CN113929867B - Casting film liquid and preparation method thereof, high-barrier composite film and preparation method thereof - Google Patents
Casting film liquid and preparation method thereof, high-barrier composite film and preparation method thereof Download PDFInfo
- Publication number
- CN113929867B CN113929867B CN202111083846.2A CN202111083846A CN113929867B CN 113929867 B CN113929867 B CN 113929867B CN 202111083846 A CN202111083846 A CN 202111083846A CN 113929867 B CN113929867 B CN 113929867B
- Authority
- CN
- China
- Prior art keywords
- silicate
- dimensional material
- groups
- water
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a casting film liquid and a preparation method thereof, and a high-barrier composite film and a preparation method thereof, wherein the casting film liquid comprises the following components: a curable aqueous acrylic material and a silicate two-dimensional material; wherein the silicate two-dimensional material has an aspect ratio of not less than 100. According to the invention, the silicate two-dimensional material in the casting film liquid is uniformly dispersed in a self-assembly mode, and when the casting film liquid is solidified to form a film, the silicate two-dimensional material is uniformly distributed in a network structure formed by crosslinking of the curable water-based acrylic material and is crosslinked with a structural framework through covalent bonds, so that on one hand, the silicate two-dimensional material is uniformly dispersed, and on the other hand, the film has higher stability and long service life; in addition, the composite film formed by the casting film liquid prolongs the permeation path of hydrogen in the polymer base material, so that the composite film has stronger gas barrier property.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a film casting solution and a preparation method thereof, and a high-barrier composite film and a preparation method thereof.
Background
Among the new energy sources, hydrogen energy has the advantages of cleanness, high efficiency, renewable energy and the like as a secondary energy source, and becomes the best substitute for the traditional energy sources (coal, petroleum and natural gas), and is one of the most potential new energy sources in the twenty-first century. The development and utilization of hydrogen energy mainly comprise three technical links of hydrogen preparation, storage, transportation and application. The current industrial hydrogen production is not difficult, but a technical bottleneck which restricts the large-scale application of hydrogen energy is that the safe, economic and efficient hydrogen storage technology is not effectively solved. The hydrogen gas storage method comprises high-pressure gas storage, low-temperature liquid storage and solid storage, and the current large-scale application method is high-pressure gas storage. Since hydrogen molecules are extremely small and permeability is extremely high, a film having excellent barrier properties to hydrogen is demanded.
At present, most of researches on hydrogen barrier are focused on materials taking graphene as a main body, but the cost of the graphene is high, and in a composite film formed by the graphene and a polymer substrate, the graphene and the polymer are connected by depending on ionic bonds or Van der Waals force, so that the stability and the service cycle of the composite film cannot be ensured, and the composite film is not beneficial to commercial popularization.
Disclosure of Invention
The invention mainly aims to provide a casting film liquid and a preparation method thereof, and a high-barrier composite film and a preparation method thereof, and aims to solve the problem of poor stability of the existing hydrogen-resistant material.
In order to achieve the above purpose, the invention provides a casting solution, which comprises the following components: a curable aqueous acrylic material and a silicate two-dimensional material; wherein the silicate two-dimensional material has an aspect ratio of not less than 100.
Optionally, the silicate two-dimensional material comprises vermiculite, montmorillonite or mica; and/or, in the film casting solution, the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material is (1-2): 1.
in addition, the invention also provides a preparation method of the casting solution, which comprises the following steps:
dispersing silicate two-dimensional material in water to obtain dispersion liquid;
dispersing a curable aqueous acrylic material in water to obtain an emulsion;
and mixing the dispersion liquid and the emulsion to obtain the casting film liquid.
Optionally, the step of dispersing the curable aqueous acrylic material in water to obtain an emulsion comprises:
under the anhydrous condition, mixing polyethylene glycol, difunctional isocyanate and dibutyltin dilaurate, and reacting at 75-90 ℃ to obtain a first mixed solution containing a primary long-chain polymer;
adding dimethylolpropionic acid into the first mixed solution to perform chain extension reaction to obtain a second mixed solution containing a second-stage long-chain polymer;
and adding a hydroxy acrylic compound into the second mixed solution, reacting at 75-90 ℃, adding p-methoxyphenol, neutralizing, adding water, and stirring strongly to form emulsion.
Optionally, the polyethylene glycol comprises polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, or polyethylene glycol 800; and/or the number of the groups of groups,
the difunctional isocyanate comprises one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate and isophorone diisocyanate; and/or the number of the groups of groups,
the hydroxy acrylic compound comprises hydroxyethyl acrylate or hydroxypropyl acrylate; and/or the number of the groups of groups,
the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2 to 2.2:1.
optionally, the mass percentage of the dispersion liquid is 1% -6%; and/or the number of the groups of groups,
the solid content of the emulsion is 5-20%.
In addition, the invention also provides a high-barrier composite film, which comprises:
the self-curing water-based acrylic acid coating comprises a body, wherein a cross-linking structure is formed on the body, and the body is made of a curable water-based acrylic acid material; the method comprises the steps of,
and a plurality of barrier layers which are arranged in the body at intervals in the thickness direction of the body in a stacked manner, wherein each barrier layer is formed by spreading a plurality of silicate two-dimensional materials, and at least part of the silicate two-dimensional materials are connected with the crosslinking structure through covalent bonds.
Optionally, the high barrier composite film has a thickness of 50 to 200 μm.
In addition, the invention also provides a preparation method of the high-barrier composite film, which comprises the following steps:
forming a coating on the surface of a substrate by using a casting solution, and then curing to obtain a high-barrier composite film;
wherein, the casting film liquid comprises the following components: a curable aqueous acrylic material and a silicate two-dimensional material; wherein the silicate two-dimensional material has an aspect ratio of not less than 100.
Optionally, the coating is irradiated by an ultraviolet lamp to be cured, the power of the ultraviolet lamp is 400-800W, and the curing time is 30-60 s.
According to the technical scheme provided by the invention, the curable aqueous acrylic material and the silicate two-dimensional material are selected as raw materials, the silicate two-dimensional material in the casting film liquid prepared by mixing the two raw materials is uniformly dispersed in a self-assembly mode, and when the film is cured and formed, the silicate two-dimensional material is uniformly distributed in a network structure formed by crosslinking the curable aqueous acrylic material and is crosslinked with a structural framework through covalent bonds, so that the silicate two-dimensional material is uniformly dispersed on one hand, and the film has relatively strong stability and long service period on the other hand; in addition, in the composite film formed by the casting film liquid, a plurality of silicate two-dimensional materials are tiled to form a plurality of barrier layers which are arranged at intervals in a laminated mode, and the permeation path of hydrogen in the polymer base material is prolonged through layer-by-layer barrier, so that the composite film has stronger gas barrier performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other related drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for preparing a high-barrier composite film according to the present invention;
fig. 2 is a schematic structural diagram of a high barrier composite film according to the present invention.
Reference numerals illustrate:
the achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "100 and/or B", including 100 schemes, or B schemes, or schemes that are satisfied by both 100 and B. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The current method for large-scale application is high-pressure gas storage. Since hydrogen molecules are extremely small and permeability is extremely high, a film having excellent barrier properties to hydrogen is demanded.
At present, most of researches on hydrogen barrier are focused on materials taking graphene as a main body, but the cost of the graphene is high, and in a composite film formed by the graphene and a polymer substrate, the graphene and the polymer are connected by depending on ionic bonds or Van der Waals force, so that the stability and the service cycle of the composite film cannot be ensured, and the composite film is not beneficial to commercial popularization.
In view of the above, the present invention provides a casting solution, which comprises the following components: a curable aqueous acrylic material and a silicate two-dimensional material; wherein the silicate two-dimensional material has an aspect ratio of not less than 100.
According to the technical scheme provided by the invention, the curable aqueous acrylic material and the silicate two-dimensional material are selected as raw materials, the silicate two-dimensional material in the casting film liquid prepared by mixing the two raw materials is uniformly dispersed in a self-assembly mode, and when the film is cured and formed, the silicate two-dimensional material is uniformly distributed in a network structure formed by crosslinking the curable aqueous acrylic material and is crosslinked with a structural framework through covalent bonds, so that the silicate two-dimensional material is uniformly dispersed on one hand, and the film has relatively strong stability and long service period on the other hand; in addition, in the composite film formed by the casting film liquid, a plurality of silicate two-dimensional materials are tiled to form a plurality of barrier layers which are arranged at intervals in a laminated mode, and the permeation path of hydrogen in the polymer base material is prolonged through layer-by-layer barrier, so that the composite film has stronger gas barrier performance.
The silicate two-dimensional material is a silicate material which is in a sheet-shaped structure as a whole and has a thickness dimension of 0.1-100nm, and the length-diameter ratio of the silicate material refers to the ratio of the longest diameter of a plane to the thickness. Any silicate two-dimensional material with the length-diameter ratio of more than 100 can be used as one of the raw materials of the casting solution. The curable aqueous acrylic material is a material capable of being crosslinked and cured, and can be combined with a silicate two-dimensional material through covalent bonds, and referring to fig. 1 and 2, when the curable aqueous acrylic material is crosslinked and cured, the curable aqueous acrylic material and the silicate two-dimensional material are self-assembled to form a crosslinked network structure, the silicate two-dimensional material is uniformly distributed in the structure and is connected with active groups on the surface of the curable aqueous acrylic material through covalent bonds, so that the dispersibility of the silicate two-dimensional material in a system is improved, and meanwhile, the connection relationship between the curable aqueous acrylic material and the silicate two-dimensional material is more stable and firm.
Specifically, in some embodiments, the silicate two-dimensional material comprises vermiculite, montmorillonite or mica, the vermiculite, the montmorillonite and the mica not only have higher length-diameter ratio, but also can be better spread to form a barrier layer when the casting film liquid which participates in the preparation is formed into a high-barrier composite film, thereby being beneficial to improving the barrier property of the film.
Furthermore, in some embodiments, the weight ratio of the curable aqueous acrylic material and the silicate two-dimensional material in the casting solution is (1-2): 1, thus, the barrier properties of the formed high-barrier composite film can be ensured.
In addition, the invention also provides a preparation method of the casting solution, and the casting solution of the embodiment can be prepared by the method. The preparation method of the casting film liquid comprises the following steps:
and step S10, dispersing the silicate two-dimensional material in water to obtain a dispersion liquid.
In this example, a certain amount of silicate two-dimensional material was weighed and added to water to be sufficiently dispersed in water to form a dispersion. The silicate two-dimensional material is a silicate two-dimensional plate-like structure material having an aspect ratio of not less than 100, and is preferably any one of vermiculite, montmorillonite and mica. Because silicate two-dimensional materials are in a sheet-like structure with extremely thin thickness, in the natural form, a plurality of monomers are generally arranged in a laminated manner, so that the dispersibility of the silicate two-dimensional materials in a medium is poor. In view of this, as a preferred embodiment, step S10 of the present embodiment may be operated as follows:
and S11, adding the silicate two-dimensional material into water, stirring until the silicate two-dimensional material is uniformly dispersed, and then, in an ice water bath, performing ultrasonic treatment at 800W to separate a plurality of silicate two-dimensional material monomers in the water from each other, so as to separate from a laminated state, and uniformly dispersing in the water to form a dispersion liquid.
Wherein, the step of separating the silicate two-dimensional material monomers from each other in the ultrasonic wave to the water and separating from the laminated state and uniformly dispersing in the water can be specifically implemented according to the following steps:
after ultrasonic treatment for 1-2 hours, freezing for 24 hours at-20 ℃, taking out, thawing, ultrasonic treatment for 1-2 hours again, and sampling to test the separation degree of silicate two-dimensional materials, wherein the test method can be Transmission Electron Microscope (TEM); if not completely separated, repeating the above steps.
In addition, the amount of silicate two-dimensional material dispersed in water is not limited, and may be adjusted according to the dispersion thereof and the component ratio with the curable aqueous acrylic material in the casting solution. In this embodiment, the mass percentage of the dispersion liquid is 1% -6%, that is, the mass percentage of the silicate two-dimensional material in the dispersion liquid is 1% -6%, in this range, not only the silicate two-dimensional material can be well dispersed, but also after mixing with the emulsion, the weight ratio of the curable aqueous acrylic material and the silicate two-dimensional material in the film casting liquid is (1-2): 1, simultaneously, the water content of the casting film liquid is prevented from being too high, so that the stability of the casting film liquid and the performance of a high-resistance film formed by subsequent solidification are further influenced.
And step S20, dispersing the curable aqueous acrylic material in water to obtain an emulsion.
The amount of the curable aqueous acrylic material in the emulsion is not limited, and can be adjusted according to the component ratio of the casting solution to the silicate two-dimensional material, and in one embodiment, the solid content of the emulsion is 5-20%, that is, the weight percentage of the curable aqueous acrylic material contained in the emulsion is 5-20%.
In some embodiments, the curable aqueous acrylic material may be prepared according to the following procedure:
wherein R is 1 Is one of the following three structures 100-c:
R 2 is (CH) 2 ) n N=200, 400, 600 or 800, for example, when polyethylene glycol 200 is used as the raw material, n=200;
R 4 the following structure (d) or (e):
further, based on the above-described flow, step S20 of the present embodiment may operate as follows:
step S21, mixing polyethylene glycol, difunctional isocyanate and dibutyltin dilaurate under anhydrous condition, and reacting at 75-90 ℃ to obtain a first mixed solution containing the primary long-chain polymer (100).
Wherein the polyethylene glycol comprises polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 or polyethylene glycol 800; the difunctional isocyanates include one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, and isophorone diisocyanate.
Referring to the reaction scheme, difunctional isocyanate reacts with polyethylene glycol under the catalysis of dibutyltin dilaurate to generate OCN-R 3 -NCO. The reaction temperature is 75-90 ℃.
Further, in order to increase the purity of the product, the step S21 is performed in an anhydrous or water-less environment, so as to avoid the reaction of the difunctional isocyanate with water to generate byproducts, which results in a decrease in yield and a decrease in purity. Specifically, in order to realize a water-free environment, step S201 may be performed between steps S21.
Step S201, after the polyethylene glycol is heated to 120-140 ℃, vacuumizing to a vacuum degree of more than 0.08MP100 so as to dehydrate the polyethylene glycol.
In addition, the above step S21 may be performed in a nitrogen atmosphere to avoid oxygen interference.
And S22, adding dimethylolpropionic acid into the first mixed solution to perform chain extension reaction to obtain a second mixed solution containing the second-stage long-chain polymer (B).
In the embodiment, dimethylolpropionic acid is added into the first mixed solution to further chain-extend the primary long-chain polymer (100), and the flexibility of the polymer is better by prolonging the length of the polymer, so that the high-barrier composite film prepared from the film casting solution is better in flexibility and the brittleness of the high-barrier composite film is reduced.
Wherein the temperature of the chain extension reaction is 75-90 ℃.
And S23, adding a hydroxy acrylic compound into the second mixed solution, reacting at 75-90 ℃, adding p-methoxyphenol, neutralizing, adding water, and stirring strongly to form emulsion.
In this example, a further hydroxy acrylic compound is added to the second mixed solution to react to form compound (C), thereby curing the aqueous acrylic material. Wherein the hydroxy acrylic compound comprises hydroxyethyl acrylate or hydroxypropyl acrylate.
In addition, the molar ratio of the hydroxyacrylic compound to the difunctional isocyanate is from 2 to 2.2:1, so that the end part of the primary long chain polymer (100) can be ensured to retain isocyanate groups, and further, when the subsequent high-barrier composite film is cured to form a film, the surface hydroxyl groups of the silicate two-dimensional material can be connected with the isocyanate groups through chemical bonds.
The reaction time is not limited, and may be controlled so that the solid content of the final emulsion is 5 to 20% according to actual needs, for example, the solid content demand.
In addition, in order to ensure the stability of the emulsion, p-methoxyphenol is added to the reaction solution after the reaction is completed, so that a stable emulsion can be obtained.
And step S30, mixing the dispersion liquid and the emulsion to obtain a casting film liquid.
In this example, the dispersion and the emulsion were mixed to obtain a casting solution. In the film casting solution, the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material is (1-2): 1.
in addition, the present invention further provides a high-barrier composite film 100, referring to fig. 2, the high-barrier composite film 100 includes a body 10 and a plurality of barrier layers 20, the body 10 is formed with a cross-linking structure 11, and the material of the body 10 includes a curable aqueous acrylic material; a plurality of barrier layers 20 are disposed in the body 10 at intervals in the thickness direction of the body 10 and stacked, each of the barrier layers 20 is formed by spreading a plurality of silicate two-dimensional materials 1, and at least part of the silicate two-dimensional materials 1 is covalently bonded to the crosslinked structure 11.
As shown in fig. 2, the high barrier composite film 100 may be prepared from the casting solution 200 described in the above embodiment, and when the casting solution 200 is cured, the curable aqueous acrylic material in the system undergoes a crosslinking reaction to gradually form the crosslinked structure 11, during which the silicate two-dimensional material 1 self-assembles with the curable aqueous acrylic material to form a plurality of barrier layers 20 in the body 10, which are disposed at intervals along the thickness direction of the body 10, and each barrier layer 20 is formed by spreading a plurality of sheet-shaped silicate two-dimensional materials 1, so as to form a layer-by-layer barrier in the thickness direction of the body 10, thereby prolonging the permeation path of hydrogen in the polymer substrate, and making the composite film have a stronger gas barrier property.
Further, the thickness of the high-barrier composite film 100 is 50-200 μm, so that the thickness of the film layer can be reduced and the cost can be reduced while ensuring sufficient barrier performance.
In addition, the invention also provides a preparation method of the high-barrier composite film 100, referring to fig. 1, the preparation method of the high-barrier composite film 100 comprises the following steps:
in step S100, a coating layer is formed on the surface of the substrate using the casting solution 200, and then the high barrier composite film 100 is obtained by curing.
Wherein, the casting solution 200 comprises the following components: a curable aqueous acrylic material and silicate two-dimensional material 1; wherein the silicate two-dimensional material 1 has an aspect ratio of not less than 100.
Specifically, the casting solution 200 may be prepared according to the above embodiments, for example, the preparation method of the casting solution 200 includes the following steps:
in step S10, the silicate two-dimensional material 1 is dispersed in water to obtain a dispersion.
And step S20, dispersing the curable aqueous acrylic material in water to obtain an emulsion.
And step S30, mixing the dispersion liquid and the emulsion to obtain a casting film liquid 200.
Further, the curable aqueous acrylic material is a photocurable material, and based on this, in step S100, the curing treatment step may be implemented by irradiating the coating layer with an ultraviolet lamp, where the power of the ultraviolet lamp is 400-800W, and the curing time is 30-60S.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
Adding silicate two-dimensional material (vermiculite, microlite 963+, with length-diameter ratio of 230) into water, stirring until the silicate two-dimensional material is uniformly dispersed, performing ultrasonic treatment in an ice water bath at 800W for 2 hours, freezing at-20 ℃ for 24 hours, taking out the silicate two-dimensional material, performing ultrasonic treatment again for 2 hours after thawing, and enabling a plurality of silicate two-dimensional material monomers in the water to be mutually peeled off from each other and separated from a lamination state so as to be uniformly dispersed in the water to form a dispersion liquid with the mass percentage of 3%.
After the polyethylene glycol 200 is heated to 130 ℃, vacuum is pumped to a vacuum degree of more than 0.08MPa and then the polyethylene glycol is kept for 2 hours, so that the polyethylene glycol is dehydrated. Then, in a nitrogen atmosphere, mixing dehydrated polyethylene glycol 200, difunctional isocyanate (isophorone diisocyanate) and dibutyltin dilaurate, and reacting at 80 ℃ to obtain a first mixed solution containing a primary long-chain polymer (A); adding dimethylolpropionic acid into the first mixed solution, and performing chain extension reaction at 80 ℃ to obtain a second mixed solution containing a second-stage long-chain polymer (B); the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2.1:1, adding a hydroxy acrylic compound (hydroxypropyl acrylate) into the second mixed solution, reacting at 90 ℃, then adding p-methoxyphenol, uniformly mixing, and cooling to 20 ℃. And (3) eliminating nitrogen protection, adding triethylamine for neutralization, and adding deionized water for emulsification under strong stirring to obtain emulsion with the solid content of 10%.
According to the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material in the casting solution of 1.5:1, mixing the dispersion liquid and the emulsion to obtain a casting film liquid.
And (3) taking a glass substrate, spraying a film casting solution on the surface of the glass substrate by using a spray can to form a coating, then irradiating the coating for 30s by using an ultraviolet lamp with the power of 600W, heating and drying, and uncovering the film to obtain the high-barrier composite film with the thickness of 120 mu m.
Example 2
Adding silicate two-dimensional material (montmorillonite, length-diameter ratio is 115) into water, stirring until the silicate two-dimensional material is uniformly dispersed, performing ultrasonic treatment in an ice water bath at 800W for 2 hours, freezing at-20 ℃ for 24 hours, taking out and thawing, performing ultrasonic treatment again for 2 hours, and enabling a plurality of silicate two-dimensional material monomers in the water to be mutually peeled off and separated from a lamination state, so that the silicate two-dimensional material monomers are uniformly dispersed in the water to form dispersion liquid with mass percent of 5%.
After the polyethylene glycol 400 is heated to 120 ℃, vacuum is pumped to a vacuum degree of more than 0.08MPa and then the polyethylene glycol is kept for 2 hours, so that the polyethylene glycol is dehydrated. Then, in a nitrogen atmosphere, mixing dehydrated polyethylene glycol 400, difunctional isocyanate (toluene diisocyanate) and dibutyltin dilaurate, and reacting at 80 ℃ to obtain a first mixed solution containing a primary long-chain polymer (A); adding dimethylolpropionic acid into the first mixed solution, and performing chain extension reaction at 80 ℃ to obtain a second mixed solution containing a second-stage long-chain polymer (B); the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2.05:1, adding a hydroxy acrylic compound (hydroxyethyl acrylate) into the second mixed solution, reacting at 80 ℃, then adding p-methoxyphenol, uniformly mixing, and cooling to 20 ℃. And (3) eliminating nitrogen protection, adding triethylamine for neutralization, and adding deionized water for emulsification under strong stirring to obtain emulsion with the solid content of 10%.
According to the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material in the casting solution of 1.5:1, mixing the dispersion liquid and the emulsion to obtain a casting film liquid.
And (3) spraying the casting solution on the surface of the glass substrate by using a spray can to form a coating, irradiating the coating for 45s by using an ultraviolet lamp with the power of 600W, heating and drying, and uncovering the coating to obtain the high-barrier composite film with the thickness of 150 mu m.
Example 3
Adding silicate two-dimensional material (montmorillonite, length-diameter ratio is 115) into water, stirring until the silicate two-dimensional material is uniformly dispersed, performing ultrasonic treatment in an ice water bath at 800W for 2 hours, freezing at-20 ℃ for 24 hours, taking out and thawing, performing ultrasonic treatment again for 2 hours, and enabling a plurality of silicate two-dimensional material monomers in the water to be mutually peeled off and separated from a lamination state, so that the silicate two-dimensional material monomers are uniformly dispersed in the water to form dispersion liquid with mass percent of 6%.
After the polyethylene glycol 400 is heated to 140 ℃, vacuum is pumped to a vacuum degree of more than 0.08MPa and then the polyethylene glycol is kept for 2 hours, so that the polyethylene glycol is dehydrated. Then, in a nitrogen atmosphere, mixing dehydrated polyethylene glycol 800, difunctional isocyanate (diphenylmethane-4, 4' -diisocyanate) and dibutyltin dilaurate, and reacting at 75 ℃ to obtain a first mixed solution containing a primary long-chain polymer (A); adding dimethylolpropionic acid into the first mixed solution, and performing chain extension reaction at 75 ℃ to obtain a second mixed solution containing a second-stage long-chain polymer (B); the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2.2:1, adding a hydroxy acrylic compound (hydroxypropyl acrylate) into the second mixed solution, reacting at 80 ℃, then adding p-methoxyphenol, uniformly mixing, and cooling to 20 ℃. And (3) eliminating nitrogen protection, adding triethylamine for neutralization, and adding deionized water for emulsification under strong stirring to obtain emulsion with the solid content of 5%.
According to the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material in the casting solution of 1.5:1, mixing the dispersion liquid and the emulsion to obtain a casting film liquid.
And (3) taking a glass substrate, spraying a film casting solution on the surface of the glass substrate by using a spray can to form a coating, then irradiating the coating for 45s by using an ultraviolet lamp with the power of 800W, heating and drying, and uncovering the film to obtain the high-barrier composite film with the thickness of 50 mu m.
Example 4
Adding silicate two-dimensional material (mica, length-diameter ratio is 156) into water, stirring until the silicate two-dimensional material is uniformly dispersed, and then, in an ice water bath, carrying out ultrasonic treatment at 800W to a plurality of silicate two-dimensional material monomers in the water to mutually peel off, separating from a laminated state, and uniformly dispersing in the water to form a dispersion liquid with the mass percent of 4%.
Heating polyethylene glycol 400 to 130 ℃, vacuumizing to a vacuum degree of more than 0.08MPa so that the polyethylene glycol 400 is dehydrated, mixing polyethylene glycol 400, difunctional isocyanate (isophorone diisocyanate) and dibutyltin dilaurate, and reacting at 90 ℃ to obtain a first mixed solution containing a primary long-chain polymer (A); adding dimethylolpropionic acid into the first mixed solution, and performing chain extension reaction at 90 ℃ to obtain a second mixed solution containing a second-stage long-chain polymer (B); the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2.2:1, adding a hydroxy acrylic compound (acrolein hydroxyethyl) into the second mixed solution, reacting at 75 ℃, then adding p-methoxyphenol, uniformly mixing, and cooling to 20 ℃. And (3) eliminating nitrogen protection, adding triethylamine for neutralization, and adding deionized water for emulsification under strong stirring to obtain emulsion with the solid content of 20%.
According to the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material in the casting solution of 1:1, mixing the dispersion liquid and the emulsion to obtain a casting film liquid.
And (3) spraying the casting solution on the surface of the glass substrate by using a spray can to form a coating, then irradiating the coating for 60s by using an ultraviolet lamp with the power of 400W, heating and drying, and uncovering the coating to obtain the high-barrier composite film with the thickness of 130 mu m.
Example 5
Adding silicate two-dimensional material (vermiculite, length-diameter ratio is 230) into water, stirring until the silicate two-dimensional material is uniformly dispersed, performing ultrasonic treatment in an ice water bath at 800W for 2 hours, freezing at-20 ℃ for 24 hours, taking out and thawing, performing ultrasonic treatment again for 2 hours, and enabling a plurality of silicate two-dimensional material monomers in the water to be mutually peeled off and separated from a lamination state, so that the silicate two-dimensional material monomers are uniformly dispersed in the water to form a dispersion liquid with the mass percentage of 1%.
After the polyethylene glycol 600 is heated to 120 ℃, vacuum is pumped to a vacuum degree of more than 0.08MPa and then the polyethylene glycol is kept for 2 hours, so that the polyethylene glycol is dehydrated. Then, in a nitrogen atmosphere, mixing dehydrated polyethylene glycol 600, difunctional isocyanate (toluene diisocyanate) and dibutyltin dilaurate, and reacting at 80 ℃ to obtain a first mixed solution containing a primary long-chain polymer (A); adding dimethylolpropionic acid into the first mixed solution, and performing chain extension reaction at 80 ℃ to obtain a second mixed solution containing a second-stage long-chain polymer (B); the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2:1, adding a hydroxy acrylic compound (hydroxyethyl acrylate) into the second mixed solution, reacting at 80 ℃, then adding p-methoxyphenol, uniformly mixing, and cooling to 20 ℃. And (3) eliminating nitrogen protection, adding triethylamine for neutralization, and adding deionized water for emulsification under strong stirring to obtain emulsion with the solid content of 10%.
The weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material in the casting solution is 2:1, mixing the dispersion liquid and the emulsion to obtain a casting film liquid.
And (3) spraying a film casting solution on the surface of the glass substrate by using a spray can to form a coating, irradiating the coating 45 by using an ultraviolet lamp with the power of 600W, heating and drying, and uncovering the film to obtain the high-barrier composite film with the thickness of 200 mu m.
Comparative example 1
Adding silicate two-dimensional material (vermiculite, length-diameter ratio is 230) into water, stirring until the silicate two-dimensional material is uniformly dispersed, performing ultrasonic treatment in an ice water bath at 800W for 2 hours, freezing at-20 ℃ for 24 hours, taking out and thawing, performing ultrasonic treatment again for 2 hours, and enabling a plurality of silicate two-dimensional material monomers in the water to be mutually peeled off and separated from a lamination state, so that the silicate two-dimensional material monomers are uniformly dispersed in the water to form a dispersion liquid with the mass percentage of 3%.
After the polyethylene glycol 600 is heated to 120 ℃, vacuum is pumped to a vacuum degree of more than 0.08MPa and then the polyethylene glycol is kept for 2 hours, so that the polyethylene glycol is dehydrated. Then, in a nitrogen atmosphere, mixing dehydrated polyethylene glycol 600, difunctional isocyanate (toluene diisocyanate) and dibutyltin dilaurate, and reacting at 80 ℃ to obtain a first mixed solution containing a primary long-chain polymer (A); adding dimethylolpropionic acid into the first mixed solution, and performing chain extension reaction at 80 ℃ to obtain a second mixed solution containing a second-stage long-chain polymer (B); the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2.05:1, adding a hydroxy acrylic compound (hydroxyethyl acrylate) into the second mixed solution, reacting at 80 ℃, then adding p-methoxyphenol, uniformly mixing, and cooling to 20 ℃. And (3) eliminating nitrogen protection, adding triethylamine for neutralization, and adding deionized water for emulsification under strong stirring to obtain emulsion with the solid content of 10%.
According to the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material in the casting solution of 1.5:1, mixing the dispersion liquid and the emulsion to obtain a casting film liquid, heating and drying, and uncovering the film to obtain the high-barrier composite film with the thickness of 200 mu m.
The high barrier composite films prepared in examples 1 to 5 and comparative example 1 were tested, and the results are shown in table 1. The detection method comprises the following steps:
the Tensile Strength and elongation at break of the film are used as criteria for judging the mechanical properties of the film, and the Tensile Strength (Tensile Strength) refers to the stress of the film when the film generates the maximum uniform plastic deformation, and the unit is MPa. Elongation at break (Elongation at break) is the ratio of displacement to original length in% when the film is broken. The film was made into 13mm 3 A5 mm standard sample was subjected to a tensile test by a micro-electronic universal tensile tester under conditions of constant temperature and humidity at 20℃and 60% RH, and the test was performed under conditions of a clamp position of 23mm and a movement of 10mm per minute. The tensile strength (MPa) can be calculated by equation 1.
Equation 1: delta t ＝P/(b×d)
Wherein: p, b, d represent the maximum stress (N), film width (cm), film thickness (cm), respectively.
δ＝(L/L 0 )/L 0 ×100％
The hydrogen permeability, solubility coefficient and diffusion coefficient of the layer-by-layer self-assembled film are tested by a differential pressure permeameter, the test temperature is 23 ℃, and the humidity is 50% RH (Relative humidity). The difference in the test pressures was the permeation rate of hydrogen at 0.1 MPa.
Table 1 performance comparison
Analysis of results: from the above table, compared with the comparative examples, each example has better mechanical properties and barrier properties, which indicates that the high barrier composite film prepared by the invention has better stability and barrier effect.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. The preparation method of the high-barrier composite film is characterized by comprising the following steps of:
adding silicate two-dimensional materials into water, stirring until the silicate two-dimensional materials are uniformly dispersed, and then, in an ice water bath, carrying out ultrasonic treatment at 800W until a plurality of silicate two-dimensional material monomers in the water are mutually peeled off and separated from a lamination state, so that the silicate two-dimensional materials are uniformly dispersed in the water to form a dispersion liquid;
dispersing a curable aqueous acrylic material in water to obtain an emulsion;
mixing the dispersion liquid and the emulsion to obtain a casting film liquid;
forming a coating on the surface of a substrate by using a casting solution, and then curing to obtain a high-barrier composite film;
irradiating the coating by an ultraviolet lamp to cure the coating, wherein the power of the ultraviolet lamp is 400-800W, and the curing time is 30-60 s;
the length-diameter ratio of the silicate two-dimensional material is not less than 100;
the silicate two-dimensional material comprises vermiculite, montmorillonite or mica; and/or the number of the groups of groups,
in the film casting solution, the weight ratio of the curable aqueous acrylic material to the silicate two-dimensional material is (1-2): 1, a step of;
the step of dispersing the curable aqueous acrylic material in water to obtain an emulsion comprises:
under the anhydrous condition, mixing polyethylene glycol, difunctional isocyanate and dibutyltin dilaurate, and reacting at 75-90 ℃ to obtain a first mixed solution containing a primary long-chain polymer;
adding dimethylolpropionic acid into the first mixed solution to perform chain extension reaction to obtain a second mixed solution containing a second-stage long-chain polymer;
and adding a hydroxy acrylic compound into the second mixed solution, reacting at 75-90 ℃, adding p-methoxyphenol, neutralizing, adding water, and stirring strongly to form emulsion.
2. The method of preparing a high barrier composite film according to claim 1, wherein the polyethylene glycol comprises polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 or polyethylene glycol 800; and/or the number of the groups of groups,
the difunctional isocyanate comprises one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate and isophorone diisocyanate; and/or the number of the groups of groups,
the hydroxy acrylic compound comprises hydroxyethyl acrylate or hydroxypropyl acrylate; and/or the number of the groups of groups,
the molar ratio of the hydroxy acrylic compound to the difunctional isocyanate is 2-2.2: 1.
3. the method for preparing the high-barrier composite film according to claim 1, wherein the mass percentage of the dispersion liquid is 1% -6%; and/or the number of the groups of groups,
the solid content of the emulsion is 5-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111083846.2A CN113929867B (en) | 2021-09-15 | 2021-09-15 | Casting film liquid and preparation method thereof, high-barrier composite film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111083846.2A CN113929867B (en) | 2021-09-15 | 2021-09-15 | Casting film liquid and preparation method thereof, high-barrier composite film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113929867A CN113929867A (en) | 2022-01-14 |
| CN113929867B true CN113929867B (en) | 2023-08-11 |
Family
ID=79276035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111083846.2A Active CN113929867B (en) | 2021-09-15 | 2021-09-15 | Casting film liquid and preparation method thereof, high-barrier composite film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929867B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010054760A1 (en) * | 2008-11-13 | 2010-05-20 | Bayer Materialscience Ag | Polyurethane dispersions for coatings having barrier properties |
| WO2012175427A2 (en) * | 2011-06-20 | 2012-12-27 | Bayer Intellectual Property Gmbh | Production of films having flexible barrier coatings containing phyllosilicates |
| WO2013052013A1 (en) * | 2011-10-06 | 2013-04-11 | Agency For Science, Technology And Research | A layered silicate/polymer composite and a method of forming the same |
| CN104136560A (en) * | 2012-02-28 | 2014-11-05 | 凸版印刷株式会社 | Aqueous coating agent and gas barrier film |
| CN112940318A (en) * | 2021-03-15 | 2021-06-11 | 深圳市通产丽星科技集团有限公司 | Method for producing organic-inorganic composite film and organic-inorganic composite film |
| CN114045107A (en) * | 2021-12-30 | 2022-02-15 | 南雄市瑞晟化学工业有限公司 | Environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10344449A1 (en) * | 2003-09-25 | 2005-04-28 | Henkel Kgaa | Adhesive composition with barrier properties |
| EP3320008B1 (en) * | 2015-07-08 | 2023-12-06 | Universiteit Gent | Novel urethane based materials, derivatives, methods of their preparation and uses |
| CN108603050A (en) * | 2016-02-03 | 2018-09-28 | 巴斯夫欧洲公司 | The mono-component aqueous coating composition containing polyurethane and phyllosilicate for oxygen obstruction coating |
| WO2017180220A1 (en) * | 2016-03-18 | 2017-10-19 | Ppg Industries Ohio, Inc. | Coating compositions, elastic barrier coatings formed therefrom, and methods of applying such coatings |
| US11015084B2 (en) * | 2017-09-20 | 2021-05-25 | Ppg Industries Ohio, Inc. | Coating compositions and elastic barrier coatings formed therefrom |
| US10829664B2 (en) * | 2019-03-15 | 2020-11-10 | Ppg Industries Ohio, Inc. | Coating compositions containing polythioethers and elastic barrier coatings formed therefrom |
-
2021
- 2021-09-15 CN CN202111083846.2A patent/CN113929867B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010054760A1 (en) * | 2008-11-13 | 2010-05-20 | Bayer Materialscience Ag | Polyurethane dispersions for coatings having barrier properties |
| WO2012175427A2 (en) * | 2011-06-20 | 2012-12-27 | Bayer Intellectual Property Gmbh | Production of films having flexible barrier coatings containing phyllosilicates |
| WO2013052013A1 (en) * | 2011-10-06 | 2013-04-11 | Agency For Science, Technology And Research | A layered silicate/polymer composite and a method of forming the same |
| CN104136560A (en) * | 2012-02-28 | 2014-11-05 | 凸版印刷株式会社 | Aqueous coating agent and gas barrier film |
| CN112940318A (en) * | 2021-03-15 | 2021-06-11 | 深圳市通产丽星科技集团有限公司 | Method for producing organic-inorganic composite film and organic-inorganic composite film |
| CN114045107A (en) * | 2021-12-30 | 2022-02-15 | 南雄市瑞晟化学工业有限公司 | Environment-friendly high-solid-content aqueous polyurethane acrylate composite emulsion and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 聚氨酯/蒙脱土复合控释肥膜材的制备与性能;伍贤东，等;《植物营养与肥料学报》;20191231;第25卷(第12期);第2053-2060页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113929867A (en) | 2022-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Price et al. | Green chemical functionalization of single-walled carbon nanotubes in ionic liquids | |
| EP2554568B1 (en) | Polyimide nanocomposite and method for preparing same | |
| TWI396724B (en) | Composition for circuit connection film and circuit connection film using the same | |
| CN111138631B (en) | Preparation method of high-strength high-barrier TPU composite material | |
| CN111087651B (en) | High-conductivity waterborne polyurethane/modified graphene composite emulsion and preparation method thereof | |
| CN114395160B (en) | Graphene modified polyurethane composite material and preparation method thereof | |
| Yang et al. | Robust and rapid responsive organic-inorganic hybrid bilayer hydrogel actuators with silicon nanoparticles as the cross-linker | |
| Roy et al. | Synergistic effect of polydopamine–polyethylenimine copolymer coating on graphene oxide for EVA nanocomposites and high-performance triboelectric nanogenerators | |
| CN115353609A (en) | Repairable and reinforced high-performance polyurethane elastomer and preparation method thereof | |
| WO2021135378A1 (en) | Graphene-based polyurethane porous nanometer material and preparation method therefor | |
| JP2004225042A (en) | Nano structure of double continuous phase of block polymer phase separation and its application | |
| CN113929867B (en) | Casting film liquid and preparation method thereof, high-barrier composite film and preparation method thereof | |
| Huang et al. | High-performance epoxy vitrimers with the joint action of dual dynamic covalent bonds | |
| JP2024055880A (en) | Telechelic polyurethanes, methods for their preparation and use | |
| CN108773842B (en) | Preparation method of graphene and graphene | |
| Gaaz et al. | Physical properties of halloysite nanotubes-polyvinyl alcohol nanocomposites using malonic acid crosslinked | |
| CN114773655B (en) | MXene mud composite film and preparation method and application thereof | |
| CN112745656B (en) | High-wear-resistance thermoplastic polyurethane composite material and preparation method thereof | |
| KR101660763B1 (en) | graphene with high conductivity, graphene sheet, and manufacturing method thereof | |
| CN111592655A (en) | Self-healing flexible composite material and preparation method thereof | |
| KR101728830B1 (en) | Preparation method for polyimide composites from monomer | |
| Lu et al. | Multifunctional fluorescent self-healing elastomers consisting of polydimethylsiloxane and carbon dots linked via a Schiff base reaction | |
| Jana et al. | Thermal stability and proton conductivity of silane based nanostructured composite membranes | |
| JP2016121318A (en) | Hydrophilic polymer, and method of producing the same | |
| CN110194943A (en) | Uvioresistant acrylic acid modified polyurethane adhesive resistant to high temperature and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |