Inorganic-organic hybrid cross-linked network high-toughness material and preparation method thereof

Abstract

The invention discloses an inorganic-organic hybrid cross-linked network high-toughness material and a preparation method thereof, and belongs to the technical field of engineering material preparation. The high-toughness material is composed of an inorganic phase component and an organic phase component, the inorganic phase component is prepared from 5 to 10 parts of amino modified silicon dioxide nanoring; the organic phase component is prepared from the following components in parts by weight: 90 to 105 parts of polycaprolactone glycol, 14.5 to 16.5 parts of isophorone diisocyanate, 0.8 to 1.5 parts of dibutyltin dilaurate, 4 to 6 parts of bis-catechol borane and 6 to 10 parts of polydopamine nano particles. The fracture performance of the material can reach 20 kJ / m or above and is far higher than-1 kJ / m of a common elastomer and-10 kJ / m of high-toughness hydrogel, and meanwhile the tensile strength of 30 MPa or above is kept. According to the material disclosed by the invention, the dynamic borate bond is utilized, after the material is in contact with a damaged section, efficient self-repairing can be realized after the material is placed at room temperature for 24 hours, and the repairing efficiency is gt; by heating and applying pressure, the whole material can be reshaped through fracture and recombination of the dynamic bonds, and green and sustainable effects are achieved.

Description

Technical Field

[0001] This invention belongs to the field of engineering material preparation technology, specifically relating to a high-toughness material with an inorganic-organic hybrid cross-linked network and its preparation method. Background Technology

[0002] In modern civil engineering infrastructure, such as hydraulic dams, underground utility tunnels, tunnels, and nuclear power plant containment structures, seepage prevention and waterproofing are crucial for ensuring long-term structural safety, durability, and functionality. These structures often operate in complex and demanding environments, bearing not only static loads such as hydrostatic pressure and foundation settlement, but also frequent dynamic loads such as earthquakes, traffic cyclic loads, and mechanical vibrations. Under repeated dynamic loads, the waterproofing materials at weak points such as concrete joints and cracks are highly susceptible to fatigue damage, interfacial debonding, and even brittle fracture, leading to leakage failure and seriously threatening the overall safety and service life of the structure.

[0003] Currently, mainstream waterproofing materials mainly include traditional asphalt-based materials, such as asphalt felt and bentonite waterproofing blankets. These materials have decent flexibility but poor durability, are prone to aging and becoming brittle, easily undergo rheological changes under long-term loads, and have poor adhesion to concrete, making them difficult to meet the high standards of modern engineering. Crystalline waterproofing materials / penetrating liquids: These waterproof by reacting with concrete to form crystals that block pores. They lack extensibility and cannot adapt to the dynamic cracking and joint displacement of concrete, limiting their applicability. Flexible epoxy resin or modified polymer mortar: These modify rigid resins by adding flexible toughening agents. While their elongation at break is improved, it is usually still at a low level (typically <50%), and microcracks easily appear and propagate rapidly under repeated high strain, resulting in insufficient fatigue resistance.

[0004] Therefore, developing a highly ductile impermeable material that combines high durability, excellent flexibility (high elongation at break), and superior fatigue resistance, and elucidating its failure mechanism under dynamic loads, is of vital importance for improving the long-term safety protection level of major national infrastructure. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a high-toughness material of inorganic-organic hybrid cross-linked network and its preparation method, to construct a new generation of high-ductility materials, aiming to form a synergistic network structure through in-situ composite and chemical bonding of organic polymers and inorganic nanounits at the molecular / nanoscale.

[0006] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a high-toughness material with an inorganic-organic hybrid crosslinked network, wherein the high-toughness material is composed of an inorganic phase component and an organic phase component; The inorganic phase component consists of 5-10 parts of amine-modified silica nanorings; The organic phase component consists of 90-105 parts polycaprolactone diol, 14-16.5 parts isophorone diisocyanate, 0.8-1.5 parts dibutyltin dilaurate, 4-6 parts bis(catechol)borane, and 6-10 parts polydopamine nanoparticles.

[0007] Furthermore, the inorganic phase component consists of 5-10 parts of amine-modified silica nanorings; The organic phase component consists of 90-105 parts polycaprolactone diol, 14-16.5 parts isophorone diisocyanate, 0.8-1.5 parts dibutyltin dilaurate, 4-6 parts bis(catechol)borane, and 6-10 parts polydopamine nanoparticles.

[0008] Furthermore, a method for preparing a high-toughness material with an inorganic-organic hybrid cross-linked network includes the following steps: S1. First, a macrocyclic amphiphilic block copolymer is synthesized and self-assembled into cyclic micelles in a selective solvent. Using the cyclic micelles as templates, silica is deposited in the crown region of the micelles by sol-gel method. The polymer template is then removed by calcination, and the surface is modified by aminopropyltriethoxysilane to obtain amino-modified silica nanorings. S2. Dopamine hydrochloride was dissolved in Tris-HCl buffer, and polymerized by vigorous stirring at room temperature for 24 hours. After centrifugation and washing, polydopamine nanospheres were obtained. S3. In a drying reactor, polycaprolactone diol is dehydrated under vacuum at 110°C for 2 hours, then cooled to 80°C, isophorone diisocyanate and dibutyltin dilaurate are added, and the reaction is carried out under nitrogen protection for 3 hours to obtain a polyurethane prepolymer with NCO terminal. S4. Disperse the amine-modified silica nanorings in anhydrous DMF and sonicate for 2 hours to ensure full dispersion to obtain a suspension. Add the suspension, bis(catechol)borane, and polydopamine nanoparticles to the polyurethane prepolymer and mix them evenly by high-speed mechanical stirring to obtain a mixed slurry. S5. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it using a stepped temperature curing method.

[0009] Furthermore, the stepped temperature curing method specifically includes: First, cure at 80℃ for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation; Then, the temperature is lowered to 60℃ and cured for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, thereby achieving covalent bonding between the inorganic and organic phases. Continue to cool to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach equilibrium.

[0010] Furthermore, the macrocyclic amphiphilic block copolymer is a cyclic PS-b-PEO, and the sol-gel method specifically utilizes the hydrolysis of tetraethyl orthosilicate (TEOS).

[0011] Furthermore, the diameter of the polydopamine nanoparticles is 95-105 nm.

[0012] Furthermore, the outer diameter of the amine-modified silica nanorings is 48-52 nm, and the inner diameter is 18-22 nm.

[0013] Furthermore, the pH value of the Tris-HCl buffer is 8.5.

[0014] The beneficial effects of this invention are as follows: 1. The inorganic phase component of the present invention, namely the amine-modified silica nanorings, can absorb and dissipate a large amount of energy through reversible deformation when subjected to external force. After unloading, it can restore its original state. Its hollow ring structure can physically "encase" the polymer chain, forming a unique, non-covalent topological mechanical interlocking crosslink, which greatly enhances the network strength and has slippage properties. Furthermore, the amine groups (-NH2) on the surface can covalently bond with the organic phase, ensuring a strong interfacial bond between the two phases and avoiding phase separation. The polycaprolactone diol, bis(catechol borane), and polydopamine nanoparticles in the organic phase can form an organic network with dual dynamic bonds. The boronic acid ester bonds are formed by the reaction of the boronic acid ester groups on the bis(catechol borane) and the catechol groups on the polydopamine nanoparticles. These bonds can undergo reversible breakage and recombination under stress, representing one of the main pathways for energy dissipation and simultaneously endowing the material with room-temperature self-healing properties. The urethane bonds in polyurethane itself, along with the abundant phenolic hydroxyl and amino groups in polydopamine, can form a dense hydrogen bond network within the structure. Hydrogen bonds exhibit faster dissociation and recombination kinetics, which can pre-passivate crack tips. This invention combines the synthesized cyclic inorganic nanostructure with a dual dynamic cross-linked organic network, resulting in a toughening mechanism and material configuration significantly superior to existing conventional materials.

[0015] 2. This invention employs a multi-stage energy dissipation mechanism. The first stage involves instantaneous dissipation under external force, where numerous weak hydrogen bonds in the network break first, dissipating energy and effectively preventing the propagation of microcracks. The second stage primarily dissipates energy as stress further concentrates, causing reversible breakage of the dynamic covalent bonds in the borate ester, absorbing a large amount of energy. These broken bonds can recombine after stress relaxation, preventing permanent damage. The third stage continues with topological dissipation. Silica nanorings, as unique inorganic components, undergo elastic deformation in their ring structure, such as being flattened or stretched, storing and releasing elastic potential energy like microsprings. This mechanism is not present in traditional nanoparticles. Furthermore, their topological interlocking allows polymer chains to slide within their rings, further dissipating energy. These three mechanisms work synergistically in time (dynamics) and space (scale), ensuring that energy is efficiently dissipated throughout the entire impact process, rather than concentrating at a single point and causing material failure.

[0016] 3. The fracture performance of the material of the present invention can reach more than 20 kJ / m², which is much higher than that of ordinary elastomers (-1 kJ / m²) and high-toughness hydrogels (-10 kJ / m²), while maintaining a tensile strength of more than 30 MPa.

[0017] 4. The material of this invention utilizes dynamic borate ester bonds. After the material comes into contact with the damaged fracture surface, it can achieve efficient self-repair after being placed at room temperature for 24 hours, with a repair efficiency of >90%. By applying pressure through heating (-100℃), the breaking and recombination of dynamic bonds can reshape the material as a whole, achieving green sustainability.

[0018] Other advantages, objectives, and features of the invention will be set forth in the following description and will be apparent to those skilled in the art in some respects, or may be learned by practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Attached Figure Description

[0019] To make the purpose, technical solution, and beneficial effects of the invention clearer, the following figures are provided for illustration: Figure 1 This is a schematic diagram of the process of the present invention. Detailed Implementation

[0020] like Figure 1 As shown, this invention provides a method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network.

[0021] Example 1 S1. First, cyclic PS-b-PEO is synthesized and self-assembled into cyclic micelles in a selective solvent (a mixed solution of DMF, DMSO and water). Using the cyclic micelles as templates, silica is deposited in the crown region of the micelles via a sol-gel method (hydrolysis of tetraethyl orthosilicate TEOS). The polymer template is then removed by calcination, and the surface is modified with aminopropyltriethoxysilane to obtain amino-modified silica nanorings (outer diameter 50 nm, inner diameter 20 nm). S2. Dopamine hydrochloride was dissolved in Tris-HCl buffer solution with a pH of 8.5, and polymerized by vigorous stirring at room temperature for 24 hours. After centrifugation and washing, polydopamine nanoparticles (100 nm) were obtained. S3. Place 98 parts of polycaprolactone diol in a dry reactor and dehydrate it under vacuum at 110°C for 2 hours. Then cool it down to 80°C, add 15.5 parts of isophorone diisocyanate and 1.2 parts of dibutyltin dilaurate, and react under nitrogen protection for 3 hours to obtain a polyurethane prepolymer with NCO end. S4. Disperse 7.5 parts of amine-modified silica nanorings in anhydrous DMF and sonicate for 2 hours to ensure full dispersion to obtain a suspension. Add the suspension, 5 parts of bis(catechol)borane, and 8 parts of polydopamine nanoparticles to the polyurethane prepolymer and mix evenly by high-speed mechanical stirring to obtain a mixed slurry. S5. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it at 80°C for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation. Then, cool it down to 60°C and cure it for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, so as to achieve covalent bonding between the inorganic and organic phases. Continue to cool it down to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach an equilibrium state, thus obtaining a high-toughness material with an inorganic-organic hybrid crosslinked network.

[0022] Example 2 S1. First, cyclic PS-b-PEO is synthesized and self-assembled into cyclic micelles in a selective solvent (a mixed solution of DMF, DMSO and water). Using the cyclic micelles as templates, silica is deposited in the crown region of the micelles via a sol-gel method (hydrolysis of tetraethyl orthosilicate TEOS). The polymer template is then removed by calcination, and the surface is modified with aminopropyltriethoxysilane to obtain amino-modified silica nanorings (outer diameter 50 nm, inner diameter 20 nm). S2. Dopamine hydrochloride was dissolved in Tris-HCl buffer solution with a pH of 8.5, and polymerized by vigorous stirring at room temperature for 24 hours. After centrifugation and washing, polydopamine nanoparticles (100 nm) were obtained. S3. Place 105 parts of polycaprolactone diol in a dry reactor and dehydrate it under vacuum at 110°C for 2 hours. Then cool it down to 80°C, add 16.5 parts of isophorone diisocyanate and 0.8 parts of dibutyltin dilaurate, and react under nitrogen protection for 3 hours to obtain a polyurethane prepolymer with NCO end. S4. Disperse 5 parts of amine-modified silica nanorings in anhydrous DMF and sonicate for 2 hours to ensure full dispersion to obtain a suspension. Add the suspension, 6 parts of bis(catechol)borane, and 6 parts of polydopamine nanoparticles to the polyurethane prepolymer and mix evenly by high-speed mechanical stirring to obtain a mixed slurry. S5. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it at 80°C for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation. Then, cool it down to 60°C and cure it for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, so as to achieve covalent bonding between the inorganic and organic phases. Continue to cool it down to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach an equilibrium state, thus obtaining a high-toughness material with an inorganic-organic hybrid crosslinked network.

[0023] The difference between Example 2 and Example 1 is that the proportions of each raw material are different, but both are within the protection scope of this invention.

[0024] Example 3 S1. First, cyclic PS-b-PEO is synthesized and self-assembled into cyclic micelles in a selective solvent (a mixed solution of DMF, DMSO and water). Using the cyclic micelles as templates, silica is deposited in the crown region of the micelles via a sol-gel method (hydrolysis of tetraethyl orthosilicate TEOS). The polymer template is then removed by calcination, and the surface is modified with aminopropyltriethoxysilane to obtain amino-modified silica nanorings (outer diameter 50 nm, inner diameter 20 nm). S2. Dopamine hydrochloride was dissolved in Tris-HCl buffer solution with a pH of 8.5, and polymerized by vigorous stirring at room temperature for 24 hours. After centrifugation and washing, polydopamine nanoparticles (100 nm) were obtained. S3. Place 90 parts of polycaprolactone diol in a dry reactor and dehydrate it under vacuum at 110°C for 2 hours. Then cool it down to 80°C, add 14.5 parts of isophorone diisocyanate and 1.2 parts of dibutyltin dilaurate, and react under nitrogen protection for 3 hours to obtain a polyurethane prepolymer with NCO end. S4. Disperse 10 parts of amine-modified silica nanorings in anhydrous DMF and sonicate for 2 hours to ensure full dispersion to obtain a suspension. Add the suspension, 4 parts of bis(catechol borane) and 10 parts of polydopamine nanoparticles to the polyurethane prepolymer and mix evenly by high-speed mechanical stirring to obtain a mixed slurry. S5. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it at 80°C for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation. Then, cool it down to 60°C and cure it for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, so as to achieve covalent bonding between the inorganic and organic phases. Continue to cool it down to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach an equilibrium state, thus obtaining a high-toughness material with an inorganic-organic hybrid crosslinked network.

[0025] The difference between Example 3 and Example 1 is that the proportions of each raw material are different, but both are within the protection scope of this invention.

[0026] This invention ensures that energy is efficiently dissipated throughout the entire impact process, from the initial impact to the final impact, through the synergistic effects of primary instantaneous dissipation, secondary primary dissipation, and tertiary topological dissipation, rather than being concentrated at a single point and causing material failure. The high-toughness materials with inorganic-organic hybrid cross-linked networks prepared in Examples 1-3 all possess ultra-high toughness, far exceeding that of ordinary elastomers (-1 kJ / m²) and high-toughness hydrogels (-10 kJ / m²), while also exhibiting high tensile strength, reaching >30 MPa. Furthermore, the high-toughness materials with inorganic-organic hybrid cross-linked networks prepared in this invention can achieve efficient self-healing after being placed at room temperature for 24 hours, with a repair efficiency >90%.

[0027] To verify the superiority of the present invention, comparative examples 1 and 2 are provided here.

[0028] Comparative Example 1 S1. Dopamine hydrochloride was dissolved in Tris-HCl buffer solution with a pH of 8.5, and polymerized by vigorous stirring at room temperature for 24 hours. After centrifugation and washing, polydopamine nanoparticles (100 nm) were obtained. S2. Place 98 parts of polycaprolactone diol in a dry reactor and dehydrate it under vacuum at 110°C for 2 hours. Then cool it down to 80°C, add 15.5 parts of isophorone diisocyanate and 1.2 parts of dibutyltin dilaurate, and react under nitrogen protection for 3 hours to obtain a polyurethane prepolymer with NCO end. S3. Add 5 parts of bis(catechol borane) and 8 parts of polydopamine nanoparticles to the polyurethane prepolymer and mix them evenly by high-speed mechanical stirring to obtain a mixed slurry. S4. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it at 80°C for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation. Then, cool it down to 60°C and cure it for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, so as to achieve covalent bonding between the inorganic and organic phases. Continue to cool it down to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach an equilibrium state, thus obtaining the material.

[0029] The difference between Comparative Example 1 and Example 1 is that no amine-modified silica nanorings were added. The material prepared in Comparative Example 1 has high hardness but insufficient "toughness," and is prone to cracking after impact, as there is no material inside to absorb or dissipate impact energy.

[0030] Comparative Example 2 S1. First, cyclic PS-b-PEO is synthesized and self-assembled into cyclic micelles in a selective solvent (a mixed solution of DMF, DMSO and water). Using the cyclic micelles as templates, silica is deposited in the crown region of the micelles via a sol-gel method (hydrolysis of tetraethyl orthosilicate TEOS). The polymer template is then removed by calcination, and the surface is modified with aminopropyltriethoxysilane to obtain amino-modified silica nanorings (outer diameter 50 nm, inner diameter 20 nm). S2. 15.5 parts of isophorone diisocyanate and 1.2 parts of dibutyltin dilaurate were reacted under nitrogen protection for 3 hours to obtain a mixture; S4. Disperse 7.5 parts of amino-modified silica nanorings in anhydrous DMF and sonicate for 2 hours to ensure full dispersion to obtain a suspension. Add the suspension to the mixture and mix evenly by high-speed mechanical stirring to obtain a mixed slurry. S5. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it at 80°C for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation. Then, cool it down to 60°C and cure it for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, so as to achieve covalent bonding between the inorganic and organic phases. Continue to cool it down to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach an equilibrium state, thus obtaining the material.

[0031] The difference between Comparative Example 2 and Example 1 is that polydopamine nanoparticles and bis(catechol)borane were not added. The material prepared in Comparative Example 2 is highly brittle, and after being subjected to impact, it cannot undergo reversible fracture and remodeling, nor can it recover its connection.

[0032] Finally, it should be noted that the above preferred 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 through the above preferred embodiments, those skilled in the art should understand that various changes can be made to it in form and detail without departing from the scope defined by the claims of the present invention.

Claims

1. A high-toughness material with an inorganic-organic hybrid cross-linked network, characterized in that: The high-toughness material is composed of inorganic phase components and organic phase components; The inorganic phase component consists of 5-10 parts of amine-modified silica nanorings; The organic phase component consists of 90-105 parts of polycaprolactone diol, 14.5-16.5 parts of isophorone diisocyanate, 0.8-1.5 parts of dibutyltin dilaurate, 4-6 parts of bis(catechol)borane, and 6-10 parts of polydopamine nanoparticles.

2. The high-toughness material of the inorganic-organic hybrid cross-linked network according to claim 1, characterized in that: The inorganic phase component is 7.5 parts of amine-modified silica nanorings; The organic phase component consists of 98 parts polycaprolactone diol, 15.5 parts isophorone diisocyanate, 0.8-1.5 parts dibutyltin dilaurate, 5 parts bis(catechol)borane, and 8 parts polydopamine nanoparticles.

3. A method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network, comprising using the high-toughness material with an inorganic-organic hybrid crosslinked network as described in claims 1-2, characterized in that: Includes the following steps, S1. First, a macrocyclic amphiphilic block copolymer is synthesized and self-assembled into cyclic micelles in a selective solvent. Using the cyclic micelles as templates, silica is deposited in the crown region of the micelles by sol-gel method. The polymer template is then removed by calcination, and the surface is modified by aminopropyltriethoxysilane to obtain amino-modified silica nanorings. S2. Dopamine hydrochloride was dissolved in Tris-HCl buffer, and polymerized by vigorous stirring at room temperature for 24 hours. After centrifugation and washing, polydopamine nanospheres were obtained. S3. Polycaprolactone diol was placed in a dry reactor and dehydrated under vacuum at 110°C for 2 hours. Then the temperature was lowered to 80°C, and isophorone diisocyanate and dibutyltin dilaurate were added. The reaction was carried out under nitrogen protection for 3 hours to obtain a polyurethane prepolymer with NCO terminal. S4. Disperse the amine-modified silica nanorings in anhydrous DMF and sonicate for 2 hours to ensure full dispersion to obtain a suspension. Add the suspension, bis(catechol)borane, and polydopamine nanoparticles to the polyurethane prepolymer and mix them evenly by high-speed mechanical stirring to obtain a mixed slurry. S5. Pour the mixed slurry into a polytetrafluoroethylene mold and cure it using a stepped temperature curing method.

4. The method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network according to claim 3, characterized in that: The stepped temperature curing method is specifically as follows: First, cure at 80℃ for 4 hours to complete the chain extension of the polyurethane prepolymer chain and the initial network formation; Then, the temperature is lowered to 60℃ and cured for 24 hours to promote the full formation of borate ester bonds and the reaction between the amine groups on the surface of A-SNRs and the residual -NCO of the prepolymer, thereby achieving covalent bonding between the inorganic and organic phases. Continue to cool to room temperature for 48 hours to allow the hydrogen bond network to fully form and reach an equilibrium state, resulting in a high-toughness material with an inorganic-organic hybrid cross-linked network.

5. The method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network according to claim 3, characterized in that: The macrocyclic amphiphilic block copolymer is cyclic PS-b-PEO, and the sol-gel method specifically utilizes the hydrolysis of tetraethyl orthosilicate (TEOS).

6. The method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network according to claim 3, characterized in that: The polydopamine nanoparticles have a diameter of 95-105 nm.

7. The method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network according to claim 3, characterized in that: The amine-modified silica nanorings have an outer diameter of 48-52 nm and an inner diameter of 18-22 nm.

8. The method for preparing a high-toughness material with an inorganic-organic hybrid crosslinked network according to claim 3, characterized in that: The pH value of the Tris-HCl buffer solution is 8.5.

Images