An intrinsic barrier water and oxygen barrier film coating and its preparation method and application

Abstract

The application discloses an intrinsic barrier water and oxygen barrier film coating and a preparation method and application thereof, and comprises multifunctional thiol monomers, multifunctionality unsaturated hydrocarbon monomers, stabilizers and photoinitiators, wherein the multifunctionality unsaturated hydrocarbon monomers comprise any one or a combination of at least two of unsaturated amide monomers, unsaturated amine monomers, alkenyl ether monomers, alkenyl carboxylic acid monomers, alkenyl carboxylic acid ester monomers, aromatic alkenyl monomers or polymeric diene monomers. The application can obtain a product with high crosslinking density by selecting specific multifunctional olefin monomers and reacting with thiol monomers, and the high crosslinking density can make the obtained film layer have better water and oxygen barrier performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis and functional materials technology, specifically relating to an intrinsically barrier water and oxygen barrier film coating, its preparation method, and its application. Background Technology

[0002] Thiol-olefin click chemistry has been widely studied and applied in fields such as photocurable coatings, optical adhesives, three-dimensional micro / nano fabrication, and biomedical materials due to its outstanding advantages such as mild reaction conditions, fast curing speed, low volume shrinkage, and insensitivity to oxygen. However, the polymer network structure formed after curing of traditional thiol-olefin systems is usually relatively loose, with weak intermolecular chain interactions and large free volume. This results in generally insufficient intrinsic barrier capabilities against small molecule gases (such as oxygen and water vapor) and organic solvents, and also generally suffers from low hardness, poor solvent resistance, and susceptibility to aging and cracking. This defect seriously restricts the engineering application of such materials in fields with stringent barrier performance requirements, such as high-end packaging, flexible electronic barrier layers, high-antioxidant food packaging, and organic photovoltaic cell encapsulation.

[0003] To address the aforementioned issues, existing technologies primarily focus on monomer molecular structure design to enhance the intrinsic barrier properties of polymers. Theoretically, higher crosslinking density leads to better barrier performance. Therefore, increasing crosslinking density is one of the most direct and effective strategies. This is mainly achieved by increasing monomer functionality (e.g., copolymerizing tetrafunctional thiols with trifunctional olefins) or shortening the crosslinking segment length, thereby reducing the free volume of the polymer, restricting the thermal motion of molecular chains, and thus extending the diffusion path of gas molecules.

[0004] On the other hand, almost all commercially available and literature-reported thiol-olefin monomers are derived from petroleum-based chemicals. For example, common monomers such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), and triallyl isocyanurate all rely on fossil fuels. This not only contradicts the current concept of sustainable green chemistry, but also introduces inherent defects in the ester bonds within the monomer structure: ester bonds are relatively weakly polar, making it difficult to form strong hydrogen bond networks; furthermore, ester bonds are prone to hydrolysis under humid, hot, or acidic / alkaline conditions, leading to a shortened material lifespan and limiting their application in environmentally sensitive fields such as flexible electronics and biomedicine.

[0005] Meanwhile, besides insufficient barrier properties, the stability of traditional thiol-olefin resin systems also faces severe challenges: conventional systems lack acid-base regulation mechanisms, making them highly susceptible to temperature, oxygen, and light exposure during production and storage. Thiol groups within the system are prone to spontaneous oxidative crosslinking, and olefin monomers are prone to premature self-polymerization, leading to abnormally high glue viscosity, gel deterioration, and severely shortened product shelf life. Furthermore, hydrolysis of ester bonds in humid or alkaline environments further degrades the resin's storage and use stability. These stability issues significantly shorten the pot life of single-component or two-component resins, limiting their practical application in industrial-grade formulations.

[0006] Meanwhile, conventional systems suffer from difficulty in precisely controlling the curing reaction rate, resulting in poor overall curing uniformity. Coatings are prone to defects such as surface stickiness, pinholes, shrinkage, and warping. Furthermore, they exhibit extremely poor adhesion to polar substrates, making them unsuitable for high-end applications such as precision bonding, coating protection, microelectronic packaging, and flexible material lamination. In addition, traditional systems use a single combination of initiators and stabilizers, lacking synergistic acid-based additives, which cannot adapt to the rapid reaction characteristics of high-functionality monomers. This leads to an imbalance in the system's acid-base environment, easily resulting in localized over-curing or incomplete curing, significantly reducing the stability and product qualification rate of the finished adhesive.

[0007] Therefore, there is an urgent need for a thiol-olefin material with excellent barrier properties, excellent storage stability, and environmental friendliness to meet application requirements. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide an intrinsically barrier water and oxygen barrier film coating, its preparation method, and its application.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides an intrinsically barrier water and oxygen barrier film coating, comprising a multifunctional thiol monomer, a multifunctional unsaturated hydrocarbon monomer, a stabilizer, and a photoinitiator, wherein:

[0011] The multifunctional unsaturated hydrocarbon monomers include any one or a combination of at least two of the following: unsaturated amide monomers, unsaturated amine monomers, alkenyl ether monomers, alkenyl carboxylic acid monomers, alkenyl carboxylic acid ester monomers, aromatic olefin monomers, or polymeric diene monomers.

[0012] This invention selects specific multifunctional olefin monomers that do not contain ester bonds, and reacts them with thiol monomers to obtain products with high crosslinking density. The higher crosslinking density enables the obtained membrane to have better water and oxygen barrier properties. At the same time, it reduces the introduction of ester bonds, reduces the possibility of ester bond hydrolysis, and improves the service life of the membrane.

[0013] Furthermore, this invention utilizes unsaturated monomers with amide bonds, which possess higher hydrolytic stability and stronger hydrogen bond formation ability. In products containing amide groups, the NH bond in each amide group can act as a strong hydrogen bond donor, while the C=O bond can act as a hydrogen bond acceptor. The resulting hydrogen bonding significantly enhances the physical crosslinking density between polymer chains. This invention has found that, at the same crosslinking density, polymers containing amide bonds often have lower free volume and higher gas barrier properties than polymers containing ester bonds. Therefore, by introducing unsaturated hydrocarbon monomers with amide bonds, this invention enables the obtained products to possess superior water and oxygen barrier properties.

[0014] Moreover, compared to the existing conventional thiol monomers and olefin monomers which are prone to Michael addition side reactions, the unsaturated hydrocarbon monomers with amide bonds preferred in this invention have better antioxidant properties, hydrolysis resistance and storage stability. When applied to water-oxygen barrier membrane coatings, they can reduce or even avoid the occurrence of side reactions, improve the pot life of the coatings, and make them meet the actual application requirements of industrial-grade formulations.

[0015] Preferably, the unsaturated amide monomer is obtained by reacting a polybasic acid and / or a polybasic acyl chloride with an amine monomer containing an unsaturated bond.

[0016] Preferably, the unsaturated amine monomer is obtained by reacting an electrophilic reagent containing active chlorine with an amine monomer containing an unsaturated bond.

[0017] The unsaturated amide monomer of the present invention is obtained by reacting a polybasic acid and / or a polybasic acyl chloride with an amine monomer containing an unsaturated bond. The polybasic acid can undergo an amidation reaction with the amine monomer, and the polybasic acyl chloride can undergo a nucleophilic substitution reaction with the amine monomer to generate an amide, so that the obtained monomer has both unsaturated and amide bonds.

[0018] The unsaturated amine monomers of the present invention are obtained by nucleophilic substitution reaction using an electrophilic reagent containing active chlorine and an amine monomer with unsaturated bonds as raw materials.

[0019] Preferably, the polyacids include any one or a combination of at least two of the following: oxalic acid, succinic acid, glutaric acid, fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, citric acid, cis-aconitic acid, isocitric acid, 1,2,3-propanetricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, D-gluconic acid, mucoic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, 2,2'-biphenyldicarboxylic acid, phenylpentacarboxylic acid, phenylpentacarboxylic acid, tetrahydrofuranpentacarboxylic acid, L-rhamnopentacarboxylic acid, galactospentacarboxylic acid, cyclopentanepentacarboxylic acid, inositol hexacarboxylic acid, phenylhexacarboxylic acid, cyclohexane hexacarboxylic acid, mannose hexacarboxylic acid, xylose hexacarboxylic acid, or sorbitol hexacarboxylic acid.

[0020] Preferably, the polyacryl chloride includes any one or a combination of at least two of succinyl chloride, adipicoyl chloride, sebacyl chloride, maleic acid chloride, fumaric acid chloride, itaconic acid chloride, 2,5-furandicarboxylic acid chloride, triacryl citrate chloride, 1,2,3,4-butanetetracarboxylic acid chloride, or pyromellitic acid tricarboxylic acid chloride.

[0021] Preferably, the electrophilic reagent containing active chlorine includes cyanuric chloride.

[0022] Preferably, the amine monomer with unsaturated bonds includes any one or a combination of at least two of allylamine, diallylamine, propargylamine, dipropargylamine, N-methylallylamine, N-ethylallylamine, N-allylethylenediamine, N-propargylethylamine, N-allylpropylamine, or N-propargylisopropylamine.

[0023] This invention selects biologically derived polybasic acids and / or polyacrylamides, which can react with amine monomers to obtain thiol-olefin monomers that have both reactivity and functionality. Using biomass raw materials not only conforms to the development direction of green and low carbon, but also these natural skeletons often have rigid cyclic structures or polar groups such as hydroxyl groups, which is beneficial to improving the packing density and barrier properties of polymers.

[0024] Preferably, the molar ratio of the polybasic acid and / or polyacryl chloride to the amine monomer with unsaturated bonds is 1:(2-10), for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 or any range between the above values, preferably 1:(3-7).

[0025] Preferably, the molar ratio of the electrophilic reagent containing active chlorine to the amine monomer with unsaturated bonds is 1:(2-10), for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10 or any range between the above values, preferably 1:(3-7).

[0026] The synthesis methods of the unsaturated amide monomers and unsaturated amine monomers provided by this invention are simple, and their application in water-oxygen barrier coatings can improve the barrier performance of water-oxygen barrier membranes.

[0027] Preferably, the molar ratio of the polyfunctional thiol monomer to the polyfunctional unsaturated hydrocarbon monomer is 1:(0.2-5), for example, 1:0.2, 1:1, 1:2, 1:3, 1:4, 1:5 or any of the above values, preferably 1:(0.8-1.2).

[0028] Preferably, the content of the stabilizer is 0.1-5% based on the total weight of the intrinsically blocking water and oxygen barrier coating, for example, 0.1%, 1%, 2%, 3%, 4%, 5% or any of the above values, preferably 0.5-3%.

[0029] Preferably, the content of the photoinitiator is 0.1-5% based on the total weight of the intrinsically blocking water and oxygen barrier film coating, for example, 0.1%, 1%, 2%, 3%, 4%, 5% or any of the above values, preferably 1-3%.

[0030] Preferably, the multifunctional thiol monomer comprises any one or a combination of at least two of the following: 1,2-ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, dimercaptodiethylene glycol, 3,6-dioxa-1,8-octanedithiol, trimethylolpropane tris(3-mercaptopropionic acid), trimethylolethane tris(3-mercaptopropionic acid), pentaerythritol tetra(3-mercaptopropionic acid), pentaerythritol tetra(mercaptoacetic acid), dipentaerythritol hexa(3-mercaptopropionic acid), or 1,3,5-tris(3-mercaptopropoxyethyl)isocyanurate.

[0031] Preferably, the multifunctional unsaturated hydrocarbon monomer includes any one or a combination of at least two of the following: unsaturated amide monomers, unsaturated amine monomers, diethylene glycol divinyl ether, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, bisphenol A diallyl ether, allyl glycidyl ether, triallyl cyanurate, 1,2-polybutadiene, or divinylbenzene.

[0032] Preferably, the photoinitiator includes 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651), 1-hydroxycyclohexylphenyl methyl ketone (Irgacure 184), 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (Irgacure 907), 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur 1173), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl 2,4,6-trimethylbenzoylphenylphosphonate (TPO-L), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure). 819), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, isopropylthioxanthone (ITX), 2,4-diethylthioxanthone (DETX), 2-chlorothioxanthone (CTX), 1-chloro-4-propoxythioxanthone (CPTX), 2-ethylanthraquinone, 9,10-dimethoxyanthracene, 2 Any one or a combination of at least two of the following: 4-bis(trichloromethyl)-6-phenyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, N-phenylglycine, triethanolamine, methyldiethanolamine, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, or phenothiazine.

[0033] Preferably, the stabilizer includes any one or a combination of at least two of phenolic stabilizers, nitrogen oxide stabilizers, acid stabilizers, or other stabilizers.

[0034] Preferably, the phenolic stabilizer comprises any one or a combination of at least two of the following: hydroquinone, catechol, resorcinol, p-methoxyphenol, o-methoxyphenol, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), tetramethylbisphenol A, bisphenol A, bisphenol F, o-tert-butylhydroquinone, mono-tert-butylhydroquinone, 2-tert-pentylhydroquinone, 3-methylcatechol, 4-methylcatechol, or 2-hydroxybiphenyl.

[0035] Preferably, the nitrogen-oxygen stabilizer comprises 2,2,6,6-tetramethylpiperidine nitroxide radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-methoxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-amino-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-acetoxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 1-oxo-2,2,6,6-tetramethyl-4-piperidine stearate, bis(2,2,6,6-tetramethyl-1-piperidineoxy) sebacate, and 2,2,6,6-tetramethyl-4-piperidine. The benzoate nitroxide radical, 1-oxo-2,2,6,6-tetramethylpiperidine-4-carboxylic acid, 5-azaspirocyclic nitroxide radical, 3-methyl-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-benzyloxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-glycidyl ether-2,2,6,6-tetramethylpiperidine nitroxide radical, polytetramethylpiperidine nitroxide radical, 1-oxo-2,2,5,5-tetramethylpyrrolidine, 3-oxo-2,2,5,5-tetramethylpyrrolidine nitroxide radical, dialkylamine nitroxide radical, morpholine nitroxide radical, or imidazoalkyl nitroxide radical, or any one or a combination of at least two of these radicals.

[0036] Preferably, the acid stabilizers include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, citric acid, tartaric acid, malic acid, lactic acid, glycolic acid, benzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, and salicylic acid. Gallic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, ascorbic acid, oleic acid, acrylic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, phosphorous acid, hypophosphoric acid, metaphosphoric acid, pyrophosphoric acid, dithionite, silicic acid, fluorosilicic acid, fluoroboric acid, selenic acid, telluric acid, arsenic acid, arsenicite, metaboric acid, or tetraboric acid.

[0037] Preferably, the other stabilizers include any one or a combination of at least two of the following: benzoquinone, methylbenzoquinone, di-tert-butylbenzoquinone, phenothiazine, aluminum salt of N-nitrosophenylhydroxylamine, triphenylphosphine, triphenyl phosphite, triisooctyl phosphite, antioxidant 1010, antioxidant 1076, antioxidant 245, antioxidant 168, antioxidant 618, phenyl salicylate, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hindered amine light stabilizer 944, or hindered amine light stabilizer 770.

[0038] Preferably, based on the total weight of the intrinsically barrier water and oxygen barrier film coating, the content of the phenolic stabilizer is 0.01-5%, for example, 0.1%, 1%, 2%, 3%, 4%, 5%, or any of the above values; the content of the nitrogen oxide stabilizer is 0.01-5%, for example, 0.1%, 1%, 2%, 3%, 4%, 5%, or any of the above values; and the content of the acid stabilizer is 0.01-5%, for example, 0.1%, 1%, 2%, 3%, 4%, 5%, or any of the above values.

[0039] The present invention can improve the stability of the water-oxygen barrier film coating by selecting at least one of phenolic stabilizers, nitrogen-oxygen stabilizers and acid stabilizers.

[0040] Preferably, the mass ratio of the stabilizer to the photoinitiator is 1:(0.1-10), for example, 1:0.1, 1:2, 1:4, 1:5, 1:6, 1:8, 1:10 or any of the above values, preferably 1:(0.3-3).

[0041] Meanwhile, by optimizing the mass ratio of stabilizer and photoinitiator, the present invention can adjust the curing time of the water-oxygen barrier film coating from 2 seconds to about 10 minutes.

[0042] The present invention preferably uses biomass platform compounds as the backbone, and introduces thiol and olefin reactive groups through amidation reaction to achieve synergy of high crosslinking density and strong hydrogen bond network at the molecular level. After curing, no additives are required, and the resulting water and oxygen barrier membrane has both excellent gas barrier performance and hydrolytic stability.

[0043] This invention optimizes the raw material ratio and component synergy system of thiol-olefin adhesives, precisely introduces suitable organic and inorganic acid composite additives for acid-base regulation, and combines functional monomers with amide structures and multi-specification high-functionality thiol and olefin monomers. It also incorporates a photoinitiation system and a precise polymerization inhibition and stabilization system. Through a composite scheme of amide polar toughening modification, high-functionality high-density crosslinking, and precise acid-controlled reaction, this invention effectively solves the problems of poor storage stability, numerous curing defects, loose crosslinking, weak adhesion, limited mechanical properties, and insufficient weather resistance of traditional adhesives. The resulting water-oxygen barrier film coating has a long storage period, controllable curing rate, dense crosslinking network, excellent adhesion performance, resistance to yellowing and aging, and compatibility with multiple substrates, significantly expanding the industrial application scenarios of thiol-olefin adhesives.

[0044] Secondly, the present invention provides a method for preparing an intrinsically barrier water and oxygen barrier film coating, the method comprising: mixing a multifunctional thiol monomer, a multifunctional unsaturated hydrocarbon monomer, a stabilizer and a photoinitiator uniformly to obtain the intrinsically barrier water and oxygen barrier film coating.

[0045] The multifunctional unsaturated hydrocarbon monomers include any one or a combination of at least two of the following: unsaturated amide monomers, unsaturated amine monomers, alkenyl ether monomers, alkenyl carboxylic acid monomers, alkenyl carboxylic acid ester monomers, aromatic olefin monomers, or polymeric diene monomers.

[0046] Preferably, the multifunctional unsaturated hydrocarbon monomer includes an unsaturated amide monomer, and the method for preparing the unsaturated amide monomer includes:

[0047] The unsaturated amide monomer is obtained by reacting a polybasic acid and / or a polyacrylamide chloride with an amine monomer containing an unsaturated bond.

[0048] Preferably, the multifunctional unsaturated hydrocarbon monomer includes an unsaturated amine monomer, and the preparation method of the unsaturated amine monomer includes:

[0049] The unsaturated amine monomer is obtained by nucleophilic substitution reaction of an electrophilic reagent containing active chlorine and an amine monomer with an unsaturated bond.

[0050] The preparation methods for unsaturated amide monomers and unsaturated amine monomers provided by this invention are efficient, mild, and have high atom economy, making them suitable for large-scale production.

[0051] In this invention, the reaction is carried out, depending on the monomer actually selected, in the presence of an optional condensing agent, an optional acid-binding agent, and an optional catalyst.

[0052] Preferably, the preparation method further includes post-treatment after the reaction is completed, the post-treatment including: washing with alkaline water, distillation or recrystallization to obtain the unsaturated amide monomer / unsaturated amine monomer.

[0053] Preferably, the reaction is carried out in solution, and the solvent used in the solution includes any one or a combination of at least two of the following: water, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, dichloromethane, chloroform, toluene, xylene, n-hexane, cyclohexane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or ethylene glycol monomethyl ether, more preferably dichloromethane and / or dimethylformamide.

[0054] Preferably, the condensing agent comprises any one or a combination of at least two of the following: 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-hydroxybenzotriazole, 6-chloro-1-hydroxybenzotriazole, benzotriazol-1-yloxytripyrrolidinylphosphine hexafluorophosphate, 2-(7-azabenzotriazol)-tetramethylurea hexafluorophosphate, or 2-(1H-benzotriazol-1-yl)tetramethylurea tetrafluoroborate; more preferably, it is any one or a combination of at least two of the following: 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, dicyclohexylcarbodiimide, or diisopropylcarbodiimide.

[0055] Preferably, the acid-binding agent includes triethylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, N-methylmorpholine, N-ethylmorpholine, tri-n-propylamine, tri-n-butylamine, N,N-dimethylaniline, N,N-diethylaniline, imidazole, 2-methylimidazolium, triethanolamine, diethanolamine, N-methylpyrrolidine, tetramethylethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[5.4.0]undec-7-ene, etc. The combination of any one or at least two of the following: cyclo[2.2.2]octane, anhydrous sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, trisodium phosphate, disodium hydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, calcium oxide, magnesium oxide, borax, sodium acetate, or potassium acetate, more preferably, any one or at least two of the following: triethylamine, diisopropylethylamine, pyridine, or anhydrous sodium carbonate.

[0056] Preferably, the catalyst comprises any one or a combination of at least two of 4-dimethylaminopyridine, pyridine, or imidazole, more preferably 4-dimethylaminopyridine.

[0057] Preferably, in the post-treatment, the alkaline solution is any one or a combination of at least two of sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, or potassium hydroxide solution, with a concentration of 1-10 mol / L, for example, 1 mol / L, 2 mol / L, 5 mol / L, 6 mol / L, 8 mol / L, 10 mol / L, or any range between the above values, preferably 5 mol / L. This invention utilizes alkaline washing to neutralize acidic substances and remove unreacted amines and acids, preventing residual ions (such as chloride ions) from affecting the purity of the product.

[0058] Preferably, the distillation is a heated vacuum distillation, with a pressure of 0.001-0.1 MPa, such as 0.001 MPa, 0.02 MPa, 0.04 MPa, 0.06 MPa, 0.08 MPa, 0.1 MPa or any of the above values, preferably 0.001 MPa; and a heating temperature of 100-200℃, such as 100℃, 120℃, 140℃, 160℃, 180℃, 200℃ or any of the above values, more preferably 150℃.

[0059] Preferably, the solution used for recrystallization is any one or a combination of at least two of the following: water, methanol, ethanol, isopropanol, n-butanol, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, dichloromethane, chloroform, toluene, xylene, n-hexane, cyclohexane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, or ethylene glycol monomethyl ether. More preferably, it is a combination of any one or at least two of the following: dichloromethane, dimethylformamide, water, or ethanol. More preferably, it is a combination of water and ethanol. The volume ratio of water to ethanol is preferably 1:(1-10), for example, 1:1, 1:3, 1:5, 1:7, 1:9, 1:10, or any range between these values. Further preferably, the volume ratio of water to ethanol is 1:(2-5).

[0060] Preferably, the reaction is carried out in solution, wherein the concentration of the organic acid in the solution is 0.1-0.5 mol / L, for example 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L or any range between the above values, preferably 0.3 mol / L.

[0061] Preferably, the reaction temperature is 20-60°C, for example, 20°C, 25°C, 30°C, 35°C, 40°C, 50°C, 60°C or any range of the above values, preferably 40°C, and the reaction time is 2-48 h, for example, 2 h, 10 h, 20 h, 30 h, 40 h, 48 h or any range of the above values, preferably 12 h.

[0062] Thirdly, the present invention provides a water-oxygen barrier membrane, which is made of the intrinsically barrier water-oxygen barrier membrane coating described in the first aspect.

[0063] The present invention also provides a method for preparing the water-oxygen barrier membrane, comprising: coating the water-oxygen barrier membrane coating described in the first aspect to obtain a wet film, subjecting the wet film to UV curing, and optionally aging the cured film to obtain the water-oxygen barrier membrane.

[0064] Preferably, the thickness of the wet film is 50-200 μm, for example, 50 μm, 75 μm, 100 μm, 125 μm, 150 μm, 175 μm, 200 μm or any of the above values.

[0065] Preferably, the light source used for UV curing is a 395 nm LED lamp with a power of 10-100 W, such as 10 W, 25 W, 40 W, 55 W, 70 W, 85 W, 100 W or any of the above values.

[0066] Preferably, the aging temperature is 50-60℃, such as 50℃, 52℃, 54℃, 55℃, 56℃, 58℃, 60℃ or any of the above values, and the time is 10-15 h, such as 10 h, 11 h, 12 h, 13 h, 14 h, 15 h or any of the above values.

[0067] Fourthly, the present invention provides an application of the water-oxygen barrier film as described in the third aspect in flexible electronic packaging, organic photovoltaics, OLED displays, or food and pharmaceutical packaging.

[0068] This invention achieves significant technological advancements and practical benefits by optimizing the synergistic effects of components, introducing acidic additives to precisely regulate the system environment, and combining amide structure modification with high-functionality crosslinking design.

[0069] (1) The present invention preferably uses a compound system of phenolic and nitrogen-oxygen composite stabilizers, combined with acid stabilizers to regulate the overall pH of the glue system, buffering the interference of alkaline impurities in the system, especially suppressing the premature polymerization problem that is very easy to occur in high-functionality monomer systems, effectively preventing thiol oxidation and olefin self-polymerization, completely solving the problems of glue storage gel and viscosity rise, greatly improving the stability of the product at room temperature and extending the shelf life;

[0070] (2) This invention utilizes the catalytic synergistic effect of a photoinitiator system combined with acidic additives to meet the reaction requirements of rapid curing of high-functionality monomers, optimize the efficiency of photoinitiation reaction, solve the problems of incomplete curing of single initiators, poor deep curing, and surface oxygen inhibition, achieve synchronous and uniform curing of the adhesive surface and deep layers, eliminate defects such as adhesive stickiness, pinholes, and uneven curing, and improve the molding quality of high crosslinking density adhesive layers.

[0071] (3) The present invention also introduces amide groups into the system, which have strong polarity and hydrogen bonding, which can effectively make up for the lack of polarity of ordinary thiol-ene systems.

[0072] (4) By selecting high-functionality monomers, the present invention can construct a three-dimensional dense cross-linked network, which greatly improves the cross-linking density, hardness, wear resistance and solvent resistance of the coating. At the same time, amide groups can form a large number of hydrogen bonds between molecular chains, which can play the role of physical cross-linking, toughening and reinforcement, perfectly solving the defect of easy cracking of high cross-linked systems, and achieving both high strength and high toughness.

[0073] (5) Moreover, polar amide groups can effectively activate the surface of polar substrates such as metals, plastics, and glass, significantly improve the interfacial adhesion, and eliminate the problems of delamination and peeling.

[0074] (6) The reaction system described in this invention has mild reaction conditions, controllable dosage of acidic additives, no residual side effects, no need for high temperature heating, rapid curing at room temperature, and is suitable for automated production line. Detailed Implementation

[0075] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0076] The terms "preferred," "more preferably," etc., used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0077] When a numerical range is disclosed in this invention, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Further, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Moreover, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0078] In the description of this invention, the reference term "and / or" includes all and any combination of one or more of the associated listed items.

[0079] In the description of this invention, the terms "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0080] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0081] The partial structures of the unsaturated amide monomer and unsaturated amine monomer described in this invention are as follows:

[0082] ;

[0083] The following provides methods for preparing some unsaturated amide monomers:

[0084] Preparation Example 1-1

[0085] This preparation example provides a method for preparing compound A1, as follows:

[0086] S1. In 600 mL of dichloromethane, add 400 g diallylamine, 10 g 4-dimethylaminopyridine, and 200 g triethylamine, and lower the temperature to 0 °C. Then, slowly add 300 g methacrylic anhydride, and then raise the temperature to room temperature and react for 12 h.

[0087] S2. After the reaction was completed, the reaction solution was washed with 5 mol / L sodium carbonate solution and dried. Dichloromethane was recovered by vacuum distillation and the target product was obtained (yield: 94%).

[0088] Preparation Examples 1-2

[0089] This preparation example provides a method for preparing compound A1, as follows:

[0090] S1. In 600 mL of dichloromethane, add 400 g diallylamine, 10 g 4-dimethylaminopyridine, and 200 g triethylamine, and lower the temperature to 0 °C. Then, slowly add 200 g methacryloyl chloride, and then raise the temperature to room temperature and react for 12 h.

[0091] S2. After the reaction was completed, the reaction solution was washed with 5 mol / L sodium carbonate solution and dried. Dichloromethane was recovered by vacuum distillation and the target product was obtained (yield: 94%).

[0092] Preparation Examples 1-3

[0093] This preparation example provides a method for preparing compound A1, as follows:

[0094] S1. Mix 400 g diallylamine, 10 g 4-dimethylaminopyridine, and 200 g triethylamine, and lower the temperature to 0°C. Then, slowly add 300 g methacrylic anhydride, and then raise the temperature to room temperature and react for 12 hours.

[0095] S2. After the reaction was completed, the reaction solution was washed with 5 mol / L sodium carbonate solution and dried. The target product was obtained by vacuum distillation (yield: 93%).

[0096] Preparation Example 2

[0097] This preparation example provides a method for preparing compound A2, as follows:

[0098] S1. In 200 mL of dichloromethane, 600 g diallylamine, 10 g 4-dimethylaminopyridine, and 200 g triethylamine were added and the temperature was lowered to 0 °C. Then 500 g pyromellitic acid chloride was slowly added, and the mixture was then brought to room temperature and reacted for 12 hours.

[0099] S2. The reaction solution was washed with 5 mol / L sodium carbonate solution, dried, purified by chromatography, and recrystallized with ethanol / water to give a colorless solid (yield: 92%).

[0100] Preparation Example 3

[0101] This preparation example provides a method for preparing compound A3, as follows:

[0102] S1. Add 300 g diallylamine, 300 g potassium carbonate and 184 g cyanuric acid to 800 mL of dioxane, and then raise the temperature to 80 °C and react for 12 h.

[0103] S2. After the reaction was completed, the reaction solution was washed with 5 mol / L sodium carbonate solution, dried, purified by chromatography, and recrystallized with ethanol / water to obtain a colorless solid (yield: 80%).

[0104] Preparation Example 4

[0105] This preparation example provides a method for preparing compound A4, as follows:

[0106] S1. In 600 mL of dichloromethane, add 248 g of 1,2,3,4-tetracarboxybutane, 800 g of EDCI, 10 g of 4-dimethylaminopyridine and 400 g of triethylamine and cool to 0 °C. Then, slowly add 400 g of diallylamine and then raise the temperature to room temperature and react for 12 h.

[0107] S2. After the reaction was completed, the reaction solution was washed with 5 mol / L sodium carbonate solution, dried, purified by chromatography, and recrystallized with ethanol / water to give a colorless solid (yield: 90%).

[0108] The preparation methods for other unsaturated amide monomers are similar, and will not be described in detail here.

[0109] The polyfunctional thiols and polyfunctional unsaturated hydrocarbon monomers used in this invention are as follows:

[0110] Example 1

[0111] This embodiment provides a water-oxygen barrier film coating and the resulting water-oxygen barrier film, as follows:

[0112] (1) Compound A1 and pentaerythritol tetra(3-mercaptopropionate) in a molar ratio of 4:3 were mixed with benzophenone (photoinitiator) and 2,6-di-tert-butyl-p-cresol (stabilizer) and defoamed to obtain the water-oxygen barrier film coating. In the water-oxygen barrier film coating, the concentrations of the photoinitiator and the stabilizer were both 1 wt%.

[0113] (2) A water-oxygen barrier film coating was applied to obtain a wet film with a thickness of 100 μm. The wet film was cured under UV light for 1 min and then aged at 60℃ for 12 h to obtain a water-oxygen barrier film.

[0114] Examples 2-4

[0115] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0116] The difference from Example 1 is that in this example, compound A1 is replaced with compounds A2 (Example 2), A3 (Example 3), and A8 (Example 4), respectively.

[0117] Example 5

[0118] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0119] The difference from Example 1 is that, in this example, compound A1 is replaced with pentaerythritol tetraallyl ether.

[0120] Example 6

[0121] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0122] The difference from Example 1 is that in this example, compound A1 is replaced with 1,6-hexanediol divinyl ether.

[0123] Examples 7-8

[0124] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0125] The difference from Example 1 is that in this example, the molar ratio of compound A1 to compound S1 is 2:1 (Example 7) and 1:2 (Example 8).

[0126] Example 9

[0127] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0128] The difference from Example 1 is that, in this example, the stabilizer is methylbenzoquinone.

[0129] Example 10

[0130] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0131] The difference from Example 1 is that, in this example, the stabilizer is 2,2,6,6-tetramethylpiperidine nitride.

[0132] Example 11

[0133] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0134] The difference from Example 1 is that, in this example, the stabilizer is acetic acid.

[0135] Example 12

[0136] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0137] The difference from Example 1 is that in this example, the stabilizer is a combination of 2,2,6,6-tetramethylpiperidine nitride and acetic acid in a mass ratio of 1:1.

[0138] Example 13

[0139] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0140] The difference from Example 1 is that in this example, the stabilizer is a combination of 2,6-di-tert-butyl-p-cresol, 2,2,6,6-tetramethylpiperidine nitride, and acetic acid in a mass ratio of 1:1:1.

[0141] Examples 14-17

[0142] This embodiment provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0143] The difference from Example 1 is that in this example, the concentration of the stabilizer is adjusted so that the mass ratio of photoinitiator to stabilizer is 3:1 (Example 14), 1:3 (Example 15), 10:1 (Example 16), and 1:10 (Example 17).

[0144] Example 18

[0145] This embodiment provides a water-oxygen barrier film coating and the resulting water-oxygen barrier film, as follows:

[0146] (1) Compound A5 and dipentaerythritol hexa(3-mercaptopropionate) in a molar ratio of 6:5 were mixed with Irgacure 651 (photoinitiator) and 2,6-di-tert-butyl-p-cresol (stabilizer) and defoamed to obtain the water-oxygen barrier film coating. In the water-oxygen barrier film coating, the concentration of photoinitiator was 5 wt% and the concentration of stabilizer was 5 wt%.

[0147] (2) A water-oxygen barrier film coating was applied to obtain a wet film with a thickness of 100 μm. The wet film was cured under UV light for 1 min and then aged at 60℃ for 12 h to obtain a water-oxygen barrier film.

[0148] Comparative Example 1

[0149] This comparative example provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0150] The difference from Example 1 is that, in this comparative example, compound A1 is replaced with triallyl isocyanurate (TAIC).

[0151] Comparative Example 2

[0152] This comparative example provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0153] The difference from Example 1 is that, in this comparative example, compound A1 is replaced with diallyl terephthalate.

[0154] Comparative Example 3

[0155] This comparative example provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0156] The difference from Example 1 is that, in this comparative example, compound A1 is replaced with diallyl fumarate.

[0157] Comparative Example 4

[0158] This comparative example provides a water-oxygen barrier coating and the resulting water-oxygen barrier film.

[0159] The difference from Example 1 is that no stabilizer was added in this comparative example.

[0160] Performance testing:

[0161] The performance of the samples provided in the examples and comparative examples was tested using the following methods:

[0162] (1) Water vapor transmission rate, in g·m -2 ·d -1 The test standard refers to GB / T 26253-2010. The test is conducted using a marked water vapor transmission detector with an infrared sensor. The test temperature is 38℃ and the relative humidity is 90%.

[0163] (2) Storage stability: The storage stability is characterized by viscosity. The viscosity test standard is GB / T 40280-2021. The water-oxygen barrier film coatings obtained in the examples and comparative examples are sealed and stored. During the storage process, the storage stability is judged by testing the viscosity of the samples daily. When the viscosity change rate is ≤5%, it is considered to have good storage stability.

[0164] The test results are as follows:

[0165] Table 1

[0166]

[0167] As can be seen from the examples and performance tests, the water-oxygen barrier membrane coating provided by the present invention has excellent storage stability. It remains stable and does not gel even after 150 days or more of storage, and the curing time is moderate, which improves the service life of the water-oxygen barrier membrane coating. At the same time, the obtained water-oxygen barrier membrane has excellent water-oxygen barrier properties.

[0168] The present invention has been illustrated through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An intrinsically barrier water and oxygen barrier film coating, characterized in that, This includes multifunctional thiol monomers, multifunctional unsaturated hydrocarbon monomers, stabilizers, and photoinitiators, among which: The multifunctional unsaturated hydrocarbon monomers include any one or a combination of at least two of the following: unsaturated amide monomers, unsaturated amine monomers, alkenyl ether monomers, alkenyl carboxylic acid monomers, alkenyl carboxylic acid ester monomers, aromatic olefin monomers, or polymeric diene monomers.

2. The intrinsically barrier water and oxygen barrier film coating according to claim 1, characterized in that, The unsaturated amide monomer is obtained by reacting a polybasic acid and / or a polybasic acyl chloride with an amine monomer containing an unsaturated bond; And / or, the unsaturated amine monomer is obtained by reacting an electrophilic reagent containing active chlorine with an amine monomer containing an unsaturated bond.

3. The intrinsically barrier water and oxygen barrier film coating according to claim 2, characterized in that, The polyacids include any one or a combination of at least two of the following: oxalic acid, succinic acid, glutaric acid, fumaric acid, itaconic acid, 2,5-furandicarboxylic acid, citric acid, cis-aconitic acid, isocitric acid, 1,2,3-propanetricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, D-gluconic acid, mucoic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, 2,2'-biphenyldicarboxylic acid, phenylpentacarboxylic acid, phenylpentacarboxylic acid, tetrahydrofuranpentacarboxylic acid, L-rhamnopentacarboxylic acid, galactospentacarboxylic acid, cyclopentanepentacarboxylic acid, inositol hexacarboxylic acid, phenylhexacarboxylic acid, cyclohexane hexacarboxylic acid, mannose hexacarboxylic acid, xylose hexacarboxylic acid, or sorbitol hexacarboxylic acid. And / or, the polyacryl chloride includes any one or a combination of at least two of succinyl chloride, adipicoyl chloride, sebacic acid chloride, maleic acid chloride, fumaric acid chloride, itaconic acid chloride, 2,5-furandicarboxylic acid chloride, triacryl citrate chloride, 1,2,3,4-butanetetracarboxylic acid chloride or pyromellitic acid tricarboxylic acid chloride; And / or, the electrophilic reagent containing active chlorine includes cyanuric chloride; And / or, the amine monomer with unsaturated bonds includes any one or a combination of at least two of allylamine, diallylamine, propargylamine, dipropargylamine, N-propargylethylamine, N-propargylisopropylamine, N-ethylallylamine, N-allylethylenediamine, N-allylpropylamine or N-methylallylamine.

4. The intrinsically barrier water and oxygen barrier film coating according to claim 2, characterized in that, The molar ratio of the polybasic acid and / or polyacryl chloride to the amine monomer with unsaturated bonds is 1:(2-10); And / or, the molar ratio of the electrophilic reagent containing active chlorine to the amine monomer with unsaturated bonds is 1:(2-10).

5. The intrinsically barrier water and oxygen barrier film coating according to any one of claims 1-4, characterized in that, The molar ratio of the polyfunctional thiol monomer to the polyfunctional unsaturated hydrocarbon monomer is 1:(0.2-5); And / or, based on the total weight of the intrinsically barrier water and oxygen barrier film coating, the content of the stabilizer is 0.1-5%; And / or, based on the total weight of the intrinsically blocking water and oxygen barrier coating, the content of the photoinitiator is 0.1-5%.

6. The intrinsically barrier water and oxygen barrier film coating according to any one of claims 1-4, characterized in that, The multifunctional thiol monomers include any one or a combination of at least two of the following: 1,2-ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, dimercaptodiethylene glycol, 3,6-dioxa-1,8-octanedithiol, trimethylolpropane tris(3-mercaptopropionic acid), trimethylolethane tris(3-mercaptopropionic acid), pentaerythritol tetra(3-mercaptopropionic acid), pentaerythritol tetra(mercaptoacetic acid), dipentaerythritol hexa(3-mercaptopropionic acid), or 1,3,5-tris(3-mercaptopropoxyethyl)isocyanurate. And / or, the multifunctional unsaturated hydrocarbon monomers include any one or a combination of at least two of the following: unsaturated amide monomers, unsaturated amine monomers, triethylene glycol divinyl ether, trimethylolpropane triallyl ether, pentaerythritol tetraallyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, bisphenol A diallyl ether, allyl glycidyl ether, triallyl cyanurate, 1,2-polybutadiene, or divinylbenzene; And / or, the stabilizer includes any one or a combination of at least two of phenolic stabilizers, nitrogen oxide stabilizers, acid stabilizers, or other stabilizers.

7. The intrinsically barrier water and oxygen barrier film coating according to claim 6, characterized in that, The phenolic stabilizers include any one or a combination of at least two of the following: hydroquinone, catechol, resorcinol, p-methoxyphenol, o-methoxyphenol, 2-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 4,4'-methylenebis(2,6-di-tert-butylphenol), tetramethylbisphenol A, bisphenol A, bisphenol F, o-tert-butylhydroquinone, mono-tert-butylhydroquinone, 2-tert-amylhydroquinone, 3-methylcatechol, 4-methylcatechol, or 2-hydroxybiphenyl. And / or, the nitrogen oxide stabilizers include 2,2,6,6-tetramethylpiperidine nitroxide radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-methoxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-oxo-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-amino-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-acetoxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 1-oxo-2,2,6,6-tetramethyl-4-piperidine stearate, bis(2,2,6,6-tetramethyl-1-piperidineoxy) sebacate, and 2,2,6,6-tetramethyl-4-piperidine. The benzoate nitroxide radical, 1-oxo-2,2,6,6-tetramethylpiperidine-4-carboxylic acid, 5-azaspirocyclic nitroxide radical, 3-methyl-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-benzyloxy-2,2,6,6-tetramethylpiperidine nitroxide radical, 4-glycidyl ether-2,2,6,6-tetramethylpiperidine nitroxide radical, polytetramethylpiperidine nitroxide radical, 1-oxo-2,2,5,5-tetramethylpyrrolidine, 3-oxo-2,2,5,5-tetramethylpyrrolidine nitroxide radical, dialkylamine nitroxide radical, morpholine nitroxide radical, or imidazoalkyl nitroxide radical, or any one or a combination of at least two of these radicals. And / or, the acid stabilizers include any one or a combination of at least two of the following: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, heptanoic acid, octanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, citric acid, tartaric acid, malic acid, lactic acid, glycolic acid, benzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, salicylic acid, gallic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, trichloroacetic acid, ascorbic acid, oleic acid, acrylic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, phosphorous acid, hypophosphoric acid, metaphosphoric acid, pyrophosphoric acid, dithionite, silicic acid, fluorosilicic acid, fluoroboric acid, selenic acid, telluric acid, arsenic acid, arsenicite, metaboric acid, or tetraboric acid. And / or, the other stabilizers include any one or a combination of at least two of the following: benzoquinone, methylbenzoquinone, di-tert-butylbenzoquinone, phenothiazine, aluminum salt of N-nitrosophenylhydroxylamine, triphenylphosphine, triphenyl phosphite, triisooctyl phosphite, antioxidant 1010, antioxidant 1076, antioxidant 245, antioxidant 168, antioxidant 618, phenyl salicylate, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hindered amine light stabilizer 944, or hindered amine light stabilizer 770; And / or, based on the total weight of the intrinsically barrier water and oxygen barrier film coating, the content of the phenolic stabilizer is 0.01-5%, the content of the nitrogen oxide stabilizer is 0.01-5%, and the content of the acid stabilizer is 0.01-5%.

8. The intrinsically barrier water and oxygen barrier film coating according to claim 5, characterized in that, The mass ratio of the stabilizer to the photoinitiator is 1:(0.1-10).

9. A method for preparing an intrinsically barrier water-oxygen barrier film coating, characterized in that, The preparation method includes: mixing a multifunctional thiol monomer, a multifunctional unsaturated hydrocarbon monomer, a stabilizer and a photoinitiator evenly to obtain the intrinsically barrier water and oxygen barrier film coating. The multifunctional unsaturated hydrocarbon monomers include any one or a combination of at least two of the following: unsaturated amide monomers, unsaturated amine monomers, alkenyl ether monomers, alkenyl carboxylic acid monomers, alkenyl carboxylic acid ester monomers, aromatic olefin monomers, or polymeric diene monomers.

10. The preparation method according to claim 9, characterized in that, The multifunctional unsaturated hydrocarbon monomers include unsaturated amide monomers, and the preparation method of the unsaturated amide monomers includes: The unsaturated amide monomer is obtained by reacting a polybasic acid and / or a polybasic acyl chloride with an amine monomer containing an unsaturated bond. And / or, the multifunctional unsaturated hydrocarbon monomer includes unsaturated amine monomers, and the preparation method of the unsaturated amine monomer includes: The unsaturated amine monomer is obtained by nucleophilic substitution reaction of an electrophilic reagent containing active chlorine and an amine monomer with an unsaturated bond.

11. A water-oxygen barrier membrane, characterized in that, The water-oxygen barrier membrane is made of the intrinsically barrier water-oxygen barrier membrane coating as described in any one of claims 1-8.

12. The application of the water-oxygen barrier film as described in claim 11 in flexible electronic packaging, organic photovoltaics, OLED displays, or food and pharmaceutical packaging.

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