Preparation method and application of functional particle loaded core-sheath structure hydraulic organic-inorganic composite material

Abstract

The application discloses a preparation method and application of a functional particle loaded skin-core structure hydraulic organic-inorganic composite material. The composite material is prepared by the following steps: dissolving an organic polymer material in a solvent, adding functional particles to obtain an organic polymer solution with the functional particles, dispersing inorganic particles into part of the organic polymer solution to obtain a blending solution, and preparing a gel with a skin-core structure by taking the blending solution and the organic polymer solution with the functional particles as skin layer solution and core layer solution respectively through a coaxial spinning technology, and obtaining the functional particle loaded skin-core structure hydraulic organic-inorganic composite material after drying the gel. The structure of the organic polymer solution can be adjusted by introducing the functional particles, the conformation and organization state of the polymer chain are influenced, and the prepared material can transmit specific physical, chemical or biological functions, so that the composite material is endowed with special functional application.

Description

Technical Field

[0001] This invention belongs to the technical field of functional composite material preparation, specifically relating to a method for preparing and applying a hydraulically-driven organic-inorganic composite material with a core-skin structure supported by functional particles. Background Technology

[0002] The research background of functional particles mainly stems from the demand for specific functional materials and the exploration of the properties of nanoscale materials. Researchers develop new particle materials by controlling the physical, chemical, and structural characteristics of particles, and apply them to multiple fields to meet various application needs. For example, magnetic particles can respond to external magnetic fields and exhibit magnetic behavior, such as ferromagnetic, paramagnetic, or superparamagnetic. This property makes magnetic particles widely applicable in the biomedical field, such as magnetic resonance imaging (MRI) contrast agents, magnetic targeted drug delivery, magnetic separation, and biosensing. Metallic nanoparticles are nanoscale in size and possess specific optical, magnetic, or chemical properties. For example, gold nanoparticles exhibit surface plasmon resonance absorption and can be used in applications such as optical sensing, catalysts, and bioimaging. Ferrite nanoparticles are magnetic and are used in medicine for magnetic resonance imaging, cancer treatment, and magnetic targeted delivery. The applications of functional particles are very broad, involving multiple fields such as medicine, energy, environment, and electronics. By precisely controlling the size, shape, composition, and surface properties of particles, their functions can be finely tuned, providing customized solutions for various applications.

[0003] Silicate cement is a fundamental raw material for many buildings and structures, as well as for initial concrete and reinforced concrete, and is a typical high-strength inorganic material. Currently, cement, after numerous improvements, is widely used in construction and related fields. However, it is worth noting that in the development of cement-based materials, the plasticity of the material during its hardening process has been neglected. Ultra-high-strength cement materials exhibit poor elongation, toughness (pseudo-toughness), flexural strength, and tensile strength, which limits its application in fields requiring detailed localization, such as architecture and art.

[0004] Currently, researchers are gradually replacing some reinforcing asbestos fibers with cellulose fibers. However, compared to asbestos cement products, cellulose-reinforced cement products are more susceptible to water damage. Moreover, existing methods for preparing cellulose-cement composites mostly rely on conventional water-based curing methods, resulting in low toughness and plasticity, and limiting their applications.

[0005] The researchers in this case had previously proposed some technologies to address the aforementioned problems, such as Patent Document 1. This technology can prepare hydraulic organic-inorganic composite materials based on organic polymers and inorganic particles. In this composite material, both organic and inorganic materials are interconnected network structures, exhibiting the characteristics of softening upon short-term contact with water and hardening upon long-term contact with water. However, this technology still has certain drawbacks, such as poor mechanical properties and elongation properties of the obtained dry fibers, the composite material being easily damaged during application, and the functionality of the composite material produced by this technology being relatively limited, failing to support specific applications of the composite material.

[0006] Patent document 1: Publication number CN113831067A.

[0007] In response to this problem, the researchers in this case proposed further improvement plans. Summary of the Invention

[0008] To overcome the shortcomings of the prior art, the present invention aims to provide a method for preparing and applying a core-shell structured hydraulic organic-inorganic composite material supported by functional particles. The material has a skin layer composed of a hydrophilic organic material with added functional particles, and a core layer composed of a blend of a hydrophilic organic material and a water-hardening inorganic material; or a skin layer composed of a blend of a hydrophilic organic material and a water-hardening inorganic material, and a core layer composed of a hydrophilic organic material with added functional particles.

[0009] The hydraulic organic-inorganic composite material with a core-skin structure prepared by this invention, incorporating functional particles, enhances the mechanical properties (fracture strength) and elongation (elongation at break) of the original composite material compared to existing technologies. Simultaneously, it endows the composite material with unique physical, chemical, or biological properties, expanding its functional application areas. The addition of functional particles can regulate the structure of the organic polymer solution, affecting the conformation and organization of the polymer chains. Furthermore, the interaction between functional particles and polymer chains can alter the degrees of freedom and orientation of the polymer chain ends or side groups, leading to changes in the spatial arrangement and microphase structure of the polymer in the organic polymer solution.

[0010] This material exhibits a significant superposition effect, fully leveraging the reinforcing properties of hydrophilic organic compounds to improve elongation and toughness (pseudo-toughness) to a certain extent, as well as enhancing flexural and tensile strength. Functional particles, acting as carriers, can deliver specific physical, chemical, or biological functions within organic polymer solutions. For example, magnetic particles can transmit magnetic responses in polymer solutions, fluorescent particles can achieve fluorescence signal transmission, and nanocatalysts can catalyze specific reactions within organic polymer solutions.

[0011] To achieve the above-mentioned objective, this invention provides a method for preparing a core-shell structured hydraulic organic-inorganic composite material with functional particle loading, comprising at least the following steps:

[0012] 1) Dissolve organic polymer materials in a non-aqueous solvent to obtain an organic polymer solution, wherein the content of organic polymers in the organic polymer solution is 0.5-2 wt%;

[0013] 2) Disperse the functional particles into a portion of the organic polymer solution obtained in step 1) to obtain an organic polymer solution containing functional particles, wherein the mass ratio of organic polymer to functional particles in the solution is 1:1-100.

[0014] 3) Disperse the inorganic particles into a portion of the organic polymer solution obtained in step 1) to obtain a blend solution, wherein the mass ratio of organic polymer to inorganic particles in the blend solution is 1:1-100;

[0015] 4) Use the organic polymer solution with functional particles obtained in step 2) as the skin layer solution or the core layer solution, and use the blend solution obtained in step 3) as the corresponding core layer solution or skin layer solution. Use coaxial spinning technology to obtain a two-phase flow with skin layer and core layer.

[0016] 5) The two-phase flow obtained in step 4) is simultaneously regenerated in a non-aqueous coagulation bath to obtain a gel with a core-skin structure;

[0017] 6) Dry the gel obtained in step 5) to obtain a core-shell structured hydraulic organic-inorganic composite material with functional particles loaded.

[0018] As a further improvement of the present invention, in step 1), the organic polymer is an organic polymer containing hydrophilic groups.

[0019] As a further improvement of the present invention, the organic polymer containing hydrophilic groups is a polysaccharide organic polymer or a polypeptide organic polymer.

[0020] As a further improvement of the present invention, the organic polymer containing hydrophilic groups is one or more of cellulose, chitin, chitosan, agar, alginic acid, hyaluronic acid, gelatin, carrageenan, and guar gum.

[0021] As a further improvement of the present invention, the non-aqueous solvent for the cellulose is LiCl / DMAc; the non-aqueous solvent for the chitin or silk is CaCl2 / methanol, CaCl2 / ethanol, or CaCl2 / formic acid.

[0022] As a further improvement of the present invention, in step 2), the functional particles are those containing Fe. 3+ Li + Ca 2+ K + Na+ Functional metal compounds, etc.

[0023] As a further improvement of the present invention, in step 3), the inorganic particles are inorganic particles or powders that harden upon contact with water.

[0024] As a further improvement of the present invention, the non-aqueous coagulation bath is one or more of methanol, ethanol, propanol, DMAc, DMF, acetone, and dichloromethane.

[0025] As a further improvement of the present invention, in step 6), the morphology of the core-shell structure hydraulic organic-inorganic composite material includes, but is not limited to, filamentous, film-like, blocky, ring-like, or tubular.

[0026] Meanwhile, this invention also relates to the application of a core-shell structured hydraulic organic-inorganic composite material supported by functional particles prepared by the above-mentioned preparation method. The functional particles serve as carriers to transmit their specific physical, chemical, or biological functions in organic polymer solutions. When the functional particles are magnetic particles, they can transmit magnetic responses in polymer solutions. When the functional particles are fluorescent particles, they can transmit fluorescence signals. When the functional particles are nanocatalysts, they can catalyze specific reactions in organic polymer solutions.

[0027] The beneficial effects of this invention are:

[0028] 1. The preparation method of the present invention involves the formation of an organic polymer network in an organic polymer solution containing functional particles; in a blended solution, hydraulic inorganic particles are encapsulated within the organic polymer network. During the drying process, volatile organic compounds in the coagulation bath gradually evaporate, and numerous functional particles are distributed in the organic polymer layer, gradually diffusing into the blended solution layer. Furthermore, the organic polymer chains and the organic polymers and inorganic particles are further bonded together through hydrogen bonds to form a hydraulic composite material.

[0029] 2. The hydraulic organic-inorganic composite material with functional particles prepared in this invention undergoes a reaction upon immersion in water, resulting in hardening and increased strength, while also exhibiting improved brittleness. The internal and external polymeric network layers effectively provide toughness, preventing network breakage during material preparation or promoting the reorganization of broken networks. Over time, the hardened hydraulic inorganic particles complete the network formation, with both organic and inorganic components forming interconnected network structures within the composite material. Therefore, it exhibits strong short-term plasticity upon contact with water and stable mechanical properties over long-term exposure. The strong short-term plasticity is primarily a characteristic of the organic polymers in the composite material, while the stable mechanical properties over long-term exposure are mainly due to the characteristics of the inorganic particles.

[0030] 3. Because the hydraulic organic-inorganic composite material with functional particles prepared in this invention has functional particles, it can regulate the structure of organic polymer solutions and affect the conformation and organizational state of polymer chains. The interaction between functional particles and polymer chains can change the degrees of freedom and orientation of the polymer chain ends or side groups, leading to changes in the spatial arrangement and microphase structure of the polymer in the organic polymer solution.

[0031] 4. In the core-shell structured hydraulic organic-inorganic composite material supported by functional particles prepared in this invention, the functional particles, acting as carriers, can transfer their specific physical, chemical, or biological functions in the organic polymer solution. For example, magnetic particles can transfer magnetic responses in the polymer solution, fluorescent particles can realize fluorescence signal transmission, and nanocatalysts can catalyze specific reactions in the organic polymer solution.

[0032] 5. The functional particle-loaded core-shell structure hydraulic organic-inorganic composite material prepared in this invention incorporates functional particles in its core layer, giving the material unique physical, chemical, or biological properties and further expanding the functional applications of the composite material. Cellulose, as a carrier material, can effectively encapsulate and protect the loaded particles from the influence of the external environment, improving its stability and durability. Simultaneously, cellulose's strong chemical stability makes it suitable for various application environments. Cellulose itself can be compounded with other functional materials to form multifunctional composite materials. By introducing functional components, such as metal nanoparticles, into the cellulose structure, more specific functions can be endowed to the cellulose-loaded particles, expanding its application areas.

[0033] 6. The core-shell structure hydraulic organic-inorganic composite material supported by functional particles prepared in this invention, compared with existing technologies, can enhance the mechanical properties (fracture strength) and elongation (elongation at break) of the original composite material, thus achieving better mechanical properties. Simultaneously, the functional particles possess unique physical, chemical, or biological properties, expanding the functional applications of the composite material. Attached Figure Description

[0034] Figure 1 This is a flowchart of the preparation method of the present invention;

[0035] Figure 2 This is a diagram illustrating the properties of the functional particle-loaded core-shell structured hydraulic organic-inorganic composite material prepared by the method of the present invention.

[0036] Figure 3 SEM image of the functional particle-loaded core-shell structured hydraulic organic-inorganic composite material prepared by the preparation method of the present invention;

[0037] Figure 4(a), (b), and (c) are elemental analysis diagrams of the functional particle-loaded core-shell structured hydraulic organic-inorganic composite materials prepared by the method of the present invention. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to specific embodiments.

[0039] It should also be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and / or processing steps closely related to the solution of the present invention are shown in the specific embodiments, while other details that are not closely related to the present invention are omitted.

[0040] Additionally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0041] The present invention provides a method for preparing a functional particle-loaded core-shell structured hydraulic organic-inorganic composite material, comprising at least the following steps:

[0042] 1) Dissolve organic polymer materials in a non-aqueous solvent to obtain an organic polymer solution, wherein the content of organic polymers in the organic polymer solution is 0.5-2 wt%;

[0043] 2) Disperse the functional particles into a portion of the organic polymer solution obtained in step 1) to obtain an organic polymer solution containing functional particles, wherein the mass ratio of organic polymer to functional particles in the solution is 1:1-100.

[0044] 3) Disperse the inorganic particles into a portion of the organic polymer solution obtained in step 1) to obtain a blend solution, wherein the mass ratio of organic polymer to inorganic particles in the blend solution is 1:1-100;

[0045] 4) Use the organic polymer solution with functional particles obtained in step 2) as the skin layer solution or the core layer solution, and use the blend solution obtained in step 3) as the corresponding core layer solution or skin layer solution. Use coaxial spinning technology to obtain a two-phase flow with skin layer and core layer.

[0046] 5) The two-phase flow obtained in step 4) is simultaneously regenerated in a non-aqueous coagulation bath to obtain a gel with a core-skin structure;

[0047] 6) Dry the gel obtained in step 5) to obtain a core-shell structured hydraulic organic-inorganic composite material with functional particles loaded.

[0048] By adopting the above technical solution, the entire preparation method is carried out in a non-aqueous system. The hydrophilic organic polymer and the hydraulic inorganic particles are in a non-aqueous coagulation bath. Based on the principle of similar compatibility, the non-aqueous good solvent of the organic polymer gradually diffuses into the non-aqueous coagulation bath. The hydrophilic organic polymer gradually forms a gel-like substance from the surface to the interior through intermolecular hydrogen bonds and other forces.

[0049] In organic polymer solutions containing functional particles, organic polymer networks are formed; in blend solutions, functional particles and hydraulic inorganic particles are encapsulated within the organic polymer network.

[0050] During the drying process, the volatile organic compounds in the coagulation bath gradually evaporate, the organic polymer network encapsulates the functional particles, and the functional particles penetrate into the blend layer; furthermore, the organic polymer chains and the organic polymers and inorganic particles are further bonded together through hydrogen bonds to form a hydraulic composite material.

[0051] When the composite material is immersed in water, the functional particles and hydraulic inorganic particles react with water and harden to generate strength. As time goes on, the functional particles and hydraulic inorganic particles harden and form a network. Both organic and inorganic materials in the composite material are interconnected network structures and permeate each other.

[0052] Therefore, the functional particle-loaded core-shell structure hydraulic organic-inorganic composite material prepared in this invention has the characteristics of strong short-term plasticity when exposed to water and stable mechanical properties when exposed to water over a long period of time. The strong short-term plasticity when exposed to water is mainly due to the characteristics of the organic polymer material in the composite material, while the stable mechanical properties when exposed to water over a long period of time are mainly due to the characteristics of the inorganic particles in the composite material.

[0053] The hydrophilic organic polymers mentioned above in this invention are one or more selected from cellulose, chitin, chitosan, agar, alginic acid, hyaluronic acid, gelatin, carrageenan, and guar gum. The selection of natural hydrophilic organic polymers is advantageous because, firstly, the raw materials are widely available, aligning with the concept of sustainable development; secondly, these substances can form good gels with inorganic minerals such as cement. Through the process of this invention, a composite material with the characteristics of softening upon short-term contact with water and hardening upon long-term contact with water is obtained.

[0054] Furthermore, functional particles refer to tiny particles with specific functions and properties, typically composed of nano- or micro-sized materials. Examples include magnetic nanoparticles and metallic nanoparticles, which possess unique physical, chemical, or biological properties and can be applied in multiple fields.

[0055] It should be noted that in some embodiments, the organic polymer containing hydrophilic groups is cellulose, and correspondingly, the non-aqueous solvent mentioned above is LiCl / DMAc (lithium chloride / N,N-dimethylacetamide).

[0056] In other embodiments, when chitosan is used as the organic polymer containing hydrophilic groups, the corresponding non-aqueous solvents are CaCl2 / methanol, CaCl2 / ethanol, and CaCl2 / formic acid.

[0057] When using water-hardening inorganic powders or granules, the aforementioned inorganic particles can be selected from one or more of cement, cement clinker, clay, or gypsum.

[0058] It should be noted that, in some specific embodiments, when selecting cement for the water-hardening inorganic powder or granules mentioned above, silicate cement, aluminate water, sulfoaluminate cement, ferroaluminate cement, fluoroaluminate cement, phosphate cement, etc. can be considered; at the same time, inorganic fillers such as calcium oxide, calcium carbonate, silicon dioxide, fly ash, alumina, and iron oxide can also be considered.

[0059] Non-aqueous coagulation baths use volatile coagulation baths other than water, such as one or more of methanol, ethanol, propanol, DMAc, DMF, acetone, and dichloromethane.

[0060] Understandably, in order to promote the subsequent regeneration of the gel, the non-aqueous coagulation bath here can be a non-aqueous coagulation bath that is compatible with the non-aqueous solvent in step 1).

[0061] In step 4), the skin solution and core solution are used to obtain a two-phase flow with a skin and a core through coaxial spinning technology. The coaxial spinning technology can be wet spinning or electrospinning.

[0062] The core-shell structured hydraulic organic-inorganic composite material obtained in step 6) can take the form of, but is not limited to, filaments, films, blocks, rings, or tubular structures. Filaments can be achieved through extrusion or injection molding, films can be achieved through casting, and blocks, rings, or tubular structures can be obtained through curing and regeneration in a corresponding mold.

[0063] Because the functional particle-loaded core-shell structure hydraulic organic-inorganic composite material prepared by this invention has the characteristics of softening in water for a short time and hardening in water for a long time, it can be softened by short-term immersion in water, then shaped and processed, and finally cured and shaped, which significantly improves the plasticity of this type of composite material and broadens its application.

[0064] Furthermore, since the functional particles loaded in the core-shell structure hydraulic organic-inorganic composite material prepared by this invention are functional particles, their unique physical, chemical or biological properties result in the composite material having corresponding special functions. The specific properties vary depending on the type of particles, such as magnetism, UV resistance, and antibacterial properties.

[0065] The content of the present invention will be further described below with reference to specific embodiments:

[0066] This invention uses an INSTRON 5943 universal testing machine. Before testing, the material is equilibrated at 25°C and 65% humidity for 12 hours. During testing, the tensile speed of the sample is 10 mm / min and the test length is 20 mm, that is, the length of the fiber sample is 20 mm under pre-tension.

[0067] In the attached diagram, Figure 1 The flowchart for preparing fibers using this method shows that the pre-prepared inner layer solution and outer layer solution are connected using a coaxial spinning needle. The inner and outer layers are simultaneously regenerated in an ethanol coagulation bath and collected by a collection device. After drying, this is one of the products prepared by this method.

[0068] Example 1

[0069] 1) Crush cellulose wood pulp with a degree of polymerization of 400-800 into fragments with a length of 0.1-0.5 mm and dry them in an oven at 60℃ for 12 hours;

[0070] 2) Weigh 18g of lithium chloride (LiCl) and 192g of N,N-dimethylacetamide (DMAc) into a 250ml sample bottle, mix them, and then dissolve them by sonication;

[0071] 3) Add 3g of the cellulose wood pulp obtained in step 1) and 297g of DMAc / LiCl solution to a three-necked flask, heat and stir for 2.5h to obtain a transparent cellulose solution with a mass fraction of 1wt%. The heating temperature is 112℃ and the stirring speed is 550rpm.

[0072] 4) Add 4.5g of the cellulose wood pulp obtained in step 1) and 295.5g of DMAc / LiCl solution to a three-necked flask, heat and stir for 2.5h to obtain a transparent cellulose solution with a mass fraction of 1.5wt%. The heating temperature is 112℃ and the stirring speed is 550rpm.

[0073] 5) Add 0.5g of silicate cement powder to the 1wt% cellulose solution in step 3), stir at 250rpm for 1min to obtain silicate cement / cellulose spinning solution, the mass of silicate cement powder is 10 times the mass of cellulose;

[0074] 6) Take two syringes, one to draw the silicate cement / cellulose spinning solution obtained in step 5) as the outer layer solution; the other to draw the cellulose spinning solution with a mass fraction of 1.5% obtained in step 6) as the inner layer solution.

[0075] 7) Place the two syringes obtained in step 7) on different push pumps, and connect the two needle tips to the same coaxial needle head at the same time.

[0076] 8) Immerse the coaxial needle from step 8) in the coagulation bath of ethanol, and simultaneously start two push pumps. The injection speed of the inner solution push pump and the injection speed of the outer solution push pump are both 0.4 mL / min, to obtain a gel with a core-skin structure.

[0077] 9) The obtained gel is dried to obtain a core-shell structured hydraulic organic-inorganic composite material.

[0078] Example 2

[0079] 1) Crush cellulose wood pulp with a degree of polymerization of 400-800 into fragments with a length of 0.1-0.5 mm and dry them in an oven at 60℃ for 12 hours;

[0080] 2) Weigh 18g of lithium chloride (LiCl) and 192g of N,N-dimethylacetamide (DMAc) into a 250ml sample bottle, mix them, and then dissolve them by sonication;

[0081] 3) Add 3g of the cellulose wood pulp obtained in step 1) and 297g of DMAc / LiCl solution to a three-necked flask, heat and stir for 2.5h to obtain a transparent cellulose solution with a mass fraction of 1wt%. The heating temperature is 112℃ and the stirring speed is 550rpm.

[0082] 4) Add 4.5g of the cellulose wood pulp obtained in step 1) and 295.5g of DMAc / LiCl solution to a three-necked flask, heat and stir for 2.5h to obtain a transparent cellulose solution with a mass fraction of 1.5wt%. The heating temperature is 112℃ and the stirring speed is 550rpm.

[0083] 5) Add 0.5g of silicate cement powder to the 1wt% cellulose solution in step 3), stir at 250rpm for 1min to obtain silicate cement / cellulose spinning solution, the mass of silicate cement powder is 10 times the mass of cellulose;

[0084] 6) Add 0.25g of Fe3O4 nanopowder to the 1.5wt% cellulose solution in step 4), stir at 250rpm for 1min to obtain Fe3O4 / cellulose spinning solution, the mass of Fe3O4 nanopowder is 2.5 times the mass of cellulose;

[0085] 7) Take two syringes, one to draw the silicate cement / cellulose spinning solution obtained in step 5) as the outer layer solution; the other to draw the Fe3O4 / cellulose spinning solution obtained in step 6) as the inner layer solution.

[0086] 8) Place the two syringes obtained in step 7) on different push pumps, and connect the two needle tips to the same coaxial needle head at the same time.

[0087] 9) Immerse the coaxial needle from step 8) in the coagulation bath of ethanol, and simultaneously start two push pumps. The injection speed of the inner solution push pump and the injection speed of the outer solution push pump are both 0.4 mL / min, to obtain a gel with a core-skin structure.

[0088] 10) The obtained gel is dried to obtain a core-shell structured hydraulic organic-inorganic composite material with functional particles loaded.

[0089] Examples 3-5

[0090] Compared with Example 2, Examples 3-5 differ in that the mass of Fe3O4 nanopowder in step 3 is changed. Apart from the above differences, all other operations are the same and will not be repeated here. The specific experimental conditions and measurement results are shown in Table 1. The changes in the mechanical properties of the composite material under dry and wet conditions are shown in Table 2 (dry state: the state immediately after preparation; wet state: the state after being placed in water).

[0091] Table 1

[0092]

[0093] Table 2

[0094]

[0095] As shown in Table 1, the fracture stress of the composite material gradually decreased with the increase of Fe3O4 nanopowder content in the outer solution, and the fracture strain also generally showed a gradual decreasing trend, with only Example 4 showing an increase in fracture strain compared to Example 3. The initial decrease in elasticity may be due to the rigidity of the particles, while the final increase in elongation at break may be due to the high Fe3O4 content inhibiting the crystallization of cellulose.

[0096] In Table 2, a negative value for the fracture stress change indicates a decrease in the mechanical properties of the composite material, making it prone to fracture when subjected to tensile stress. A larger value for the fracture strain change indicates that the material's flexibility and toughness increase after exposure to water, resulting in better material adaptability.

[0097] As can be seen from Table 2, with the increase of Fe3O4 nanopowder content in the outer solution, the strength of the composite material gradually increases under tensile stress, but the flexibility and toughness decrease after contact with water, and the editability of the material also decreases.

[0098] Figure 2 For the reason Figure 1 Demonstration of the properties of the finished product prepared by the process: Without the introduction of functional particles, the composite material is non-magnetic and cannot be attracted by a magnet; with the introduction of Fe... 3+ Afterwards, it can be attracted by a magnet, indicating that Fe 3+ The introduction of Fe3O4 imbues the composite material with magnetism. As a magnetic material, Fe3O4 exhibits magnetic response characteristics in organic polymer solutions. This allows for manipulation of the position and distribution of Fe3O4 using an external magnetic field, achieving magnetic orientation and guidance. Furthermore, Fe3O4 itself possesses certain electrical conductivity, which can introduce electrical conductivity effects into organic polymers.

[0099] Figure 3 for Figure 1 The SEM image of the finished product prepared by the process shows that the functional particles are exposed, while the remaining particles are encapsulated in cellulose.

[0100] Figure 4 for Figure 1 The elemental analysis chart of the finished product prepared by the process shows that functional particles in the cortex are observed, while the remaining particles are aggregated in the core layer.

[0101] (a) shows the fiber morphology of the prepared composite material, (b) shows the distribution of iron in the prepared composite material, and (c) shows the distribution of calcium in the prepared composite material.

[0102] Therefore, considering the flexibility and toughness of the composite material after contact with water, its ease of use, and its mechanical properties in the final form, a mass ratio of Fe3O4 nanopowder to cellulose in the outer solution between 1 and 10 can achieve better results.

[0103] Example 6

[0104] 1) Crush cellulose wood pulp with a degree of polymerization of 400-800 into fragments with a length of 0.1-0.5 mm and dry them in an oven at 60℃ for 12 hours;

[0105] 2) Weigh 18g of lithium chloride (LiCl) and 192g of N,N-dimethylacetamide (DMAc) into a 250ml sample bottle, mix them, and then dissolve them by sonication;

[0106] 3) Add 3g of the cellulose wood pulp obtained in step 1) and 297g of DMAc / LiCl solution to a three-necked flask, heat and stir for 2.5h to obtain a transparent cellulose solution with a mass fraction of 1wt%. The heating temperature is 112℃ and the stirring speed is 550rpm.

[0107] 4) Add 4.5g of the cellulose wood pulp obtained in step 1) and 295.5g of DMAc / LiCl solution to a three-necked flask, heat and stir for 2.5h to obtain a transparent cellulose solution with a mass fraction of 1.5wt%. The heating temperature is 112℃ and the stirring speed is 550rpm.

[0108] 5) Add 0.5g of silicate cement powder to the 1wt% cellulose solution in step 3), stir at 250rpm for 1min to obtain silicate cement / cellulose spinning solution, the mass of silicate cement powder is 10 times the mass of cellulose;

[0109] 6) Add 0.75g of Fe3O4 nanopowder to the 1.5wt% cellulose solution in step 4), stir at 250rpm for 1min to obtain Fe3O4 / cellulose spinning solution, the mass of Fe3O4 nanopowder is 5 times the mass of cellulose;

[0110] 7) Take two syringes, one to draw the silicate cement / cellulose spinning solution obtained in step 5) as the outer layer solution; the other to draw the Fe3O4 / cellulose spinning solution obtained in step 6) as the inner layer solution.

[0111] 8) Place the two syringes obtained in step 7) on different push pumps, and connect the two needle tips to the same coaxial needle head at the same time.

[0112] 9) Immerse the coaxial needle from step 8) in the coagulation bath of ethanol, and simultaneously start two push pumps. The injection speed of the inner solution push pump and the injection speed of the outer solution push pump are both 0.4 mL / min, to obtain a gel with a core-skin structure.

[0113] 10) The obtained gel is dried to obtain a core-shell structured hydraulic organic-inorganic composite material with functional particles loaded.

[0114] Examples 7-10

[0115] Compared with Example 6, Examples 7-10 differ in that Fe3O4 in step 3 is replaced with CaCl2, KBr, NaCl, and LiCl, respectively. Apart from the above differences, all other operations are the same and will not be repeated here. The specific experimental conditions and measurement results are shown in Table 3.

[0116] Table 3

[0117]

[0118] As shown in Table 3, the fracture stress and fracture strain of the composite material change with the type of metal salt in the outer solution. Specifically, Fe... 3+ The introduction of Li gives the fiber a higher elongation at break, but lower breaking stress. In comparison, the introduction of Li... + The fibers have high breaking stress.

[0119] In summary, the present invention provides a method for preparing a functional particle-loaded core-shell structured hydraulic organic-inorganic composite material, which combines organic polymers with inorganic substances in a non-aqueous system to obtain a hydraulic organic-inorganic composite material with the characteristics of softening upon short-term exposure to water and hardening upon long-term exposure to water.

[0120] Furthermore, since the composite material prepared in this invention is loaded with functional particles, the addition of these particles can regulate the structure of the organic polymer solution, affecting the conformation and organization of the polymer chains. The interaction between the functional particles and the polymer chains can alter the degrees of freedom and orientation of the polymer chain ends or side groups, leading to changes in the spatial arrangement and microphase structure of the polymer in the organic polymer solution.

[0121] Meanwhile, functional particles, acting as carriers, can deliver their specific physical, chemical, or biological functions in organic polymer solutions. For example, magnetic particles can transmit magnetic responses in polymer solutions, fluorescent particles can achieve fluorescence signal transmission, and nanocatalysts can catalyze specific reactions in organic polymer solutions.

[0122] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a core-shell structured hydraulic organic-inorganic composite material supported by functional particles, characterized in that, At least the following steps are included: 1) Dissolve organic polymer materials in a non-aqueous solvent to obtain an organic polymer solution, wherein the content of organic polymer in the organic polymer solution is 0.5-2 wt%; 2) Disperse functional particles into a portion of the organic polymer solution obtained in step 1) to obtain an organic polymer solution with functional particles, wherein the mass ratio of organic polymer to functional particles in the solution is 1:1-100; 3) Disperse inorganic particles into a portion of the organic polymer solution obtained in step 1) to obtain a blend solution, wherein the mass ratio of organic polymer to inorganic particles in the blend solution is 1:1-100; 4) Use the organic polymer solution with functional particles obtained in step 2) as a skin solution or a core solution, and use the blend solution obtained in step 3) as the corresponding core solution or skin solution, and use coaxial spinning technology to obtain a two-phase flow with a skin and a core; 5) The two-phase flow obtained in step 4) is simultaneously regenerated in a non-aqueous coagulation bath to obtain a gel with a core-skin structure; 6) The gel obtained in step 5) is dried to obtain a hydraulic organic-inorganic composite material with a core-skin structure supported by functional particles. In step 2), the functional particles are those containing Fe. 3+ Li + Ca 2+ Na + The organic polymer is a functional metal compound; in step 1), the organic polymer is an organic polymer containing hydrophilic groups; in step 3), the inorganic particles are inorganic particles that harden upon contact with water.

2. The method for preparing the functional particle-supported core-shell structured hydraulic organic-inorganic composite material according to claim 1, characterized in that, The organic polymer containing hydrophilic groups is a polysaccharide organic polymer or a polypeptide organic polymer.

3. The method for preparing the functional particle-supported core-shell structured hydraulic organic-inorganic composite material according to claim 2, characterized in that, The organic polymer containing hydrophilic groups is one or more of the following: cellulose, chitin, chitosan, agar, alginic acid, hyaluronic acid, gelatin, carrageenan, and guar gum.

4. The method for preparing the functional particle-supported core-shell structured hydraulic organic-inorganic composite material according to claim 3, characterized in that, The non-aqueous solvent for the cellulose is LiCl / DMAc; the non-aqueous solvent for the chitin is CaCl2 / methanol, CaCl2 / ethanol, or CaCl2 / formic acid.

5. The method for preparing the functional particle-supported core-shell structured hydraulic organic-inorganic composite material according to claim 1, characterized in that, The water-hardening inorganic particles are one or more of cement, cement clinker, or gypsum.

6. The method for preparing the functional particle-supported core-shell structured hydraulic organic-inorganic composite material according to claim 1, characterized in that, In step 6), the morphology of the core-shell structure hydraulic organic-inorganic composite material supported by functional particles includes filamentous, film-like, blocky, ring-like, or tubular.

7. The application of a functional particle-loaded core-shell structured hydraulic organic-inorganic composite material prepared by the preparation method according to any one of claims 1 to 6, characterized in that, Functional particles act as carriers to deliver their specific physical, chemical, or biological functions in organic polymer solutions.

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