CN115975329B - Nanometer silicon oxide modified composite salt-resistant material and preparation method and application thereof - Google Patents
Nanometer silicon oxide modified composite salt-resistant material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nano silicon oxide modified composite salt-resistant material, which is prepared by grafting starch on acrylamide in a water phase for cross-linking polymerization, adding a modifier or a copolymer to obtain an intermediate, and then further carrying out reaction compounding with nano silicon oxide to obtain a silicon-based hybridized organic high molecular water-absorbing salt-resistant composite resin. Meanwhile, the invention also discloses a preparation method and application of the composite salt-resistant material. According to the invention, by utilizing the characteristics that the nano silicon dioxide has an orderly distributed porous network structure and a functionalized substrate structure cannot be damaged or changed, an efficient carrier is provided for migration, adsorption and anchoring of salt ions, and the desalination efficiency is improved by utilizing the performance or functional synergistic effect among components, so that the stable and high salt tolerance of the material is further improved, and the salt damage of cultural relics is reduced.
Description
Technical Field
The invention relates to the field of functional polymers, in particular to a nano silicon oxide modified composite salt-tolerant material, a preparation method and application thereof.
Background
The pottery, the mural, the earthen site and the like are important components of excellent cultural heritage of China, but through long geological and environmental evolution, the relic site has different degrees of damage behaviors such as shortages, hollows, falling, nail lifting and the like caused by salt damage, and the essence of the damage behavior is that soluble salt in a matrix or surrounding environment where the relic is located is enriched on the surface layer of the relic through a dissolving-crystallizing process under the influence of alternating change of temperature and humidity, and the process causes damage to the relic body and greatly damages artistic works drawn on the surface of the relic. Therefore, the method intervenes in advance in the area where salt damage is easy to occur, and the searching of safe and efficient water-absorbing desalting materials is the key for solving the salt damage of cultural relics.
The super absorbent resin is a functional polymer material with a three-dimensional network structure with certain crosslinking degree, and the molecular structure of the super absorbent resin contains a large number of strong hydrophilic groups such as carboxyl, hydroxyl, amido, sulfonic acid group and the like. Compared with the traditional water-absorbing materials such as sponge, cellulose and silica gel, the high water-absorbing resin has the characteristics of high water absorption capacity, high water absorption rate, strong water retention capacity, no toxicity, no harm and the like, is often used as a repairing material for cultural relic protection, for example, chinese patent CN101307120A discloses a water-absorbing material and application, introduces a preparation method of starch grafted acrylamide resin suitable for cultural relic repairing protection, and has the advantages of rich raw material sources, low cost, high water absorption, biodegradability and the like. Because of the particularity of relic sites and the desalting requirement, the super absorbent resin is required to have certain salt tolerance and high water absorption rate in terms of performance because the super absorbent resin does not contain acidic or basic groups structurally. Therefore, improvement of the structure of the super absorbent resin is needed to improve the salt tolerance of the resin material to meet the demands of the field of cultural relic restoration and protection.
At present, a great deal of literature reports how to improve the salt tolerance of water-absorbent resins, mainly comprising the steps of introducing a nonionic monomer insensitive to salt ions, compounding with clay, forming an interpenetrating network with a hydrophilic polymer, copolymerizing anions and cations, and the like, for example, patent CN102617807A, CN102250276A, CN101270173A discloses a preparation method of clay modified organic composite water-absorbent salt-tolerant materials, and experimental results show that the addition of clay inorganic matters with a three-dimensional layered structure and a plurality of hydroxyl groups and active points on the surface improves the water-absorbent desalting performance of the composite materials. Patent CN102827381a discloses a novel interpenetrating network super absorbent resin with excellent salt tolerance, which is an interpenetrating polymer network structure formed by using interpenetrating network technology to interpenetrate sodium polyvinyl alcohol in a graft polymer of starch and acrylic acid. Although the method improves the salt tolerance of the material, the migration of soluble salts in the material is still in a passive adsorption state.
Disclosure of Invention
The invention aims to solve the technical problem of providing a nano silicon oxide modified composite salt-resistant material for reducing the salt damage of cultural relics.
The invention aims to provide a preparation method of the nano silicon oxide modified composite salt-resistant material.
The third technical problem to be solved by the invention is to provide the application of the nano silicon oxide modified composite salt-tolerant material.
In order to solve the problems, the nano silicon oxide modified composite salt-tolerant material is characterized in that: the material is prepared by grafting starch on acrylamide in a water phase for cross-linking polymerization, adding a modifier or a copolymer to obtain an intermediate, and then further carrying out reaction compounding with nano silicon oxide to obtain the silicon-based hybridized organic high polymer water-absorbing salt-resistant composite resin.
The preparation method of the nano silicon oxide modified composite salt-tolerant material comprises the following steps:
preparation of modified starch-acrylamide polymer:
dispersing starch in deionized water with the mass of 5-10 times of that of the starch, heating to 80-90 ℃ under the protection of nitrogen after the starch is uniformly dispersed, carrying out gelatinization treatment for 25-55 min, and cooling the system to 60-70 ℃; then sequentially adding an initiator aqueous solution with the concentration of 0.002-0.03 g/mL and a sodium sulfite aqueous solution with the concentration of 0.0006-0.002g/mL; after initiating reaction for 15min at 50-70 ℃, sequentially adding a modifier, a monomer acrylamide aqueous solution with the concentration of 0.075-0.125 g/mL and a cross-linking agent aqueous solution with the concentration of 0.000125-0.0005 g/mL, and carrying out graft polymerization at 50-65 ℃ under the protection of nitrogen; stopping introducing nitrogen after the reaction is finished, adding methanol for leaching treatment, fully drying the obtained solid at 60-80 ℃, and then crushing to obtain the modified starch-acrylamide polymer;
the mass of the initiator is 0.01-0.15 times of the mass of the starch; the mass of the sodium sulfite is 0.003-0.01 times of that of the starch; the mass of the modifier is 0.5-1.0 times of that of the starch; the mass of the monomer acrylamide is 3-5 times of that of the starch; the mass of the cross-linking agent is 0.005-0.02 times of the mass of the starch; the dosage of the methanol is 1-3 times of the total volume of the synthetic materials;
preparation of nano silicon oxide microspheres:
sequentially adding absolute ethyl alcohol, deionized water and ammonia water into a reaction bottle, stirring at 40 ℃ for 10min to uniformly mix the solution, then adding tetraethyl silicate (TEOS), and stirring in a water bath at 40 ℃ for reflux reaction for 24h; after the reaction is finished, centrifugally separating out a product, and repeatedly centrifugally washing with absolute ethyl alcohol and deionized water until the supernatant is neutral; drying the washed product at 80 ℃ to obtain nano silicon oxide microspheres; the volume ratio of the absolute ethyl alcohol to the deionized water to the ammonia water to the tetraethyl silicate is 40:4.5:3.5:1, a step of;
preparing a nano silicon oxide modified composite salt-resistant material:
dispersing the modified starch-acrylamide polymer in acetonitrile with the volume of 5-30 times of that of the modified starch-acrylamide polymer, adding the nano silicon oxide microspheres and anhydrous potassium carbonate, slowly dropwise adding a coupling agent in batches under stirring, and heating and refluxing for 24 hours under the protection of nitrogen; cooling to room temperature after the reaction is finished, separating out a product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain the nano silicon oxide modified composite salt-resistant material; the mass of the nano silicon oxide microspheres is 0.3-0.8 times of that of starch; the mass of the anhydrous potassium carbonate is 0.08-0.1 times of that of the starch; the mass of the coupling agent is 0.2-0.4 times of that of the starch.
The initiator in the step (A) is one or more than two of potassium persulfate, sodium sulfite, sodium persulfate, potassium permanganate, ammonium persulfate or sodium peroxide.
In the step, the cross-linking agent is one of glycerol, dimethylacrylamide, N' -methylenebisacrylamide or polyethylene glycol dimethacrylate.
The modifier in the step (A) is one or more than two of polyvinyl alcohol, kaolin, bentonite, a 13X molecular sieve and a 5A molecular sieve.
The coupling agent in the step III is one or more than two of 3-aminopropyl triethoxysilane (APTES), aminopropyl triethoxysilane (KH 550) or mercaptopropyl trimethoxysilane (KH 590).
The application of the nano silicon oxide modified composite salt-tolerant material is characterized in that: the composite salt-resistant material is used for water absorption and desalination treatment for repairing and protecting cultural relics or earthen sites.
Adding the composite salt-resistant material into deionized water with the mass of 100-1000 times of that of the composite salt-resistant material to form a viscous fluid which is uniformly dispersed, and uniformly coating the viscous fluid on a carrier KC-X60 non-woven fabric to obtain the KC-X60 applied desalination material with adsorption air permeability containing the composite salt-resistant material.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the surface to initiate monomer polymerization reaction to link the organic polymer on the surface of silicon dioxide, fully plays the respective advantages of the organic polymer and nano silicon oxide, not only realizes the dispersion of the material on the nano scale, but also enables the material to obtain ordered reticular multi-pore distribution on the basis of interpenetrating three-dimensional reticular structure.
2. The composite material obtained by the invention is continuously grafted and modified on the basis of organic groups after modifying different types of organic functional groups, and the characteristics that nano silicon dioxide has an orderly distributed porous network structure and a functionalized substrate structure cannot be damaged or changed are utilized, so that an efficient carrier is provided for migration, adsorption and anchoring of salt ions, and the desalting efficiency is improved by utilizing the performance or functional synergistic effect among components, so that the stable and high salt tolerance performance of the material is further improved, and the salt damage of cultural relics is reduced.
3. The invention modifies the starch grafted acrylamide polymer assembly, utilizes the grafted polymer in the composite material to absorb water, and transfers free inorganic salt in the salt-containing matrix into the composite material in the water migration process.
4. The addition of the modifier and the copolymer improves the interpenetrating crosslinking degree of the resin, and the addition of the nano silicon oxide effectively modifies the organic groups, so that the organic parts of the hybrid material are uniformly distributed.
5. The composite material does not contain strong acid or alkali groups, is acid-base neutral, and the aqueous solution is neutral after absorption, so that the composite material is particularly suitable for water absorption desalination treatment of cultural relics restoration protection by strictly controlling acid and alkali.
6. The raw materials of starch, acrylamide, ammonia and the like used in the preparation process are easy to obtain or prepare, the cost is low, the preparation method is simple, and the reaction condition is mild.
7. The composite material obtained by the invention is convenient to use, has good adaptability for removing salt on the surface of the earthen site, and effectively inhibits the damage of repeated dissolution-crystallization on the earthen site caused by the change of the ambient temperature and the humidity of the soluble salt on the surface of the matrix through the rapid migration of the salt on the surface.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is an infrared spectrum of a composite salt-tolerant material modified by nano silicon oxide.
FIG. 2 is a diagram of a scanning electron microscope of the nano silicon oxide modified composite salt-tolerant material.
Detailed Description
A composite salt-resistant material modified by nano silicon oxide is prepared through grafting starch to acrylamide, cross-linking polymerization in aqueous phase, adding modifier or copolymer to obtain intermediate, and reaction with nano silicon oxide to obtain silicon-base hybridized organic high-molecular water-absorbing salt-resistant resin.
The preparation method comprises the following steps:
preparation of modified starch-acrylamide polymer:
dispersing starch in deionized water with the mass of 5-10 times of that of the starch, heating to 80-90 ℃ under the protection of nitrogen after the starch is uniformly dispersed, carrying out gelatinization treatment for 25-55 min, and cooling the system to 60-70 ℃; then sequentially adding an initiator aqueous solution with the concentration of 0.002-0.03 g/mL and a sodium sulfite aqueous solution with the concentration of 0.0006-0.002g/mL; after initiating reaction for 15min at 50-70 ℃, sequentially adding a modifier, a monomer acrylamide aqueous solution with the concentration of 0.075-0.125 g/mL and a cross-linking agent aqueous solution with the concentration of 0.000125-0.0005 g/mL, and carrying out graft polymerization at 50-65 ℃ under the protection of nitrogen; stopping introducing nitrogen after the reaction is finished, adding methanol for leaching treatment, fully drying the obtained solid at 60-80 ℃, and then crushing to obtain the modified starch-acrylamide polymer.
Wherein: the initiator is one or more than two of potassium persulfate, sodium sulfite, sodium persulfate, potassium permanganate, ammonium persulfate or sodium peroxide. The mass of the initiator is 0.01-0.15 times, preferably 0.05-0.13 times of the mass of the starch.
The sodium sulfite is 0.003-0.01 times, preferably 0.006-0.01 times, the starch.
The modifier is one or more than two of polyvinyl alcohol, kaolin, bentonite, 13X molecular sieve and 5A molecular sieve. The mass of the modifier is 0.5-1.0 times of the mass of the starch.
The mass of the monomer acrylamide is 3-5 times of that of the starch.
The cross-linking agent is one of glycerol, dimethylacrylamide, N' -methylenebisacrylamide or polyethylene glycol dimethacrylate. The cross-linking agent is 0.005 to 0.02 times, preferably 0.005 to 0.015 times the mass of the starch.
The dosage of the methanol is 1-3 times of the total volume of the synthesized materials.
Preparation of nano silicon oxide microspheres:
sequentially adding absolute ethyl alcohol, deionized water and ammonia water into a reaction bottle, stirring at 40 ℃ for 10min to uniformly mix the solution, then adding tetraethyl silicate (TEOS), and stirring in a water bath at 40 ℃ for reflux reaction for 24h; after the reaction is finished, centrifugally separating out a product, and repeatedly centrifugally washing with absolute ethyl alcohol and deionized water until the supernatant is neutral; and drying the washed product at 80 ℃ to obtain the nano silicon oxide microspheres.
Wherein: the volume ratio (mL/mL) of absolute ethyl alcohol, deionized water, ammonia water and tetraethyl silicate is 40:4.5:3.5:1.
preparing a nano silicon oxide modified composite salt-resistant material:
dispersing the modified starch-acrylamide polymer in acetonitrile with the volume of 5-30 times of that of the modified starch-acrylamide polymer, adding nano silicon oxide microspheres and anhydrous potassium carbonate, slowly dropwise adding a coupling agent in batches under stirring, and heating and refluxing for 24 hours under the protection of nitrogen; and cooling to room temperature after the reaction is finished, separating out a product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain the nano silicon oxide modified composite salt-resistant material.
Wherein: the mass of the nano silicon oxide microsphere is 0.3-0.8 times of that of the starch.
The mass of the anhydrous potassium carbonate is 0.08-0.1 times of the mass of the starch.
The coupling agent is one or more of 3-aminopropyl triethoxysilane (APTES), aminopropyl triethoxysilane (KH 550) or mercaptopropyl trimethoxysilane (KH 590). The mass of the coupling agent is 0.2-0.4 times of the mass of the starch.
Application of a nano silicon oxide modified composite salt-resistant material: the composite salt-resistant material is used for the water-absorbing desalination treatment of cultural relics or earthen site restoration protection, and can transfer soluble salts which cause damage of the earthen site, the cultural relics and the like from a matrix to the invented water-absorbing composite salt-resistant material under the requirement of not damaging the surface morphology and the like as much as possible, and fix the transferred salts in the water-absorbing desalination composite material, thereby reducing the salt damage of cultural relics.
The specific process is as follows:
adding the composite salt-resistant material into deionized water with the mass of 100-1000 times of that of the composite salt-resistant material to form a viscous fluid which is uniformly dispersed, uniformly coating the viscous fluid on a carrier KC-X60 non-woven fabric, and for uniformity, coating the first layer of coating material once after drying to obtain the KC-X60 applied desalination material containing the composite salt-resistant material and having adsorption and air permeability.
When in use, the desalination material is pretreated according to the surface morphology and state of the needed desalination earthen site, and then the wet desalination composite material is applied to the surface of the site for salt migration and fixation.
Embodiment 1a preparation method of a nano silicon oxide modified composite salt-tolerant material comprises the following steps:
preparation of modified starch-acrylamide polymer:
soaking 5.0g of starch in 25mL of deionized water, continuously stirring for 30min to uniformly disperse the starch, heating to 80-85 ℃ under the protection of nitrogen for gelatinization for 25min, cooling to 60 ℃ while the system is semitransparent colloid; then 25mL of an aqueous solution containing 0.36g of potassium persulfate and 0.018g of sodium sulfite was added; after initiating reaction for 15min at 50-70 ℃, adding 2.56g of kaolin and 200mL of aqueous solution containing 20.0g of acrylamide and 0.042g of cross-linking agent N, N' -methylenebisacrylamide, and carrying out polymerization reaction for 2h at 65 ℃ under the protection of nitrogen; stopping introducing nitrogen after the reaction is finished, adding 100mL of methanol until the reaction product is immersed, leaching, fully drying the obtained solid at 60-80 ℃, crushing, and sieving with a 100-mesh sieve to obtain 20.0195g of modified starch-acrylamide polymer.
Preparation of nano silicon oxide microspheres:
adding 80mL of absolute ethyl alcohol, 9mL of deionized water and 7mL of ammonia water into a 500mL three-neck round-bottom flask in sequence, stirring at 40 ℃ for 10min to uniformly mix the solution, then rapidly adding 2mL of tetraethyl silicate (TEOS), and stirring in a water bath at 40 ℃ for reflux reaction for 24h; after the reaction is finished, centrifugally separating out a product, and repeatedly centrifugally washing with absolute ethyl alcohol and deionized water until the supernatant is neutral; and drying the washed product at 80 ℃ to obtain 0.48g of nano silicon oxide microsphere powder. And preparing the product in batches according to the actual dosage until the product with the required dosage is obtained.
Preparing a nano silicon oxide modified composite salt-resistant material:
dispersing the modified starch-acrylamide polymer in 100mL of acetonitrile, adding 2.0g of nano silicon oxide microspheres and 0.4g of anhydrous potassium carbonate, slowly dropwise adding 2mL of LAPTES in batches under stirring, and heating and refluxing for 24h under the protection of nitrogen; after the reaction is finished, cooling to room temperature, separating out a product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain 23.4692g of nano-silica modified composite salt-resistant material.
The composite salt-resistant material has an ordered layered reticular distribution morphology (see figure 2). Infrared analysis at 3426cm -1 And 1091cm -1 The absorption peaks are respectively Si-OH and Si-O-Si vibration peaks; after modification of APTES-COOH, the infrared spectrum was as 2935 cm -1 And 2855 cm -1 A new peak appears at the position, and the methylene stretching vibration peak of the modifier is shown in figure 1. This demonstrates that the nano-silica forms a composite organic functional material with the organic groups of the starch-acrylamide.
[ desalting experiments ]
The experiment was performed at room temperature (around 25 ℃).
Weighing 2.0g of the obtained material, adding 400mL of deionized water to form a viscous fluid with uniform dispersion, uniformly coating the viscous fluid on a carrier KC-X60 non-woven fabric, standing for 2h, drying at 80 ℃ for 6h, taking out, and cooling for later use.
The application material was cut into 4cm x 2cm pieces for use. Before the experiment, a proper amount of sodium chloride with the salt content of 1 percent NaCl and 1 percent Na is scraped 2 SO 4 And (3) measuring the surface soil of the test block by ion chromatography after the surface soil of the test block is dissolved and balanced in 50mL solution with the weight of 0.1-0.2 g, wherein the measured value is the background concentration (content) of salt in the salt-containing test block. And then soaking the cut KC-X60 desalting paper coated with the water-absorbing desalting material in deionized water for about 1min, then applying the soaked KC-X60 desalting paper on the surface of a test block, taking down the test block after the salinity distribution balance is achieved (the humidity of the applied desalting test paper is about 10 percent), applying the new desalting paper again, repeating for 5 times, then taking a certain amount of surface soil layer (0.1-0.1 mg) to constant volume in 50mL of deionized water for ion chromatography measurement, and determining the salinity of the surface soil of the desalted test block.The measurement results are shown in tables 1-2.
TABLE 1 removal rate of salt ion content in surface soil before and after desalting of NaCl test block with salt content of 1%
TABLE 2 salt content 1% Na 2 SO 4 Salt ion content and ion removal rate in surface soil before and after desalting test block
Embodiment 2 a preparation method of a nano silicon oxide modified composite salt-tolerant material comprises the following steps:
preparation of modified starch-acrylamide polymer:
soaking 5.0g of starch in 25mL of deionized water, continuously stirring for 30min to uniformly disperse the starch, heating to 80-85 ℃ under the protection of nitrogen for gelatinization for 55min, cooling to 60 ℃ while the system is semitransparent colloid; then 25mL of an aqueous solution containing 0.75g of ammonium persulfate and 0.05g of sodium sulfite was added; after initiating reaction for 15min at 50-70 ℃, adding 5.0g of 13X molecular sieve and 200mL of aqueous solution containing 15.0g of acrylamide and 0.08g of cross-linking agent polyethylene glycol dimethacrylate, and carrying out polymerization reaction for 2h at 65 ℃ under the protection of nitrogen; stopping introducing nitrogen after the reaction is finished, adding 100mL of methanol until the reaction product is immersed, leaching, fully drying the obtained solid at 60-80 ℃, crushing, and sieving with a 100-mesh sieve to obtain 23.3219g of modified starch-acrylamide polymer.
The preparation of the nano silicon oxide microspheres is the same as in example 1.
Preparation of the nano silicon oxide modified composite salt-tolerant material is the same as that of example 1.
[ desalting experiments ]
The experiment was performed at room temperature (around 25 ℃).
Weighing 2.0g of the obtained material, adding 900mL of deionized water to form a viscous fluid with uniform dispersion, uniformly coating the viscous fluid on a carrier KC-X60 non-woven fabric, standing for 2h, drying at 80 ℃ for 6h, taking out, and cooling for later use.
The experimental conditions were the same as in example 1, except that the treated test pieces had a salt content of 2% NaCl, 2% Na 2 SO 4 The weight of the mixture is 0.1-0.2 g, and other treatment methods are the same as in example 1. The measurement results are shown in tables 3-4.
TABLE 3 salt ion content and ion removal rate in surface soil before and after desalting of NaCl test block with salt content of 2%
TABLE 4 salt content 2% Na 2 SO 4 Salt ion content and ion removal rate in surface soil before and after desalting test block
Example 3a method for preparing a nano-silica modified composite salt-tolerant material was the same as example 1. Wherein: 25g of acrylamide, 5g of polyvinyl alcohol as a modifier and KH550 as a coupling agent.
[ desalting experiments ]
The experimental conditions and the treatment method are the same as in example 2.
The NaCl removal rate in the salt-containing test block reaches 96.2 percent, and Na is used for removing sodium chloride 2 SO 4 The removal rate is 93.6%, caSO 4 The removal rate is 90.8%.
Example 4 a method for preparing a nano-silica modified composite salt-tolerant material was the same as example 1. Wherein: 3.5g of bentonite and 590 g of coupling agent are used as modifier.
[ desalting experiments ]
The experimental conditions were the same as in example 1 and the treatment was the same as in example 2.
The NaCl removal rate in the salt-containing test block reaches 95.6 percent, and Na is used for removing sodium chloride 2 SO 4 The removal rate is 94.1 percent, caSO 4 The removal rate was 91.1%.
Claims (6)
1. The preparation method of the nano silicon oxide modified composite salt-resistant material comprises the following steps:
preparation of modified starch-acrylamide polymer:
dispersing starch in deionized water with the mass of 5-10 times of that of the starch, heating to 80-90 ℃ under the protection of nitrogen after the starch is uniformly dispersed, carrying out gelatinization treatment for 25-55 min, and cooling the system to 60-70 ℃; then sequentially adding an initiator aqueous solution with the concentration of 0.002-0.03 g/mL and a sodium sulfite aqueous solution with the concentration of 0.0006-0.002g/mL; after initiating reaction for 15min at 50-70 ℃, sequentially adding a modifier, a monomer acrylamide aqueous solution with the concentration of 0.075-0.125 g/mL and a cross-linking agent aqueous solution with the concentration of 0.000125-0.0005 g/mL, and carrying out graft polymerization at 50-65 ℃ under the protection of nitrogen; stopping introducing nitrogen after the reaction is finished, adding methanol for leaching treatment, fully drying the obtained solid at 60-80 ℃, and then crushing to obtain the modified starch-acrylamide polymer; the modifier is one or more than two of polyvinyl alcohol, kaolin, bentonite, 13X molecular sieve and 5A molecular sieve;
the mass of the initiator is 0.01-0.15 times of the mass of the starch; the mass of the sodium sulfite is 0.003-0.01 times of that of the starch; the mass of the modifier is 0.5-1.0 times of that of the starch; the mass of the monomer acrylamide is 3-5 times of that of the starch; the mass of the cross-linking agent is 0.005-0.02 times of the mass of the starch; the dosage of the methanol is 1-3 times of the total volume of the synthetic materials;
preparation of nano silicon oxide microspheres:
sequentially adding absolute ethyl alcohol, deionized water and ammonia water into a reaction bottle, stirring at 40 ℃ for 10min to uniformly mix the solution, then adding tetraethyl silicate, and stirring in a water bath at 40 ℃ for reflux reaction for 24h; after the reaction is finished, centrifugally separating out a product, and repeatedly centrifugally washing with absolute ethyl alcohol and deionized water until the supernatant is neutral; drying the washed product at 80 ℃ to obtain nano silicon oxide microspheres; the volume ratio of the absolute ethyl alcohol to the deionized water to the ammonia water to the tetraethyl silicate is 40:4.5:3.5:1, a step of;
preparing a nano silicon oxide modified composite salt-resistant material:
dispersing the modified starch-acrylamide polymer in acetonitrile with the volume of 5-30 times of that of the modified starch-acrylamide polymer, adding the nano silicon oxide microspheres and anhydrous potassium carbonate, slowly dropwise adding a coupling agent in batches under stirring, and heating and refluxing for 24 hours under the protection of nitrogen; cooling to room temperature after the reaction is finished, separating out a product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain the nano silicon oxide modified composite salt-resistant material; the mass of the nano silicon oxide microspheres is 0.3-0.8 times of that of starch; the mass of the anhydrous potassium carbonate is 0.08-0.1 times of that of the starch; the mass of the coupling agent is 0.2-0.4 times of that of the starch.
2. The method for preparing the nano silicon oxide modified composite salt-tolerant material according to claim 1, which is characterized in that: the initiator in the step (A) is one or more than two of potassium persulfate, sodium sulfite, sodium persulfate, potassium permanganate, ammonium persulfate or sodium peroxide.
3. The method for preparing the nano silicon oxide modified composite salt-tolerant material according to claim 1, which is characterized in that: in the step, the cross-linking agent is one of glycerol, dimethylacrylamide, N' -methylenebisacrylamide or polyethylene glycol dimethacrylate.
4. The method for preparing the nano silicon oxide modified composite salt-tolerant material according to claim 1, which is characterized in that: the coupling agent in the step III is one or more than two of 3-aminopropyl triethoxysilane, aminopropyl triethoxysilane or mercaptopropyl trimethoxysilane.
5. The application of the nano silicon oxide modified composite salt-tolerant material prepared by the method of claim 1, which is characterized in that: the composite salt-resistant material is used for water absorption and desalination treatment for repairing and protecting cultural relics or earthen sites.
6. The use of a nano silicon oxide modified composite salt-tolerant material according to claim 5, wherein: adding the composite salt-resistant material into deionized water with the mass of 100-1000 times of that of the composite salt-resistant material to form a viscous fluid which is uniformly dispersed, and uniformly coating the viscous fluid on a carrier KC-X60 non-woven fabric to obtain the KC-X60 applied desalination material with adsorption air permeability containing the composite salt-resistant material.
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