CN112940318B - Method for producing organic-inorganic composite film and organic-inorganic composite film - Google Patents

Method for producing organic-inorganic composite film and organic-inorganic composite film Download PDF

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CN112940318B
CN112940318B CN202110278469.1A CN202110278469A CN112940318B CN 112940318 B CN112940318 B CN 112940318B CN 202110278469 A CN202110278469 A CN 202110278469A CN 112940318 B CN112940318 B CN 112940318B
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vermiculite
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inorganic composite
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CN112940318A (en
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刘晓东
罗山
何业
陈寿
彭晓华
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Shenzhen Tongchan Lixing Technology Group Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • 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
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    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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Abstract

The invention provides a preparation method of an organic-inorganic composite film and the organic-inorganic composite film, in the preparation method of the organic-inorganic composite film, firstly, epoxy acrylate modified chitosan is prepared, and silane modifier is used for carrying out surface modification on a nano vermiculite sheet to obtain the modified nano vermiculite sheet; uniformly mixing the modified chitosan and the modified nano-vermiculite sheets, adding a catalyst, and preparing into film-forming slurry; and then preparing the film-forming slurry into a film shape, crosslinking and curing the modified chitosan and the modified nano vermiculite sheets, and drying to obtain the organic-inorganic composite film consisting of the modified chitosan and the modified nano vermiculite sheets. The preparation method of the organic-inorganic composite film provided by the invention has the advantages of simple and efficient processing mode, environmental protection and no toxicity, can solve the problems of agglomeration and orientation arrangement of inorganic nanoparticles in an organic matrix, and has excellent mechanical property and barrier property.

Description

Method for producing organic-inorganic composite film and organic-inorganic composite film
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method of an organic-inorganic composite film and the organic-inorganic composite film.
Background
The high-barrier packaging materials commonly used at present are plastic packaging films, such as PA/PE, PET/PA/PE co-extrusion films and the like. Although the plastic packaging film has good oxygen and water vapor barrier properties, the plastic packaging film has great environmental pollution because of containing non-degradable materials. In order to replace a plastic packaging film to obtain a high-barrier packaging material with less influence on the environment, a common scheme at present is to add graphene oxide, flat double-walled carbon nanotubes, silicate nanosheets and the like into an organic base material to obtain an organic-inorganic composite material.
In a common preparation method of the organic-inorganic composite material, inorganic nanoparticles are added into a polymer matrix in a solution polymerization, melt blending or solution blending mode. However, due to the nano effect of the inorganic nanoparticles, the problems of agglomeration and orientation arrangement of the inorganic nanoparticles in the polymer matrix are easily caused, and the development of the organic-inorganic composite material industry is limited.
Disclosure of Invention
The invention mainly aims to provide a preparation method of an organic-inorganic composite film, and aims to solve the problem that the conventional preparation method of the organic-inorganic composite film is difficult to solve the problems of agglomeration and orientation arrangement of inorganic nanoparticles in a polymer matrix.
In order to achieve the above object, the present invention provides a method for preparing an organic-inorganic composite film, comprising the steps of:
dissolving chitosan in an acid solution, adding epoxy acrylate and persulfate catalysts, and reacting at 50-80 ℃ to obtain a modified chitosan solution;
separating the solid modified chitosan from the modified chitosan solution;
dispersing the nano vermiculite sheets and a silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid substance, namely the modified nano vermiculite sheets;
dispersing the modified chitosan and the modified nano vermiculite sheets in water, and adding a catalyst to obtain film forming slurry;
and preparing the film-forming slurry into a film shape, curing, crosslinking and drying to obtain the organic-inorganic composite film.
Optionally, the step of separating the solid modified chitosan from the modified chitosan solution comprises:
adding a precipitation solvent into the modified chitosan solution to precipitate a solid in the modified chitosan solution, and then separating the solid to obtain modified chitosan;
wherein the precipitation solvent comprises at least one of methanol, ethanol, ethylene glycol and isopropanol.
Optionally, the step of dissolving chitosan in an acid solution, adding epoxy acrylate and persulfate catalyst, and reacting at 50-80 ℃ to obtain the modified chitosan solution comprises:
the mass ratio of the chitosan to the epoxy acrylate is 1 (0.5-1.5); and/or the presence of a gas in the gas,
the mass ratio of the chitosan to the persulfate catalyst is 1 (0.03-0.05); and/or the presence of a gas in the gas,
the persulfate catalyst comprises at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
Optionally, the steps of dispersing the nano vermiculite pieces and the silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid substance, namely the modified nano vermiculite pieces, comprise:
the mass ratio of the nano vermiculite pieces to the silane modifier is 1 (0.8-1.2); and/or the presence of a gas in the gas,
the silane modifier comprises at least one of vinyltrimethoxysilane, vinyltriethoxysilane and vinyltrichlorosilane.
Optionally, the step of dispersing the nano vermiculite pieces and the silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid, namely the modified nano vermiculite pieces, comprises the following steps:
NaOH is used for regulating the PH value to be 9-11.
Optionally, the step of dispersing the nano vermiculite pieces and the silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid substance, namely the modified nano vermiculite pieces, comprises the following steps of:
dissolving a silane modifier in an organic solution to obtain a silane modifier solution;
dispersing the nano vermiculite sheets in water to obtain a nano vermiculite sheet dispersion liquid;
and mixing the silane modifier solution and the nano vermiculite sheet dispersion liquid, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid, namely the modified nano vermiculite sheet.
Optionally, the step of dispersing the modified chitosan and the modified nano-vermiculite sheets in water, and adding a catalyst to obtain a film-forming slurry comprises:
the mass ratio of the modified chitosan to the modified nano vermiculite pieces is (0.8-1.2): 1.
Optionally, the step of dispersing the modified chitosan and the modified nano-vermiculite sheets in water, and adding a catalyst to obtain a film-forming slurry comprises:
the catalyst comprises at least one of dibenzoyl peroxide, ammonium ceric nitrate, ammonium ferrous sulfate and potassium persulfate.
Optionally, the step of preparing the film-forming slurry into a film shape, curing, crosslinking and drying to obtain the organic-inorganic composite film includes:
and preparing the film-forming slurry into a film shape, placing the film-forming slurry into a microwave with the radiation power of 500-800W for 2-10 min to enable the modified chitosan and the modified nano-vermiculite sheet to be cured and crosslinked at the temperature of 60-120 ℃, and then drying to obtain the organic-inorganic composite film.
The invention further provides an organic-inorganic composite membrane prepared by the preparation method of the organic-inorganic composite membrane.
According to the preparation method of the organic-inorganic composite membrane disclosed by the technical scheme of the invention, the epoxy acrylate is used for modifying the chitosan so as to improve the water solubility of the chitosan and introduce double bonds into the modified chitosan; carrying out surface modification on the nano vermiculite sheet by using a silane modifier, and introducing double bonds on the surface of the nano vermiculite sheet; uniformly mixing the modified chitosan and the modified nano-vermiculite slices, adding a catalyst, and preparing into film-forming slurry; preparing the film-forming slurry into a film shape, and polymerizing double bonds in the modified chitosan and the double bonds on the surface of the modified nano-vermiculite sheet under a thermal condition or a light condition to form a cross-linked structure, namely cross-linking and curing; and then drying to obtain the organic-inorganic composite membrane consisting of the modified chitosan and the modified nano vermiculite sheets.
In the preparation method of the organic-inorganic composite membrane, the modified nano-vermiculite sheet is of a sheet structure with a high aspect ratio, and the chain segment of the modified chitosan is short. The modified nano vermiculite sheets and the modified chitosan are uniformly mixed and cross-linked and cured to form a bionic brick-mud structure, wherein the modified nano vermiculite sheets are bricks, and the modified chitosan is cement and plays a role in filling joints as an adhesive.
By forming a bionic brick-mud structure, the organic-inorganic composite film obtains a regular organic-inorganic multi-stage ordered structure, and the problems of poor dispersibility, agglomeration and low addition of inorganic nanoparticles in an organic base material are effectively solved; the problem of orientation arrangement of inorganic nanoparticles in an organic base material is solved by utilizing the covalent bond effect between organic and inorganic components; and the interface acting force between the two components is enhanced by utilizing the covalent bond, and the oxygen-resistant and water vapor-resistant performance is improved.
On the other hand, in the bionic brick mud structure, the modified chitosan serving as cement has a foam-like structure, and a large number of gaps are formed in the foam-like structure, and can effectively increase the permeation path of gas molecules in the composite membrane, so that the organic-inorganic composite membrane can play a remarkable heat insulation role when being heated, and high barrier property is obtained. Meanwhile, the organic-inorganic composite membrane has certain toughness and flexibility and better mechanical property due to the regular arrangement of vermiculite. In summary, the preparation method of the organic-inorganic composite membrane provided by the invention has the advantages of simple and efficient processing mode, environmental protection and no toxicity, can solve the problems of agglomeration and orientation arrangement of inorganic nanoparticles in an organic matrix, and has excellent mechanical properties and barrier properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic flow chart illustrating a method for preparing an organic-inorganic composite film according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of a cross-section of an embodiment of an organic-inorganic composite film provided by the present invention;
fig. 3 is still another scanning electron microscope photograph of a cross section of the organic-inorganic composite film shown in fig. 2.
The reference numbers illustrate:
reference numerals Name (R) Reference numerals Name (R)
100 Organic-inorganic composite film 2 Modified chitosan
1 Modified nano vermiculite sheet
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if directional indications (such as up, down, left, right, front, back, outer, inner, 8230; \8230;) are involved in the embodiment of the present invention, the directional indications are only used to explain the relative position relationship between the components, the motion condition, etc. in a specific posture (as shown in the figure), and if the specific posture is changed, the directional indications are correspondingly changed.
In addition, if there is a description relating to "first", "second", etc. in the embodiments of the present invention, the description of "first", "second", etc. is for descriptive purposes only and is not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B", including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The existing organic-inorganic composite material preparation method has the problems of inorganic nano particles agglomeration and orientation arrangement in an organic base material.
In view of the above, the present invention provides a method for preparing an organic-inorganic composite film, which aims to improve the problems of dispersibility and orientation arrangement of inorganic nanoparticles in an organic substrate by forming a bionic brick-clay structure, and obtain a high-barrier organic-inorganic composite film with uniform texture. Fig. 1 is a schematic flow chart illustrating an embodiment of a method for manufacturing an organic-inorganic composite film 100 according to the present invention. Referring to fig. 1, a method for preparing an organic-inorganic composite film 100 according to the present invention includes the steps of:
s10, dissolving chitosan in an acid solution, adding epoxy acrylate and persulfate catalysts, and reacting at 50-80 ℃ to obtain a modified chitosan solution;
in this step, chitosan is dissolved in an acid solution to increase the solubility of chitosan. Uniformly mixing chitosan and epoxy acrylate, adding persulfate serving as a catalyst, heating to 50-80 ℃, and keeping the temperature for 0.5-3 h, wherein the epoxy acrylate and hydroxyl on the chitosan undergo a ring-opening reaction to generate ether, so as to obtain modified chitosan 2, and the epoxy acrylate provides double bonds to the modified chitosan 2.
The invention is not limited to the solute component of the acid solution in this step, and optionally, in the embodiment of the invention, the solute of the acid solution includes at least one of hydrochloric acid, acetic acid and citric acid. And optionally, the mass fraction of the acid solution is 1-5%; optionally, the mass fraction of chitosan in the acid solution is 1% -5%, and the acid solution can better dissolve chitosan.
The present invention is not limited to the mass ratio of chitosan to epoxy acrylate in this step, and optionally, in the embodiment of the present invention, the mass ratio of chitosan to epoxy acrylate is 1: (0.5-1.5) to introduce a proper amount of double bonds into the modified chitosan 2.
Also, the present invention is not limited with respect to the kind of the persulfate in this step, and optionally, the persulfate includes at least one of ammonium persulfate, potassium persulfate and sodium persulfate. The present invention is not limited with respect to the mass ratio of chitosan to persulfate, alternatively, in the embodiment of the present invention, the mass ratio of chitosan to persulfate is 1: (0.03-0.05). In this ratio, persulfate accelerates the reaction rate of chitosan and epoxy acrylate.
S20, separating solid modified chitosan 2 from the modified chitosan solution;
the present invention is not limited to the method for separating solid modified chitosan 2 from the modified chitosan solution, and may be obtained by evaporation, for example. In the embodiment of the present invention, preferably, step S20 specifically includes:
adding a precipitation solvent into the modified chitosan solution to precipitate a solid in the modified chitosan solution, and then separating the solid to obtain modified chitosan 2;
wherein the precipitation solvent comprises at least one of methanol, ethanol, ethylene glycol and isopropanol.
In this step, the modified shell sugars have very low solubility in the precipitating solvents methanol, ethanol, ethylene glycol and isopropanol. Adding a large amount of precipitation solvent into the modified chitosan solution to reduce the solubility of the modified chitosan 2 in the solution and precipitate, and separating out solid matters to obtain the modified chitosan 2.
Further, the solid modified chitosan 2 is washed with ethanol or acetone for a plurality of times (for example, 1 to 3 times), and dried at 50 to 80 ℃ to obtain the modified chitosan 2 with higher purity.
S30, dispersing the nano vermiculite pieces and a silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid substance, namely the modified nano vermiculite pieces 1;
in the step, optionally, the nano vermiculite sheet is of a sheet structure, the longitudinal dimension of the nano vermiculite sheet is 0.05-0.2 μm, and the transverse dimension of the nano vermiculite sheet is 1-3 μm. Under the alkaline condition, the silane modifier is hydrolyzed to generate Si-OH which is subjected to condensation reaction with hydroxyl on the surface of the nano vermiculite sheet to obtain the modified nano vermiculite sheet 1, and the silane modifier provides double bonds for the modified nano vermiculite sheet 1.
For the kind of silane modifier in this step, optionally, the silane modifier comprises one or more of vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltrichlorosilane. The three silane modifiers contain double bonds, and the double bonds are introduced on the surface of the modified nano vermiculite sheet 1 after the silane modifiers react with the surface of the nano vermiculite sheet.
The invention is not limited with respect to the mass ratio of the nano-vermiculite pieces to the silane modifier in this step, alternatively, in the embodiment of the invention, the mass ratio of the nano-vermiculite pieces to the silane modifier is 1: (0.8-1.2) to introduce a proper amount of double bonds on the surface of the modified nano-vermiculite sheet 1.
In order to uniformly mix the silane modifier and the nano-vermiculite sheet, preferably, the step S30 specifically includes:
s301, dissolving a silane modifier in an organic solution to obtain a silane modifier solution;
s302, dispersing the nano vermiculite pieces in water to obtain nano vermiculite piece dispersion liquid;
s303, mixing the silane modifier solution and the nano vermiculite piece dispersion liquid, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid, namely the modified nano vermiculite piece 1.
In step S301, preferably, the silane modifier is dissolved in the organic solution to obtain a mass fraction w 1 % of silane modifier solution, wherein w is more than or equal to 1% 1 ％≤3％。
In the step, the silane modifier is dissolved in an organic solution to improve the solubility of the silane modifier and promote the hydrolysis of the silane modifier.
The invention is not limited with respect to the composition of the solute in the organic solution in this step. Optionally, the solute of the organic solution comprises one or more of methanol, ethanol, acetone, tetrahydrofuran; and the volume ratio of the solute to the water is (0.1-0.5): 1.
in step S302, preferably, the nano-vermiculite flakes are dispersed in water to obtain the powder with the mass fraction w 2 % of the nano vermiculite sheet dispersion liquid, wherein w is more than or equal to 1% 2 ％≤3％。
In the step, the nano vermiculite sheets are promoted to be uniformly dispersed in water by adopting ultrasonic, stirring and other modes.
Furthermore, preferably, the mass fraction w of the silane modifier solution 1 % of the dispersion liquid of the vermiculite nano-tablets and the mass fraction w of the dispersion liquid of the vermiculite nano-tablets 2 % of the silane modifier is the same, so that the silane modifier and the nano vermiculite sheets in the same proportion are obtained by obtaining the silane modifier solution and the nano vermiculite sheet dispersion liquid in a certain mass ratio, and the calculation process of the mixing proportion of the silane modifier and the nano vermiculite sheets is simplified.
In step S303, the PH is optionally adjusted to 9 to 11 using NaOH. Preferably, in the embodiment of the invention, 1mol/L NaOH solution is used to adjust the pH value to 9-11.
In addition, preferably, the silane modifier solution and the nano vermiculite piece dispersion are mixed, the pH value is adjusted to 9-11, the mixture is stirred for 8-15 hours at normal temperature, and after the reaction is finished, solid-liquid separation is carried out to obtain a solid substance, namely the modified nano vermiculite piece 1. In the step, stirring can promote the silane modifier to fully contact with the nano vermiculite sheets, so that the silane modifier is uniformly distributed on the surfaces of the nano vermiculite sheets.
Further, the modified nano-vermiculite sheet 1 is washed for a plurality of times (for example, 1 to 3 times) by using deionized water, and is dried at 50 to 100 ℃ to obtain the modified nano-vermiculite sheet 1 with higher purity.
S40, dispersing the modified chitosan 2 and the modified nano vermiculite slices 1 in water, and adding a catalyst to obtain film forming slurry;
in the step, amino (-NH) on the molecular chain of the chitosan is modified 2 ) Hydrolyzing to form ammonium ions (NH 4 +) with positive charges, carrying out negative charges on hydroxide ions (-OH) on the surface of the modified nano-vermiculite sheet, uniformly stirring the modified chitosan and the modified nano-vermiculite sheet, and adsorbing the modified chitosan on the surface of the modified nano-vermiculite sheet uniformly through positive and negative charge attraction to form film-forming slurry.
The invention does not limit the mass ratio of the modified chitosan 2 to the modified nano vermiculite slices 1 in the step, and optionally, the mass ratio of the modified chitosan 2 to the modified nano vermiculite slices 1 is (0.8-1.2): 1. In the organic-inorganic composite film formed by the modified chitosan and the modified nano-vermiculite sheets, the modified nano-vermiculite sheets play a role in blocking oxygen and water vapor, so that the proportion of the modified nano-vermiculite sheets in the organic-inorganic composite film cannot be too low, otherwise, the organic-inorganic composite film has poor barrier property. However, the proportion of the modified nano-vermiculite in the organic-inorganic composite film is not too high, which causes difficulty in film formation, or the mechanical property of the organic-inorganic composite film is poor, and only within the proportion range, the organic-inorganic composite film simultaneously obtains good mechanical property and high barrier property.
The invention is not limited to the kind and addition amount of the catalyst in this step, and optionally, the catalyst includes at least one of dibenzoyl peroxide, ammonium ceric nitrate, ammonium ferrous sulfate, and potassium persulfate.
In order to uniformly mix the modified chitosan 2 and the modified nano-vermiculite sheet 1, preferably, the step S40 specifically comprises:
s401, dissolving modified chitosan 2 in water to obtain a modified chitosan solution;
s402, dispersing the modified nano vermiculite slices 1 in water to obtain modified nano vermiculite slice dispersion liquid;
and S403, mixing the modified chitosan solution and the modified nano vermiculite sheet dispersion liquid, and adding a catalyst to obtain film forming slurry.
More preferably:
in step S401, the modified chitosan 2 is dissolved in water to obtain the product with the mass fraction of w 3 % of modified chitosan solution, wherein w is more than or equal to 1% 3 ％≤3％。
In step S402, the modified nano-vermiculite sheets 1 are dispersed in water to obtain the modified nano-vermiculite sheets with the mass fraction w 4 % of modified nano vermiculite sheet dispersion liquid, wherein w is more than or equal to 1% 4 ％≤3％。
More preferably, the mass fraction w of the modified chitosan solution 3 And the mass fraction w of the modified nano vermiculite sheet for heat dissipation 4 The same is carried out to simplify the calculation process of the mixing ratio of the modified chitosan 2 and the modified nano-vermiculite sheets 1.
S50, preparing the film-forming slurry into a film shape, curing, crosslinking and drying to obtain the organic-inorganic composite film.
In the step, double bonds in the modified chitosan 2 and double bonds on the surface of the modified nano-vermiculite sheet 1 are polymerized under a thermal condition or a light condition to form a cross-linked structure.
The modified nano vermiculite sheet 1 is of a lamellar structure with a high aspect ratio, and after the modified nano vermiculite sheet 1 and the modified chitosan 2 are uniformly mixed, crosslinked and cured, the modified nano vermiculite sheet 1 and the modified chitosan 2 form a bionic brick-mud structure, wherein the modified nano vermiculite sheet 1 is a brick, and the modified chitosan 2 is cement and plays a role in filling joints as an adhesive.
By forming a bionic brick-mud structure, the organic-inorganic composite film obtains a regular organic-inorganic multistage ordered structure, and the problems of poor dispersibility, agglomeration and low addition of inorganic nanoparticles in an organic base material are effectively solved; the problem of the orientation arrangement of inorganic nano particles in an organic base material is solved by utilizing the covalent bond effect between organic and inorganic components; and the interface acting force between the two components is enhanced by utilizing the covalent bond, and the oxygen-resistant and water vapor-resistant performance is improved.
On the other hand, referring to fig. 2 and 3, fig. 2 is a scanning electron microscope image of a cross section of an embodiment of the organic-inorganic composite film provided in the present invention, and fig. 3 is another scanning electron microscope image of a cross section of the organic-inorganic composite film shown in fig. 2. Regular ordered lamellar structures and foam-like structures located between the lamellar structures can be seen from a scanning electron microscope image of a cross section, wherein the main component of the lamellar structures is modified nano-vermiculite sheets 1, and the main component of the foam-like structures is modified chitosan 2. A large number of gaps can be observed among layers of a laminated structure formed by the modified nano vermiculite sheets 1, and the gaps can effectively increase the permeation path of gas molecules in the composite membrane, so that the organic-inorganic composite membrane can play a remarkable heat insulation role when being heated, and high barrier property is obtained. Meanwhile, the organic-inorganic composite membrane has certain toughness and flexibility and higher mechanical property due to the regular arrangement of vermiculite. In summary, the preparation method of the organic-inorganic composite membrane provided by the invention has the advantages of simple and efficient processing mode, environmental protection and no toxicity, can solve the problems of agglomeration and orientation arrangement of inorganic nanoparticles in an organic matrix, and has excellent mechanical properties and barrier properties.
The present invention is not limited with respect to the specific conditions for the crosslinking curing in this step. Photo-crosslinking may be used, for example, or thermal crosslinking may be used, for example, in embodiments of the invention. Preferably, the step of preparing the film-forming slurry into a film shape, curing, crosslinking and drying to obtain the organic-inorganic composite film comprises:
preparing the film-forming slurry into a film shape, placing the film-forming slurry into a microwave with the radiation power of 500-800W for 2-10 min so as to enable the modified chitosan and the modified nano vermiculite sheets to be cured and crosslinked at the temperature of 60-120 ℃, and then drying to obtain the organic-inorganic composite film.
The film-forming slurry can be uniformly heated and rapidly heated by adopting a microwave heating mode so as to promote the composite material to be rapidly and uniformly crosslinked, and the modified chitosan-modified nano-vermiculite sheet composite film is prepared.
It should be noted that, in the preparation method of the organic-inorganic composite film provided by the present invention, the order of the preparation steps of the modified chitosan 2 and the preparation steps of the modified nano-vermiculite sheet 1 is not limited. In one embodiment of the present invention, as described above, the preparation step of the modified chitosan 2 is prior to the preparation step of the modified nano-vermiculite sheet 1. In another embodiment of the present invention, the preparation step of the modified nano-vermiculite sheet 1 is prior to the preparation step of the modified chitosan 2, and specifically, the preparation method of the organic-inorganic composite membrane comprises the following steps:
dispersing the nano vermiculite sheets and a silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid substance, namely the modified nano vermiculite sheets 1;
dissolving chitosan in an acid solution, adding epoxy acrylate and persulfate catalysts, and reacting at 50-80 ℃ to obtain a modified chitosan solution;
separating solid modified chitosan 2 from the modified chitosan solution;
dispersing the modified chitosan 2 and the modified nano-vermiculite sheets 1 in water, and adding a catalyst to obtain film-forming slurry;
and preparing the film-forming slurry into a film shape, and curing, crosslinking and drying to obtain the organic-inorganic composite film.
The invention further provides an organic-inorganic composite membrane prepared by the preparation method of the organic-inorganic composite membrane.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
(1) Dissolving 10g of Chitosan (CS) in 2% acetic acid aqueous solution by mass fraction to prepare 2% CS solution by mass fraction, adding 12g of epoxy acrylate (GMA), adding 0.5g of potassium persulfate (KPS) as a catalyst, heating to 80 ℃, reacting for 12h, and preparing epoxy acrylate modified Chitosan (CHQ) solution; the specific chemical reaction formula is as follows:
Figure BDA0002976325390000111
(2) Adding 500ml ethanol into CHQ solution to separate out solid matter from CHQ solution, centrifuging to separate out solid matter, washing with ethanol for 2 times, and drying at 60 deg.C to obtain CHQ;
(3) Dissolving 10g of Vinyltrimethoxysilane (VTMS) in an ethanol aqueous solution (the volume ratio of ethanol to water is 0.2 to 1), stirring for 1h to uniformly disperse the ethanol aqueous solution, and preparing a VMTS solution with the mass fraction of 1%; diluting 7.8wt% of the nano vermiculite piece dispersion liquid into 1wt% of the nano vermiculite piece dispersion liquid, and performing ultrasonic treatment for 1h. Mixing 500g of VTMS solution and 500g of nano vermiculite piece dispersion liquid, adjusting the pH value to 10 by using 1mol/L of NaOH solution, stirring for 12 hours at normal temperature, and centrifugally separating solid substances after reaction to obtain vinyltrimethoxysilane modified nano vermiculite pieces (MVMT); the specific chemical reaction formula is as follows, wherein the molecular formula of the vermiculite is (Mg, fe, al) 3 [(Si,Al) 4 O 10 (OH) 2 ]·4H 2 And O, the main bodies on the left side and the right side of the reaction formula are all nano vermiculite sheets, the surfaces of the nano vermiculite sheets on the left side of the reaction formula are provided with a plurality of hydroxyl groups, and the right side of the reaction formula is the generated modified nano vermiculite sheets.
Figure BDA0002976325390000112
(4) Respectively preparing 10g of CHQ and 10g of MVMT into 2% aqueous solution, mixing the two solutions according to a mass ratio of 1; the specific chemical reaction formula is as follows;
Figure BDA0002976325390000121
under the condition that the relative humidity (RH%) of air is 100%, the Oxygen Transmission Rate (OTR) of the organic-inorganic composite membrane is 7.53 +/-0.24cm3/m < 2 >. Atm.day by adopting an oxygen transmission rate tester; the water vapor transmission rate (WTR) of the organic-inorganic composite film is measured by a water vapor transmission rate tester to be 2.13 +/-0.12 g/m < 2 >. 24h.
Example 2
(1) Dissolving 10g of Chitosan (CS) in 2% acetic acid aqueous solution by mass fraction to prepare 2% CS solution by mass fraction, adding 12g of epoxy acrylate (GMA), adding 0.5g of potassium persulfate (KPS) as a catalyst, heating to 80 ℃, reacting for 12h, and preparing epoxy acrylate modified Chitosan (CHQ) solution;
(2) Adding 500ml ethanol into CHQ solution to separate out solid matter from CHQ solution, centrifuging to separate out solid matter, washing with ethanol for 2 times, and drying at 60 deg.C to obtain CHQ;
(3) Dissolving 10g of Vinyltrimethoxysilane (VTMS) in an ethanol aqueous solution (the volume ratio of ethanol to water is 0.2 to 1), stirring for 1h to uniformly disperse the ethanol aqueous solution, and preparing a VMTS solution with the mass fraction of 1%; diluting 7.8wt% of the nano vermiculite piece dispersion liquid into 1wt% of the nano vermiculite piece dispersion liquid, and performing ultrasonic treatment for 1h. Mixing 500g of VTMS solution and 500g of nano-vermiculite sheet dispersion liquid, adjusting the pH value to 10 by using 1mol/L of NaOH solution, stirring for 12 hours at normal temperature, and centrifugally separating solid substances after reaction to obtain vinyltrimethoxysilane modified nano-vermiculite sheets (MVMT);
(4) Respectively preparing 8g of CHQ and 10g of MVMT into aqueous solution with the mass fraction of 2%, mixing the two aqueous solutions according to the mass ratio of 1.
Under the condition that the relative humidity (RH%) of air is 100%, the Oxygen Transmission Rate (OTR) of the organic-inorganic composite membrane is 1.26 +/-0.04cm 3/m < 2 >. Atm.day by adopting an oxygen transmission rate tester; the water vapor transmission rate (WTR) of the organic-inorganic composite film is 1.17 +/-0.09 g/m < 2 >. 24h measured by a water vapor transmission rate tester.
Example 3
(1) Dissolving 10g of Chitosan (CS) in 2% acetic acid aqueous solution by mass fraction to prepare 2% CS solution by mass fraction, adding 12g of epoxy acrylate (GMA), adding 0.5g of potassium persulfate (KPS) as a catalyst, heating to 80 ℃, reacting for 12h, and preparing epoxy acrylate modified Chitosan (CHQ) solution;
(2) Adding 500ml ethanol into CHQ solution to precipitate solid in CHQ solution, centrifuging to separate out solid, washing with ethanol for 2 times, and drying at 60 deg.C to obtain CHQ;
(3) Dissolving 10g of Vinyltrimethoxysilane (VTMS) in an ethanol aqueous solution (the volume ratio of ethanol to water is 0.2 to 1), stirring for 1h to uniformly disperse the ethanol aqueous solution, and preparing a VMTS solution with the mass fraction of 1%; diluting 7.8wt% of the nano vermiculite piece dispersion liquid into 1wt% of the nano vermiculite piece dispersion liquid, and carrying out ultrasonic treatment for 1 hour. Mixing 500g of VTMS solution and 500g of nano-vermiculite sheet dispersion liquid, adjusting the pH value to 10 by using 1mol/L of NaOH solution, stirring for 12 hours at normal temperature, and centrifugally separating solid substances after reaction to obtain vinyltrimethoxysilane modified nano-vermiculite sheets (MVMT);
(4) Respectively preparing 12g of CHQ and 10g of MVMT into 2% aqueous solution, mixing the two solutions according to a mass ratio of 1.
Under the condition that the relative humidity (RH%) of the air is 100%, the Oxygen Transmission Rate (OTR) of the organic-inorganic composite membrane is 11.9 +/-0.19cm3/m 2. Atm. Day by adopting an oxygen transmission rate tester; the water vapor transmission rate (WTR) of the organic-inorganic composite film is 3.69 +/-0.36 g/m < 2 >. 24h measured by a water vapor transmission rate tester.
Example 4
(1) Dissolving 10g of Chitosan (CS) in 2% acetic acid aqueous solution by mass fraction to prepare 2% CS solution by mass fraction, adding 12g of epoxy acrylate (GMA), adding 0.5g of potassium persulfate (KPS) as a catalyst, heating to 80 ℃, reacting for 12h, and preparing epoxy acrylate modified Chitosan (CHQ) solution;
(2) Adding 500ml ethanol into CHQ solution to separate out solid matter from CHQ solution, centrifuging to separate out solid matter, washing with ethanol for 2 times, and drying at 60 deg.C to obtain CHQ;
(3) Dissolving 10g of Vinyltrimethoxysilane (VTMS) in an ethanol aqueous solution (the volume ratio of ethanol to water is 0.2 to 1), stirring for 1h to uniformly disperse the ethanol aqueous solution, and preparing a VMTS solution with the mass fraction of 1%; diluting 7.8wt% of the nano vermiculite piece dispersion liquid into 1wt% of the nano vermiculite piece dispersion liquid, and performing ultrasonic treatment for 1h. Mixing 500g of VTMS solution and 500g of nano-vermiculite sheet dispersion liquid, adjusting the pH value to 10 by using 1mol/L of NaOH solution, stirring for 12 hours at normal temperature, and centrifugally separating solid substances after reaction to obtain vinyltrimethoxysilane modified nano-vermiculite sheets (MVMT);
(4) Respectively preparing 11g of CHQ and 10g of MVMT into aqueous solutions with the mass fraction of 2%, mixing the two solutions according to the mass ratio of 1.
Under the condition that the relative humidity (RH%) of air is 100%, the Oxygen Transmission Rate (OTR) of the organic-inorganic composite membrane is 9.19 +/-0.23cm 3/m < 2 >. Atm.day by adopting an oxygen transmission rate tester; the water vapor transmission rate (WTR) of the organic-inorganic composite film is 2.92 +/-0.37 g/m < 2 >. 24h measured by a water vapor transmission rate tester.
Example 5
(1) Dissolving 10g of Chitosan (CS) in 2% acetic acid aqueous solution by mass fraction to prepare 2% CS solution by mass fraction, adding 12g of epoxy acrylate (GMA), adding 0.5g of potassium persulfate (KPS) as a catalyst, heating to 80 ℃, and reacting for 12h to prepare epoxy acrylate modified Chitosan (CHQ) solution;
(2) Adding 500ml ethanol into CHQ solution to separate out solid matter from CHQ solution, centrifuging to separate out solid matter, washing with ethanol for 2 times, and drying at 60 deg.C to obtain CHQ;
(3) Dissolving 10g of Vinyltrimethoxysilane (VTMS) in an ethanol aqueous solution (the volume ratio of ethanol to water is 0.2: 1), stirring for 1h to uniformly disperse the mixture, and preparing a VMTS solution with the mass fraction of 1%; diluting 7.8wt% of the nano vermiculite piece dispersion liquid into 1wt% of the nano vermiculite piece dispersion liquid, and performing ultrasonic treatment for 1h. Mixing 500g of VTMS solution and 500g of nano vermiculite piece dispersion liquid, adjusting the pH value to 10 by using 1mol/L of NaOH solution, stirring for 12 hours at normal temperature, and centrifugally separating solid substances after reaction to obtain vinyltrimethoxysilane modified nano vermiculite pieces (MVMT);
(4) Respectively preparing 9g of CHQ and 10g of MVMT into aqueous solutions with the mass fraction of 2%, mixing the two solutions according to the mass ratio of 1.
Under the condition that the relative humidity (RH%) of air is 100%, an oxygen transmission rate tester is adopted to measure the Oxygen Transmission Rate (OTR) of the organic-inorganic composite membrane to be 4.14 +/-0.33cm 3/m < 2 >. Atm.day; the water vapor transmission rate (WTR) of the organic-inorganic composite film is 1.77 +/-0.58 g/m < 2 >. 24h measured by a water vapor transmission rate tester.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1. A method for preparing an organic-inorganic composite film, comprising the steps of:
dissolving chitosan in an acid solution, adding epoxy acrylate and persulfate catalysts, and reacting at 50-80 ℃ to obtain a modified chitosan solution;
separating the solid modified chitosan from the modified chitosan solution;
dispersing the nano vermiculite sheets and a silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid substance, namely the modified nano vermiculite sheets; the silane modifier provides double bonds into the modified nano-vermiculite flakes;
dispersing the modified chitosan and the modified nano vermiculite slices in water, and adding a catalyst to obtain film forming slurry;
preparing the film-forming slurry into a film shape, and curing, crosslinking and drying to obtain an organic-inorganic composite film;
the method comprises the following steps of dissolving chitosan in an acid solution, adding epoxy acrylate and persulfate catalysts, and reacting at 50-80 ℃ to obtain a modified chitosan solution:
the mass ratio of the chitosan to the epoxy acrylate is 1 (0.5-1.5); the mass ratio of the chitosan to the persulfate catalyst is 1 (0.03-0.05); the persulfate catalyst comprises at least one of ammonium persulfate, potassium persulfate and sodium persulfate;
dispersing the nano vermiculite sheets and the silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid, namely the modified nano vermiculite sheets: the mass ratio of the nano vermiculite pieces to the silane modifier is 1 (0.8-1.2); the silane modifier comprises at least one of vinyltrimethoxysilane, vinyltriethoxysilane and vinyltrichlorosilane.
2. The method of preparing the organic-inorganic composite membrane according to claim 1, wherein the step of separating the modified chitosan in a solid state from the modified chitosan solution comprises:
adding a precipitation solvent into the modified chitosan solution to precipitate a solid in the modified chitosan solution, and then separating the solid to obtain modified chitosan;
wherein the precipitation solvent comprises at least one of methanol, ethanol, ethylene glycol and isopropanol.
3. The method for preparing an organic-inorganic composite membrane according to claim 1, wherein the step of dispersing the nano vermiculite sheets and the silane modifier in an organic solution, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is completed to obtain a solid substance, i.e., the modified nano vermiculite sheets, comprises:
NaOH is used for regulating the pH value to 9-11.
4. The method for preparing the organic-inorganic composite membrane according to claim 1, wherein the step of dispersing the nano-vermiculite pieces and the silane modifier in an organic solution, adjusting the pH value to 9 to 11, and performing solid-liquid separation after the reaction is completed to obtain a solid substance, namely the modified nano-vermiculite pieces, comprises:
dissolving a silane modifier in an organic solution to obtain a silane modifier solution;
dispersing the nano vermiculite slices in water to obtain nano vermiculite slice dispersion liquid;
and mixing the silane modifier solution and the nano vermiculite sheet dispersion liquid, adjusting the pH value to 9-11, and performing solid-liquid separation after the reaction is finished to obtain a solid, namely the modified nano vermiculite sheet.
5. The method for preparing an organic-inorganic composite membrane according to claim 1, wherein the step of dispersing the modified chitosan and the modified nano-vermiculite flakes in water and adding a catalyst to obtain a membrane-forming slurry comprises:
the mass ratio of the modified chitosan to the modified nano vermiculite pieces is (0.8-1.2): 1.
6. The method for preparing an organic-inorganic composite membrane according to claim 1, wherein the step of dispersing the modified chitosan and the modified nano-vermiculite flakes in water and adding a catalyst to obtain a membrane-forming slurry comprises:
the catalyst comprises at least one of dibenzoyl peroxide, ammonium ceric nitrate, ammonium ferrous sulfate and potassium persulfate.
7. The method of preparing an organic-inorganic composite film according to claim 6, wherein the step of preparing the film-forming slurry into a film shape, curing, crosslinking, and drying to obtain the organic-inorganic composite film comprises:
and preparing the film-forming slurry into a film shape, placing the film-forming slurry into a microwave with the radiation power of 500-800W for 2-10 min to enable the modified chitosan and the modified nano-vermiculite sheet to be cured and crosslinked at the temperature of 60-120 ℃, and then drying to obtain the organic-inorganic composite film.
8. An organic-inorganic composite film produced by the method for producing an organic-inorganic composite film according to any one of claims 1 to 7.
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