mg/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, preferably
Ground, 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；Reaction temperature in step (A3) is 60~90 DEG C, and mixing speed is 600~800rmp.
Further, in step (D), the coating processes of graphene coating solution are roll coating process, spin coating proceeding or blade coating
Technique.Quickly and easily graphene coating solution can be coated on by roll coating process, spin coating proceeding or doctor blade process poly-
It closes on object film.Graphene coating solution technique is not suitable for spraying process or dipping process.
The present invention improves existing redox graphene solution manufacturing method.
The step of preparation process of drug packages film (B) specifically includes the 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 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 the graphene oxide solution that concentration is 0.1-5.0mg/mL；
(B5) graphene oxide solution of preparation is mixed with reducing agent according to mass ratio 1:3, normal-temperature reaction 2 minutes, it
It is diluted to the redox graphene solution of various concentration afterwards.
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.
Compared with prior art, the present invention having the following advantages and benefits:
1, the present invention increases light by the Photocurable adhesive of the imitative mussel polymer preparation of hyperbranched cation significantly
The adhesive strength of solidification adhesive and thin polymer film, thus, the graphite ene coatings that Photocurable adhesive and graphene are constituted exist
Combination on thin polymer film is stronger, and coating effect is more preferable, meanwhile, just because of coating effect significantly improves, thus one
Determine the preparation process that drug packages film is simplified in degree；
2, of the invention since the adhesive strength of Photocurable adhesive and graphene also dramatically increases, it is solid to can reduce light
Change accounting of the adhesive in graphite ene coatings, and then improves the translucency of drug packages film；
3, compared to existing graphene composite film, drug packages film obtained by the present invention reduces vapor significantly
Transit dose and oxygen transit dose can satisfy the requirement of most drugs packaging；
4, coating processes of the present invention are simple, it is only necessary to coat a graphene coating solution；Moreover, preparation process
Under the premise of ensuring preferably to coat effect, corona step used in the prior art is eliminated, technique is not only reduced
Cost simplifies processing step, also shortens working hour, has extensive promotional value；
5, 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 are according to the trade mark, abbreviation and corresponding use
On the way, 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,
The 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 in PEGMEA,
The molar ratio for the first reaction mixture that RAFT reagent and all monomers for participating in polymerization are constituted is 1:2:100.2,3,4- tri-
Benzoyl-(2- amino-ethyl) acrylamide between hydroxy benzoyl: N- (2- amino-ethyl) (methyl) acrylamide hydrochloric acid
Salt: 4- azido -2,3,5,6- phenyl tetrafluoride carboxyethyl amine (methyl) acrylamide: the molar percentage of PEGDMEA:PEGEA
For 40%:30%:5%:15%:10%.After mixing evenly by resulting second reaction mixture, lead to 20~25min of argon gas to remove
Remove oxygen therein.Mixed system is placed in 70 DEG C, is stirred to react under conditions of 700rmp up to reaching expected conversion ratio, is obtained
To the product of required molecular weight.At the end of reaction, in air by reaction system exposure, and it is quickly cooled down and terminates in cold water
Reaction.After product is further purified with methylene chloride and ether, the imitative mussel polymerization of the hyperbranched cation of light brown adhesive is obtained
Object P1.The imitative mussel polymer P 1 of hyperbranched cation is dissolved in second alcohol and water (volume ratio 1:1) later, obtaining concentration is
The binder aqueous solution S1 of 15wt%.
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 production of required molecular weight
Object.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
After product is further purified in ether, the imitative mussel polymer P 2 of the hyperbranched cation of light brown adhesive is obtained.It later will be hyperbranched
The imitative mussel polymer P 2 of cation is dissolved in second alcohol and water (volume ratio 1:1), and it is water-soluble to obtain the adhesive that concentration is 15wt%
Liquid 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) third
Acrylamide 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 molecule
The product of amount.At the end of reaction, in air by reaction system exposure, and it is quickly cooled down in cold water and terminates reaction.Use dichloro
After product is further purified in methane and ether, the imitative mussel polymer P 3 of the hyperbranched cation of light brown adhesive is obtained.Later will
The hyperbranched imitative mussel polymer P 3 of cation is dissolved in second alcohol and water (volume ratio 1:1), obtains the bonding that concentration is 15wt%
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 concentration is 15mg/mL is prepared by existing Hummers method, will prepare
Graphene oxide solution mixed with the hydrazine hydrate solution of 98wt% with the mass ratio of 1:3, normal-temperature reaction is diluted to after 2 minutes
The redox graphene solution of various concentration；
Then, three pieces of PET films are cleaned, and be ultrasonically treated to remove the pollutant on PET film surface；
Binder aqueous solution S1~S3 prepared in 1~embodiment of embodiment 3 is added molten to redox graphene
It in liquid, stirs evenly, is configured to graphene coating solution L1, L2 and L3.Wherein, in L1, L2 and L3, graphene and adhesive
Ratio be 1:0.06~1:0.08.
Graphene coating solution L1~L3 is distinguished into roller coating, spin coating, blade coating in three pieces of PET films, and is dried at 40 DEG C
Processing 8 hours, to form graphite ene coatings.Ultimately form graphene coating layer thickness be 40nm drug packages film M1, M2 and
M3。
Embodiment 5:
Comparative example 1 uses PVC solid medicinal stiff sheet, and comparative example 2 uses PVDC solid medicinal stiff sheet.
Drug packages film M1, M2, M3, comparative example 1 and the comparison of identical graphene coating layer thickness are detected according to national standards
The physical parameter of example 2, obtained physical parameter are as shown in table 1:
The physical parameter of each drug packages film of table 1
| Project | Unit | M1 | M2 | M3 | Comparative example 1 | Comparative example 2 |
| Steam penetrating capacity | g/m2.atm.day | 0.28 | 0.36 | 0.38 | 1.01 | 0.42 |
| Oxygen transit dose | cc/m2.atm.day | 0.23 | 0.29 | 0.33 | 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 later,
Period continues to stir, and 80ml distilled water is then added into reaction solution, and controls temperature in 80 DEG C of reaction 15min, then to reaction
Be added in liquid a certain amount of 15% hydrogen peroxide until bubble generate, while hot filter and with hydrochloric acid and deionized water wash filter cake up to
Filtrate is in neutrality, and it is spare that graphene oxide aqueous dispersions are made；Before graphene oxide water solution, by graphene oxide solution
With deionized water dilution ultrasound 1 hour, the graphene oxide solution that concentration is 0.1-5mg/mL is obtained.
It is later the hydrazine hydrate solution of 15mg/mL graphene oxide solution and 98wt% with the matter of 1:3 by the concentration of preparation
Amount normal-temperature reaction 2 minutes, is then diluted to the redox graphene solution of required concentration than mixing.
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 using water as solvent,
Preparation 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 used to limit this hair the foregoing is merely a specific embodiment of the invention
Bright protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all
It is included within protection scope of the present invention.
Claims (10)
1. a kind of drug packages film, the graphite ene coatings including thin polymer film and coating on the polymer film, the stone
Black ene coatings include graphene and Photocurable adhesive, which is characterized in that the Photocurable adhesive includes hyperbranched cation
Imitative mussel polymer, the hyperbranched imitative mussel polymer of cation includes more ortho-phenolic hydroxyl benzophenone acrylamide monomers, sun
Ion monomer and photoresponse monomer.
2. a kind of drug packages film according to claim 1, which is characterized in that the hyperbranched imitative mussel polymerization of cation
Object has structure shown in formula I:
In the formula I, x=2~10, y=10~30, z=40~100, w=1~15, u=10~40, K=0~7, n=10
~80, m=5~45；
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,
3. a kind of drug packages film according to claim 1, which is characterized in that graphene and light in the graphite ene coatings
The mass ratio of solidification adhesive is 1:0.01~1:0.2.
4. a kind of drug packages film according to claim 1, which is characterized in that the graphite ene coatings with a thickness of 20~
500nm。
5. a kind of drug packages film according to claim 1, which is characterized in that the thin polymer film is polypropylene, gathers
Ethylene, polyethylene terephthalate, any one of polyvinyl chloride, polybutylene terephthalate (PBT).
6. a kind of preparation method of drug packages film according to any one of claims 1 to 5, which is characterized in that including following
Step:
(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；
(B) redox graphene solution is prepared；
(C) binder aqueous solution prepared in step (A) is added to the redox graphene solution prepared into step (B)
In, it stirs evenly, is configured to graphene coating solution；
(D) graphene coating solution is coated on thin polymer film, is dried to form graphite ene coatings.
7. a kind of preparation method of drug packages film according to claim 6, 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 the binder aqueous solution that concentration is 0.1~5mg/mL；
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.
8. a kind of preparation method of drug packages film according to claim 7, 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%.
9. a kind of preparation method of drug packages film according to claim 7, which is characterized in that described in step (A1)
The molar ratio of initiator, RAFT reagent and the first reaction mixture is 1:2:100；Reaction temperature in step (A3) is 60~90
DEG C, mixing speed is 600~800rmp.
10. a kind of preparation method of drug packages film according to claim 6, which is characterized in that in step (D), graphite
The coating processes of ene coatings solution are roll coating process, spin coating proceeding or doctor blade process.
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| CN103692743A (en) * | 2013-12-19 | 2014-04-02 | 重庆绿色智能技术研究院 | Graphene composite thin film material and preparation method thereof |
| WO2017004174A1 (en) * | 2015-06-30 | 2017-01-05 | Purdue Research Foundation | Adhesives and methods of making the same |
| CN108165120A (en) * | 2018-01-17 | 2018-06-15 | 苏州烯时代材料科技有限公司 | For the high-termal conductivity graphite ene coatings and preparation method and application of radiator |
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| WO2017004174A1 (en) * | 2015-06-30 | 2017-01-05 | Purdue Research Foundation | Adhesives and methods of making the same |
| CN108165120A (en) * | 2018-01-17 | 2018-06-15 | 苏州烯时代材料科技有限公司 | For the high-termal conductivity graphite ene coatings and preparation method and application of radiator |
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| CN112280087A (en) * | 2020-09-30 | 2021-01-29 | 浙江大学衢州研究院 | High-gas-barrier-property oriented composite film |
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