CN113463388A - Inorganic/polymer composite membrane for preventive protection of paper cultural relics and preparation method thereof - Google Patents
Inorganic/polymer composite membrane for preventive protection of paper cultural relics and preparation method thereof Download PDFInfo
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention belongs to the field of polymer fiber, in particular to an inorganic/polymer composite membrane for the preventive protection of paper cultural relics and a preparation method thereof, which comprises the steps of firstly dissolving a carbon source material in water, and then carrying out hydrothermal reaction to obtain carbon nanospheres; uniformly mixing and dissolving the synthesized nano carbon spheres and a titanium dioxide precursor in a solvent, and then carrying out hydrothermal reaction to obtain a composite nano material with a core-shell structure; then dissolving a high molecular polymer and the composite nano material in a solvent to form a uniform high molecular solution for electrostatic spinning to obtain a composite fiber membrane; and dissolving an acrylate monomer and a light curing agent in water, spraying the curing liquid on the composite fiber membrane, and finally irradiating by using an ultraviolet lamp for curing and forming to obtain a final product. The composite fiber prepared by the invention can effectively achieve the performances of super-hydrophobicity, ultraviolet shielding, antibiosis, bacteriostasis and the like without changing the texture and the pigment of the paper cultural relic.
Description
Technical Field
The invention relates to the field of polymer fibers, in particular to an inorganic/polymer composite film for preventive protection of paper cultural relics and a preparation method thereof.
Background
The paper cultural relics are used as a carrier for bearing history and culture and are important for cultural heritageThe component part comprises a large amount of precious cultural history materials and records and is one of the cultural relics which are most difficult to preserve for a long time. Because the main raw material of the paper cultural relics is plant fiber such as cellulose, and the cellulose has oxygen bridges for connecting glucose into long chains to attract H+And easily oxidizable group (-CH) in the cellulose structure2OH and-OH) makes it susceptible to a series of chemical reactions that initiate the breaking of cellulose chains. Therefore, in the preservation process, the paper cultural relics are easily broken under the influence of environmental factors such as humidity, microorganisms, ultraviolet rays and the like, the mechanical strength is reduced, bacteria and pests are bred, further, the damages such as yellowing, brittle fracture, breakage and the like are caused, and the preservation life and the ornamental and research values are greatly reduced.
Desirable characteristics of materials used to preserve paper products should include flexibility, transparency, cohesion, long-term durability and reversibility, while the protection method should be fast, capable of wide use and harmless to paper articles. Some scientific studies to improve paper strength include silk screen lamination, mylar encapsulation, radiation polymerization, parylene processes and graft co-coating methods. However, all of these methods have some inevitable disadvantages. The web itself is susceptible to aging, resulting in aging of the protected paper product, while the polyester film changes the appearance, optical properties, texture and thickness of the paper and becomes rigid after the aging process. Whether the radiation method has positive or negative influence on the paper vestige is not determined. Parylene protection needs to be performed in vacuum, involving complex processes and stringent conditions. Direct resin coating also leads to rapid paper aging due to concentration differences between the surface and the interior of the paper, which are caused by poor wetting between the resin and the paper fibers. Graft polymerization provides good protection of cellulose-based substrates and introduces the advantages of graft polymers, such as resistance to biological attack. Consolidation is achieved by a grafting process that is difficult to separate. However, the difficulty of reversibility seems to be the biggest obstacle in application. Therefore, there is an urgent need for a method for preserving paper that is efficient, convenient, harmless, and stable for a long period of time.
In the aspect of paper cultural relic protection, researchers have developed composite fiber membranes for paper cultural relic protection, but some problems also exist. For example, a patent of a method for protecting paper documents by using electrostatic spinning fiber membranes (publication number CN 108425272B) has been granted, in which ultraviolet shielding agents and polymers are directly doped to obtain composite fiber membranes to protect paper cultural relics, only composite fiber membranes with good hydrophobicity and ultraviolet shielding effect are obtained, the damage of fungi and bacteria to the paper cultural relics is ignored, and the damage of microorganisms to the cultural relics cannot be slowed down. At present, composite fiber materials with super-hydrophobicity, high ultraviolet shielding property and high antibacterial activity cannot be obtained by compounding single nanoparticles and macromolecules and are used for preventive protection of paper cultural relics. In addition, the functional nanoparticles can be abraded and fall off during the use process through simple doping, and the original excellent performance is lost.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: the method uses simple materials, has multiple functions, can be used for a long time, is simple and convenient to operate, has reasonable cost, can be prepared in a large scale and is safe to use, and the inorganic/polymer composite membrane for the preventive protection of the paper cultural relics and the preparation method thereof.
The invention also aims to provide the inorganic/polymer composite membrane for the preventive protection of the paper cultural relics, which is prepared by the method. The inorganic ultraviolet shielding agent/polymer composite membrane for the preventive protection of paper cultural relics combines a high-performance inorganic nano material and a polymer fiber membrane.
The purpose of the invention is realized by the following scheme:
a preparation method of an inorganic/polymer composite membrane for the preventive protection of paper cultural relics comprises the following steps:
s1, synthesis of a high-performance inorganic nano material: dissolving a carbon source material in water, and then carrying out hydrothermal reaction to obtain carbon nanospheres; uniformly mixing and dissolving the synthesized nano carbon spheres and a titanium dioxide precursor in a solvent, and then carrying out hydrothermal reaction to obtain a composite nano material with a core-shell structure;
s2, preparing a spinning solution and carrying out electrostatic spinning: dissolving a high molecular polymer and the composite nano material in a solvent to form a uniform high molecular solution; performing electrostatic spinning by using the composite fiber membrane as a spinning solution to obtain a composite fiber membrane;
s3, photocuring treatment: and (3) dissolving an acrylate monomer and a light curing agent in water to prepare a curing liquid, spraying the curing liquid on the composite fiber membrane, and finally irradiating by using an ultraviolet lamp for curing and forming to obtain a final product.
The carbon source material in the step S1 is preferably at least one of D-anhydrous glucose, L- (-) -xylose, D- (+) -maltose monohydrate, fructose, and sucrose, and the mass fraction thereof in water is 0.01% to 20%;
the temperature of the hydrothermal reaction in the step S1 is 120-200 ℃, and the time of the hydrothermal reaction is 3-12 h;
the precursor of titanium dioxide in step S1 is preferably at least one of tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate, and the mass fraction of the precursor in the mixed solution is 0.5% to 15%;
the mass ratio of the carbon nanospheres to the titanium dioxide precursor in the step S1 is preferably 1: 0.1-1.2.
In the step S1, the temperature of the second hydrothermal reaction is 120-200 ℃, and the reaction time is 1-5 h.
The solvent in step S1 is preferably at least one of absolute ethyl alcohol, water, and absolute methyl alcohol.
The mass ratio of the composite nano material to the high molecular polymer in the step S2 is 0-0.8: 1, and the using amount of the composite nano particles is not 0.
In step S2, the polymer is preferably at least one of polyvinylidene fluoride, polyacrylonitrile, hydrogenated poly (styrene-butadiene-styrene), and polystyrene-polybutadiene-polystyrene block copolymer.
The solvent in step S2 is at least one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, and acetone.
In the step S2, the spinning parameters are that the spinning nozzle is connected with 0.5-50 kV voltage (positive or negative), the collecting device is connected with 0-50 kV voltage (positive or negative, opposite to the potential of the spinning nozzle, or grounded); the distance between the spinning nozzle and the collecting device is 5-50 cm, and the feeding speed of the spinning solution is 0.1-30 mL/h. The spinning environment temperature is 5-60 ℃, and the relative humidity is 25-95%.
In the step S3, the acrylate monomer is preferably at least one of pure acrylate, 1, 6-hexanediol diacrylate and pentaerythritol triacrylate, and the mass fraction of the acrylate monomer in the mixed solution is 0.5-15%;
the light curing agent in the step S3 is preferably at least one of benzoin ethyl ether, dialkoxy acetophenone, chlorinated acetophenone and benzophenone;
the photocuring time in the step S3 is preferably 0.01-1S; in the step S3, the mass ratio of the light curing agent to the acrylate monomer is preferably 0-0.8: 1, and the dosage of the light curing agent is not 0.
In the step S3, the power of the ultraviolet lamp is preferably 24-60W.
An inorganic/polymer composite membrane for the preventive protection of paper cultural relics is prepared by the method. The prepared fiber membrane is cut into a proper size, and then the paper cultural relics are wrapped, so that the multifunctional protection and durable effect is achieved.
Compared with the prior art, the invention has the following beneficial effects:
1. the synthesis method of the nano particles provided by the invention has the advantages that the raw materials are easy to obtain, and the large-scale stable preparation can be carried out. Meanwhile, through compounding with the carbon material, the absorption value of the nano particles in a visible light wave band is more than 20 times higher than that of the traditional titanium dioxide, the nano particles have a good visible light shielding effect, the ultraviolet absorption performance of the nano particles is more than 10 times higher than that of the traditional titanium dioxide, and meanwhile, the nano particles have extremely strong antibacterial performance.
2. The composite fiber prepared by the invention can effectively achieve the performances of super-hydrophobicity, ultraviolet shielding, antibiosis, bacteriostasis and the like without changing the texture and the pigment of the paper cultural relic. Meanwhile, the nano-sized and micron-sized fibers with the average diameter can be obtained by regulating and controlling spinning parameters and the types of macromolecules.
3. The invention has simple process, reliable quality and high repeatability. The prepared composite fiber membrane can be used for the preventive protection of paper cultural relics.
Drawings
Fig. 1 is a scanning electron microscope photograph of the nanocarbon spheres prepared in example 1.
Fig. 2 is a scanning electron microscope photograph of the composite nanoparticle prepared in example 2.
Fig. 3 is a transmission electron microscope photograph of the composite nanoparticle prepared in example 2.
Fig. 4 is a graph of the uv-vis absorption of the composite nanoparticles prepared in example 3 with pure titanium dioxide.
FIG. 5 is a scanning electron micrograph of a composite fiber, wherein FIG. 5a is a scanning electron micrograph of a nanofiber prepared in example 4; fig. 5b is a scanning electron microscope photograph of the micron-sized fiber prepared in example 1.
FIG. 6 is a scanning electron micrograph of a composite fiber, wherein FIG. 6a is a scanning electron micrograph of a composite fiber prepared according to example 1; fig. 6b is a scanning electron micrograph of the composite fiber prepared in example 2.
Fig. 7 is a contact angle graph of the composite fiber prepared in example 3.
Fig. 8 is an antibacterial experimental graph of the composite fiber prepared in example 5.
Detailed Description
The present invention will be further described with reference to the following specific examples and accompanying drawings, which should not be construed as limiting the invention thereto.
Example 1
Dissolving 0.5g D-anhydrous glucose in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 10h at 180 ℃, and washing with distilled water and ethanol for multiple times to obtain the nano carbon spheres with uniform appearance and size. Uniformly dispersing 0.5g of carbon nanospheres and 0.2g of butyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3h at 160 ℃, and washing with ethyl alcohol for multiple times to obtain the composite nanoparticles with the core-shell structure.
Dissolving polyvinylidene fluoride and composite nanoparticles in a mixed solvent of N, N-dimethylformamide and acetone (mass ratio of 4: 1) to form a polymer solution with the mass fraction of 12 wt%, wherein the mass ratio of the composite nanoparticles to the polymer is 0.8: 1.
The spinneret is connected with a voltage of +15kV, and the receiving device is connected with a voltage of-1 kV. The distance between the spinneret and the receiver was 15cm, and the spinning solution was fed at a rate of 3 mL/h. The temperature of the spinning environment is 25 ℃ and the relative humidity is 60 percent. And after spinning is finished, completely volatilizing the solvent to obtain a fiber final product.
Dissolving 10g of pure acrylate and 5g of benzoin ethyl ether in water to prepare a curing liquid, spraying the curing liquid on the composite fiber membrane, and finally irradiating the composite fiber membrane by using a 60W ultraviolet lamp for 1s for curing and forming to obtain a final product.
Example 2
Dissolving 0.25g D- (+) -maltose monohydrate in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 10 hours at 180 ℃, and washing for multiple times by using distilled water and ethanol to obtain the carbon nanospheres with uniform appearance and size. Uniformly dispersing 0.2g of carbon nanospheres and 0.2g of butyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3h at 160 ℃, and washing with ethyl alcohol for multiple times to obtain the composite nanoparticles with the core-shell structure.
Dissolving polyvinylidene fluoride and composite nanoparticles in a mixed solvent of N, N-dimethylformamide and acetone (mass ratio of 4: 1) to form a polymer solution with the mass fraction of 12 wt%, wherein the mass ratio of the composite nanoparticles to the polymer is 0.4: 1.
The spinneret is connected with a voltage of +13kV, and the receiving device is connected with a voltage of-3 kV. The distance between the spinneret and the receiving device was 15cm, and the spinning solution feeding speed was 2 mL/h. The temperature of the spinning environment is 25 ℃ and the relative humidity is 60 percent. And after spinning is finished, completely volatilizing the solvent to obtain a fiber final product.
Dissolving 8g of 1, 6-hexanediol diacrylate and 2g of benzoin ethyl ether in water to prepare a curing liquid, spraying the curing liquid on the composite fiber membrane, and finally irradiating the composite fiber membrane by using a 30W ultraviolet lamp for 2 seconds for curing and forming to obtain a final product.
Example 3
Dissolving 0.1g of sucrose in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 6h at 180 ℃, and washing with distilled water and ethanol for multiple times to obtain the carbon nanospheres with uniform appearance and size. Uniformly dispersing 0.5g of carbon nanospheres and 0.2g of ethyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3h at 160 ℃, and washing with ethanol for multiple times to obtain the composite nanoparticles with the core-shell structure.
Dissolving hydrogenated poly (styrene-butadiene-styrene) and composite nanoparticles in a mixed solvent of tetrahydrofuran to form a high polymer solution with the mass fraction of 14 wt%, wherein the mass ratio of the composite nanoparticles to the high polymer is 0.6: 1.
The spinneret is connected with a voltage of +14kV, and the receiving device is connected with a voltage of-2 kV. The distance between the spinneret and the receiving device was 15cm, and the spinning solution feeding speed was 1 mL/h. The temperature of the spinning environment is 25 ℃ and the relative humidity is 60 percent. And after spinning is finished, completely volatilizing the solvent to obtain a fiber final product.
Dissolving 6g of pentaerythritol triacrylate and 6g of dialkoxyacetophenone in water to prepare a curing liquid, spraying the curing liquid on the composite fiber membrane, and finally irradiating the composite fiber membrane by using a 40W ultraviolet lamp for 1.5 seconds for curing and forming to obtain a final product.
Example 4
Dissolving 0.15g L- (-) xylose in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 8h at 160 ℃, and washing for multiple times by using distilled water and ethanol to obtain the carbon nanospheres with uniform appearance and size. Uniformly dispersing 0.5g of carbon nanospheres and 0.4g of propyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3h at 160 ℃, and washing with ethyl alcohol for multiple times to obtain the composite nanoparticles with the core-shell structure.
Dissolving polyacrylonitrile and composite nanoparticles in a mixed solvent of tetrahydrofuran to form a polymer solution with the mass fraction of 10 wt%, wherein the mass ratio of the composite nanoparticles to the polymer is 1: 1.
The spinneret is connected with a voltage of +16kV, and the receiving device is connected with a voltage of-0.5 kV. The distance between the spinneret and the receiving device was 15cm, and the spinning solution feeding speed was 0.3 mL/h. The temperature of the spinning environment is 25 ℃ and the relative humidity is 60 percent. And after spinning is finished, completely volatilizing the solvent to obtain a fiber final product.
Dissolving 10g of pentaerythritol triacrylate and 3g of chlorinated acetophenone in water to prepare a curing solution, spraying the curing solution on the composite fiber membrane, and finally irradiating by using a 40W ultraviolet lamp for 1.5s for curing and forming to obtain a final product.
Example 5
Dissolving 0.05g of sucrose in 50mL of distilled water, adding the solution into a high-pressure hydrothermal reaction kettle, reacting for 10h at 160 ℃, and washing with distilled water and ethanol for multiple times to obtain the carbon nanospheres with uniform appearance and size. Uniformly dispersing 0.5g of carbon nanospheres and 0.6g of ethyl titanate in 30mL of absolute ethyl alcohol, adding the mixture into a high-pressure hydrothermal reaction kettle, reacting for 3h at 160 ℃, and washing with ethanol for multiple times to obtain the composite nanoparticles with the core-shell structure.
Dissolving polyacrylonitrile and composite nanoparticles in a mixed solvent of dichloromethane to form a high molecular solution with the mass fraction of 18 wt%, wherein the mass ratio of the composite nanoparticles to polyvinylidene fluoride is 0.5: 1.
The spinneret is connected with a voltage of +18kV, and the receiving device is connected with a voltage of-1 kV. The distance between the spinneret and the receiving device was 15cm, and the spinning solution feeding speed was 0.5 mL/h. The temperature of the spinning environment is 25 ℃ and the relative humidity is 60 percent. And after spinning is finished, completely volatilizing the solvent to obtain a fiber final product.
Dissolving 10g of pure acrylate and 8g of benzophenone in water to prepare a curing solution, spraying the curing solution on the composite fiber membrane, and finally irradiating the composite fiber membrane for 1s by using a 60W ultraviolet lamp for curing and forming to obtain a final product.
FIG. 1 is a scanning electron microscope photograph of carbon nanospheres prepared by the technical method provided by the invention, and the average diameter of the nanoparticles is about 300 nm. FIG. 2 is a scanning electron micrograph of composite nanoparticles prepared by the technical method provided by the present invention, with an average diameter of about 320 nm. FIG. 3 is a TEM image of the composite nanoparticles prepared by the method of the present invention, with an average diameter of about 320 nm.
FIG. 5 is a scanning electron micrograph of a fibrous membrane prepared by the technical process provided by the present invention. The nano-sized and micron-sized fibers with the average diameter can be obtained by regulating and controlling spinning parameters and the types of macromolecules.
FIG. 4 is a diagram of the UV-visible absorption of composite nanoparticles and pure titanium dioxide prepared by the technical process provided by the present invention. Tests show that the composite nano particles have very high absorption values in ultraviolet and visible light bands, and the titanium dioxide has high absorption peaks only in the ultraviolet band.
FIG. 6 is a scanning electron micrograph of 2 composite fibers prepared by the technical process provided by the present invention (a figure obtained by example 1 and b figure obtained by example 2).
FIG. 7 is a photograph showing the contact angle of the composite fiber prepared by the technical method disclosed in the present invention, which exceeds 150 degrees, and has substantially super-hydrophobic property.
FIG. 8 is a photograph of a composite fiber bacteriostatic photo prepared by the technical method disclosed by the invention, which shows an obvious bacteriostatic circle and has certain bacteriostatic property.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an inorganic/polymer composite membrane for the preventive protection of paper cultural relics is characterized by comprising the following steps:
s1, synthesis of a high-performance inorganic nano material: dissolving a carbon source material in water, and then carrying out hydrothermal reaction to obtain carbon nanospheres; uniformly mixing and dissolving the synthesized nano carbon spheres and a titanium dioxide precursor in a solvent, and then carrying out hydrothermal reaction to obtain a composite nano material with a core-shell structure;
s2, preparing a spinning solution and carrying out electrostatic spinning: dissolving a high molecular polymer and the composite nano material in a solvent to form a uniform high molecular solution; performing electrostatic spinning by using the composite fiber membrane as a spinning solution to obtain a composite fiber membrane;
s3, photocuring treatment: and (3) dissolving an acrylate monomer and a light curing agent in water to prepare a curing liquid, spraying the curing liquid on the composite fiber membrane, and finally irradiating by using an ultraviolet lamp for curing and forming to obtain a final product.
2. The method of claim 1, wherein: the carbon source material in the step S1 is at least one of D-anhydrous glucose, L- (-) -xylose, D- (+) -maltose monohydrate, fructose, and sucrose; the mass fraction of the carbon source material in water is 0.01-20%.
3. The method of claim 1, wherein: the precursor of the titanium dioxide in the step S1 is at least one of tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate; the mass fraction of the mixed solution is 0.5-15%.
4. The method of claim 1, wherein: in the step S1, the mass ratio of the carbon nanospheres to the titanium dioxide precursor is 1: 0.1-1.2.
5. The method of claim 1, wherein: the temperature of the hydrothermal reaction in the step S1 is 120-200 ℃, and the time of the hydrothermal reaction is 3-12 h; in the step S1, the temperature of the second hydrothermal reaction is 120-200 ℃, and the reaction time is 1-5 h.
6. The method of claim 1, wherein: in the step S3, the acrylate monomer is at least one of pure acrylate, 1, 6-hexanediol diacrylate, and pentaerythritol triacrylate; the mass fraction of the mixed solution is 0.5-15%.
7. The method of claim 1, wherein: the solvent in step S2 is at least one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, and acetone; in the step S3, the light curing agent is at least one of benzoin ethyl ether, dialkoxyacetophenone, chlorinated acetophenone, and benzophenone.
8. The method of claim 1, wherein: in the step S3, the mass ratio of the light curing agent to the acrylate monomer is 0-0.8: 1; the amount of the light curing agent is not 0.
9. The method of claim 1, wherein: in the step S2, the spinning parameters are that the spinning nozzle is connected with 0.5-50 kV voltage, and the collecting device is connected with 0-50 kV voltage; the distance between the spinning nozzle and the collecting device is 5-50 cm, and the feeding speed of the spinning solution is 0.1-30 mL/h; the spinning environment temperature is 5-60 ℃, and the relative humidity is 25-95%; in the step S3, the power of the ultraviolet lamp is 24-60W.
10. The inorganic/polymer composite film for the preventive protection of paper cultural relics, which is prepared by the method of any one of claims 1 to 9.
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Inventor after: Wang Linge Inventor after: Feng Guiju Inventor after: Zhang Di Inventor after: Jia Yifan Inventor after: Yu Qianqian Inventor before: Wang Linge Inventor before: Zhang Di Inventor before: Jia Yifan Inventor before: Yu Qianqian |