CN120818176B - An antistatic aerogel for 3D printing, its preparation method and application - Google Patents
An antistatic aerogel for 3D printing, its preparation method and applicationInfo
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- CN120818176B CN120818176B CN202511325033.8A CN202511325033A CN120818176B CN 120818176 B CN120818176 B CN 120818176B CN 202511325033 A CN202511325033 A CN 202511325033A CN 120818176 B CN120818176 B CN 120818176B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
The invention belongs to the technical field of aerogel materials, and particularly relates to an antistatic aerogel for 3D printing and a preparation method and application thereof. The preparation method comprises the steps of (1) dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and aniline monomers in an acidic solvent to obtain a monomer mixed solution, (2) stirring and dissolving polyamide in the monomer mixed solution, (3) initiating reaction to obtain a polyaniline modified polyamide solution, and (4) freeze-drying to obtain the antistatic aerogel for 3D printing. By controlling synthesis conditions, a core-shell structure of the acid doped polyaniline coated inorganic nano-particles is formed, and a good conductive path is formed in polyamide with a small polyaniline addition amount. The antistatic aerogel for 3D printing can be used for technologies such as photo-curing molding and fused deposition of polyurethane resin in 3D printing technology, and the antistatic performance and mechanical property of 3D printing products are improved.
Description
Technical Field
The invention belongs to the technical field of aerogel materials, and particularly relates to an antistatic aerogel for 3D printing and a preparation method and application thereof.
Background
3D printing technology is one of the advanced Additive Manufacturing (AM) technologies. It is a process of adding and joining material layer by layer to form an article, AM is contrary to Subtractive Manufacturing (SM), which is the removal of material from a bulk (i.e., machining) to form a desired product. One major advantage of AM over SM is that it can accurately produce more complex shapes, which have attracted considerable attention in the development of advanced manufacturing materials due to its high manufacturing efficiency, high scalability, low cost, etc.
With the rapid development of 3D printing technology over the years, it has been widely used and has made great progress in various fields. Firstly, 3D printing techniques are ideal choices for aerospace components because they have complex geometries, require simultaneous consideration of structure, heat dissipation and air flow effects, reduce wastage and provide complex shapes through 3D printing custom-manufactured production, and are characterized by small batches of parts, 3D printing techniques are relatively convenient and do not require expensive equipment such as molds compared to conventional techniques for small batches of production.
Secondly, 3D printing techniques are also widely used in the biomedical field. 3D printing techniques enable 3D printing of biocompatible materials, cells and supporting components into complex 3D functional living tissue. 3D bioprinting is being applied in regenerative medicine to address the need for tissues and organs that are suitable for transplantation. 3D bioprinting has been used for the generation and transplantation of a variety of tissues including skin, bone, vascular grafts, tracheal splints, cardiac tissue and cartilage structures.
3D printing techniques have also found application in automated architecture. The 3D printing manufacture has the advantages of high precision, strong perforating capability, various design possibilities and the like, so that the 3D printing manufacture has certain reliability in the building industry, such as geometric complexity and hollow structure.
In addition, 3D printing technology is currently being applied to various production fields, namely clothing, electronic products, automobiles, robots, military, oceanography, and the like, as a common production method. Among the 3D printing techniques described above, the most widely used printing material is a resin material such as polyurethane. Polyurethane has been widely used in 3D printing technology due to its good mechanical strength and toughness and excellent processability. However, as a resin material, the antistatic property is poor, and a high-voltage discharge phenomenon caused by charge accumulation occurs during the use process, which interferes with the normal operation of the apparatus.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the antistatic aerogel for 3D printing, and the antistatic material is of a porous gel structure, so that the resin material is fully soaked in the printing process, the compatibility of the resin material with polyurethane resin and other materials is improved, and the antistatic performance of the printing material is further improved on the basis of improving the mechanical property of the printing material.
In order to improve the antistatic property of the resin, it is generally necessary to add a conductive filler. The preparation method of the polymer conductive composite material can be divided into two main types from the angle of the addition mode of the conductive filler, namely an in-situ polymerization method and a solution blending method, wherein the conductive filler and the polymer are prepared into a nano composite material in a physical dispersion mode before or after polymerization, and the polymer is prepared into a polymer nano composite material by prefabricating a conductive three-dimensional structure and then performing polymer infiltration polymerization. In the previous work, the inventor respectively adopts in-situ polymerization (CN 118667223A) and post infiltration (CN 118702962A, CN118812911A, CN118834412A and the like) processes to prepare aerogel powder with certain conductive performance. The in-situ polymerization method needs polymerization of various raw materials, the preparation process is complex, and the preparation time of the subsequent infiltration process is longer, so that the three-dimensional conductive matrix is firstly constructed, and a complicated infiltration process is needed, in the process, infiltration components are easy to disperse unevenly to generate micron-sized aggregates, and the performance of the composite material is reduced. In order to solve the problems, the invention takes polyamide as aerogel matrix, and prepares the acid doped polyaniline conductive particles directly in polyamide solution.
In order to achieve the above purpose, the invention adopts the following specific technical scheme:
the preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Dispersing inorganic nano particles modified by the epoxy group-containing silane coupling agent and aniline monomer in an acidic solvent, and standing for a period of time to obtain a monomer mixed solution, wherein the reaction solution can be specifically kept for 1-2 hours to promote the formation of hydrogen bonds between the aniline monomer and the epoxy group-containing silane coupling agent;
(2) Stirring and dissolving polyamide in the monomer mixed solution to obtain a polyamide mixed solution;
(3) Dropwise adding an initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution;
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing. The freeze-drying technique is a simple, economical and environmentally friendly drying method. The ice crystal sublimation principle is utilized to reduce the temperature of the solvent below the freezing point, so that the water is converted into ice. And then under higher vacuum degree, the ice is sublimated into steam directly, so that a gas-liquid interface can be eliminated, and a curved liquid level is avoided to form in the holes, thereby reducing the drying stress and obtaining the aerogel with a complete framework. In particular, after the completion of the reaction, heating may be appropriately performed to promote dispersion of the components and then freeze-drying may be performed.
In the invention, polyamide is selected as the matrix resin of the antistatic aerogel for 3D printing, because the structural difference between polymers can directly reflect the compatibility between the polymers. Polyurethane is a block polymer with urethane bonds as repeating units, while characteristic groups in polyamide are amide bonds, the urethane bonds and the amide bonds have similar structures and can serve as hydrogen bond donors and acceptors of each other, so that the polyurethane and the polyamide have better compatibility from the structural point of view. The polyurethane and the polyamide also have respective performance advantages, and the polyurethane has unique properties such as high tensile strength, high elongation at break, good wear resistance, low-temperature elasticity and the like due to microphase separation. The polyamide has good mechanical, electrical and thermal properties and exhibits a high temperature resistance, and both polyurethane and polyamide can be used as second components for performance improvement. In addition, the polyamide generally has a higher melting point (generally above 240 ℃) and high tensile strength, and the polyamide is adopted as a matrix structure of the aerogel, so that the mechanical property of the aerogel can be improved, and the mechanical strength of the polyurethane composite material is improved. More importantly, polyamide is easily soluble in acidic solvents relative to thermoplastic resin materials such as polyimide and polyurethane. The intrinsic polyaniline and the derivative thereof are electrical insulators, and have lower conductivity, however, the conductivity can be improved by ten orders of magnitude after being doped by proton acid. The doping process of polyaniline is reversible, when polyaniline is doped by protonic acid, only positive charge is introduced, and the electron number on the main chain is not changed, namely only proton transfer exists, namely, the polyaniline is essentially an intramolecular oxidation-reduction reaction, the electron structure is also greatly changed, and when the polyaniline is doped, the imino group on the molecular chain and protonic acid form a half-ketone free radical cation, and meanwhile, the electron transfer on the nitrogen atom forms a conductive bipolar crystal lattice, so that the polyaniline has conductivity. The invention polymerizes polyaniline in situ in polyamide acid solution, skillfully and directly utilizes the acid solvent in the polyamide solution to dope polyaniline, not only simplifies the production process, but also ensures that the acid doped polyaniline is uniformly dispersed in the polyamide matrix.
However, polyaniline synthesized by directly adding an aniline monomer into a polyamic acid solution has poor dispersibility, and is difficult to form a conductive path. In order to uniformly disperse polyaniline in a polyamide aerogel network, the invention introduces inorganic nano particles modified by the epoxy group-containing silane coupling agent as a nucleating agent for polyaniline, and the inorganic nano particles modified by the epoxy group-containing silane coupling agent as rigid particles can play a role in enhancing and improve the mechanical property of polyamide aerogel powder. The epoxy group on the surface of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent is easy to form a hydrogen bond with the amino group on the aniline monomer, and when the initiator is added, the aniline monomer takes the inorganic nano-particles modified by the epoxy group-containing silane coupling agent as a core to form the polyaniline-coated inorganic nano-particles. The polyaniline modified inorganic nano particles formed by in-situ polymerization in the polyamic acid solution have the triple technical effects of doping, enhancement and conduction, namely, firstly, polyamide dissolved in the acid solution is used as matrix resin of aerogel to play a skeleton role, secondly, acid in the polyamide solution plays a role in dissolving polyamide, and the polyamide can be doped to improve the conductivity of the polyaniline, and the inorganic nano particles modified by the epoxy group-containing silane coupling agent play a role in enhancing rigid particles, and more importantly, the inorganic nano particles can serve as nucleating agents of aniline monomers to form polyaniline nano particles with core-shell structures in situ in the polyamide solution, so that the dispersion performance of the polyaniline is improved, the formation of a conductive path is promoted, and the conductivity of the aerogel is greatly improved under the condition of adding less conductive filler. On the contrary, polyaniline on the surfaces of the inorganic particles not only has the effect of enhancing conductivity, but also has good compatibility with polyurethane and polyamide which are nitrogen-containing organic matters, and the polyaniline is adopted to coat the inorganic nano particles, so that the compatibility of the inorganic nano particles with resins such as polyamide and polyurethane can be improved, and the dispersion and mechanical properties can be improved.
Notably, attention should be paid to the order of addition of the epoxy group-containing silane coupling agent modified inorganic nanoparticles and the aniline monomer. Firstly preparing an acidic solution of inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer, and then adding polyamide into the acidic solution to gradually dissolve the polyamide. If the inorganic nano-particles modified by the epoxy group-containing silane coupling agent and the aniline monomer are directly added into an acidic solution of the polyamide, the nucleation of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent can be influenced due to the existence of the nitrogen-containing group in the polyamide, so that the formation of an organic-inorganic core-shell structure is not facilitated.
In an embodiment, the epoxy group-containing silane coupling agent in the step (1) is at least one of gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane, and 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane. Compared with the coupling agent containing amino silane, the epoxy group contains an oxygen-containing ether bond with higher activity, can form a hydrogen bond with an amino group on an aniline monomer to form a stronger bonding effect, so that the inorganic nano particles can perform nucleation effect and are not influenced by the polyamide of the nitrogen-containing polymer in the formic acid solution. The amino group on the silane coupling agent has no oxygen-containing active functional group, is not easy to form a hydrogen bond and other bonding actions with an aniline monomer which also contains the amino group, is easy to be influenced by polyamide in solution, can only play a role in improving the compatibility of inorganic nano particles and matrix resin, and cannot play a nucleation role.
In an embodiment, the inorganic nanoparticles in the step (1) are at least one of nano silica, nano zirconium dioxide, nano silicon carbide, nano silicon nitride and nano boron carbide.
In one embodiment, the inorganic nanoparticles have a particle size of 10 to 100nm. Specifically, the value may be any of 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, and 100nm. The inorganic nano particles with proper particle size can have the functions of nucleation, dispersion and enhancement, and the mechanical property of the 3D printing antistatic material is improved.
In one embodiment, the acidic solvent is a formic acid solution. Specifically, an aqueous formic acid solution having a concentration of 88% by weight can be used.
In one embodiment, the mass ratio of the epoxy group-containing silane coupling agent modified inorganic nanoparticles to the aniline monomer in the step (1) is (0.05-0.5): 1. The modified inorganic nano-particles are rich in epoxy groups on the surfaces, and the epoxy groups are easy to form hydrogen bonds with amino groups on aniline monomers, so that the nucleation effect of the inorganic nano-particles is enhanced. In particular, the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is (0.05-0.4) 1, further (0.1-0.35) 1, and still further (0.1-0.3) 1. The proper amount of inorganic nano particles can play a role in reinforcing and nucleating rigid particles, can avoid the problems that the particles are too much to agglomerate and polyaniline cannot be completely coated, can promote the formation of polyaniline core-shell structures, and can improve the compatibility of the inorganic nano particles and polyamide resin.
In one embodiment, the specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent in the step (1) comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1-2h at 40-60 ℃, filtering, washing and drying to obtain the epoxy group-containing silane coupling agent modified inorganic nano-particles.
In one embodiment, the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nanoparticles in the step (1) is (0.5-1): 1.
In one embodiment, the polyamide in step (2) is at least one of polyamide 6, polyamide 66, polyamide 46, polyamide 56, polyamide 610, polyamide 1010, and polyamide 12.
In one embodiment, the polyamide concentration in the polyamide compound solution in step (2), i.e. the mass of polyamide to the mass of solvent, is 1 to 10wt%.
In one embodiment, the mass ratio of aniline monomer to polyamide in step (2) is (0.2-0.8): 1. Specifically, any of 0.2:1,0.3:1,0.4:1,0.5:1,0.6:1,0.7:1, or 0.8:1 may be used. The polyaniline monomer is excessively small in dosage, which is unfavorable for the formation of conductive paths and the antistatic performance, and the aerogel structure is easily affected by excessive dosage, which is unfavorable for the improvement of the mechanical properties of 3D printing products.
In one embodiment, the initiator in the step (3) is at least one of ammonium persulfate and potassium persulfate, and specifically, the initiator is dropwise added in the form of an aqueous solution.
In one embodiment, the molar ratio of initiator to aniline monomer in step (3) is (0.1-1): 1.
In one embodiment, the reaction temperature in step (3) is 0-5 ℃ and the reaction time is 10-20 hours.
On the other hand, the invention also provides the antistatic aerogel for 3D printing, which is prepared by the method, and is an aerogel material with a three-dimensional porous structure, and the aerogel material is used as reinforcing and antistatic fillers of 3D printing resin materials such as polyurethane and the like, so that the mechanical property and antistatic capacity of a printing product can be improved.
In addition, the invention also provides application of the antistatic aerogel for 3D printing and a prepared 3D printing polyurethane material, and the antistatic aerogel for 3D printing can be used for a photocuring forming technology, a selective laser sintering technology, a fused deposition technology or a layered entity manufacturing technology in a 3D printing technology. Specifically, the 3D printing polyurethane material includes a polyurethane resin material and an antistatic aerogel for 3D printing. Further, a photo-curing molding technique or a fused deposition technique may be employed. In particular, fused deposition techniques are used to prepare polyurethane materials. The printing temperature in the fused deposition technique is not particularly limited, and is generally 190-220 ℃, and can be specifically adjusted according to the production process.
The synthesis of the antistatic aerogel for 3D printing comprises the steps of firstly effectively controlling geometric parameters (particle size and particle size distribution of nanoparticles), spatial distribution parameters (uniformity), volume fraction (content) and the like of polyaniline nanoparticles in a composite system, particularly controlling synthesis conditions to ensure that polyaniline particles in the system are at least in a nanoscale range in one dimension (namely controlling the primary structure of the nanoparticles), and secondly controlling the secondary structure of nanoparticle aggregates, wherein the method comprises the steps of controlling agglomeration of modified polyaniline nanoparticles and distribution of the nanoparticles in a polyamide matrix resin material, forming a good conductive path with a small polyaniline addition amount, and improving the antistatic performance of the antistatic aerogel for 3D printing.
The beneficial effects are that:
The invention polymerizes polyaniline in situ in polyamide acid solution, skillfully and directly utilizes the acid solvent in the polyamide solution to dope polyaniline, not only simplifies the production process, but also ensures that the acid doped polyaniline is uniformly dispersed in the polyamide matrix. The invention introduces inorganic nano particles modified by the epoxy group-containing silane coupling agent as a nucleating agent for polyaniline and a rigid particle reinforcing agent for polyamide aerogel powder. The inorganic nano particles modified by the epoxy group-containing silane coupling agent are used as nucleating agents of aniline monomers, the polyaniline nano particles with core-shell structures are formed in situ in the polyamide solution, the dispersion performance of polyaniline is improved, the formation of conductive paths is promoted, and the conductivity of aerogel is greatly improved under the condition of adding less conductive fillers. By controlling the agglomeration of modified polyaniline nano particles and the distribution of nano particles in a polyamide matrix resin material, a good conductive path is formed with a small polyaniline addition amount, and the antistatic performance of the antistatic aerogel for 3D printing is improved.
Drawings
FIG. 1 is a scanning electron microscope image of the antistatic aerogel for 3D printing prepared in example 10;
FIG. 2 is a perspective view of particles obtained by acid dissolution of the antistatic aerogel for 3D printing prepared in example 10;
fig. 3 is a particle transmission electron microscope image of the antistatic aerogel for 3D printing prepared in comparative example 1 obtained by acid dissolution.
The specific preparation method of the particles shown in fig. 2 and 3 comprises the steps of respectively dissolving and dispersing the antistatic aerogel for 3D printing prepared in example 10 and comparative example 1 in formic acid solution by ultrasonic, filtering to obtain precipitate, washing with a large amount of deionized water to obtain aqueous dispersion of the precipitate, separating the precipitate by adopting a centrifugal method, settling the precipitate at the bottommost part due to the large density of silicon dioxide, and drying the bottommost precipitate to obtain the particles.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments.
Example 1
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.1:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 2 hours at 40 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.5:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle size D50 of the inorganic nano-particles is 50nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.2:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.6:1, the reaction temperature is 0 ℃, and the reaction time is 13h.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 2
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.35:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1h at 60 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 1:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl triethoxysilane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 50nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.62:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.9:1, the reaction temperature is 0 ℃, and the reaction time is 20 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 3
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.05:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 50 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.48:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.8:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 4
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.12:1;
the specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 48 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 1:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl triethoxysilane, the inorganic nano-particles are nano-silica, and the volume average particle size D50 of the inorganic nano-particles is 35nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.58:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.9:1, the reaction temperature is 0 ℃, and the reaction time is 10 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 5
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.5:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 50 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.48:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.8:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 6
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.17:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.7h at 45 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.6:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl triethoxysilane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.4:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.7:1, the reaction temperature is 0 ℃, and the reaction time is 15 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 7
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.2:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 50 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.8:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.8:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 8
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.25:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.3h at 55 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 50nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.55:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.7:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 9
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.3:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.4 hours at a temperature of 47 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.7:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl triethoxysilane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 60nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.43:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.7:1, the reaction temperature is 0 ℃, and the reaction time is 19h.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Example 10
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.2:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 50 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.48:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.8:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Comparative example 1
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dispersing the inorganic nano particles modified by the silane coupling agent containing the amino group and the aniline monomer in a formic acid solvent, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the silane coupling agent containing the amino group to the aniline monomer is 0.2:1;
The specific preparation process of the inorganic nano-particles modified by the amino group-containing silane coupling agent comprises the steps of uniformly dispersing the amino group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 50 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the amino group-containing silane coupling agent, wherein the mass ratio of the amino group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the amino group-containing silane coupling agent is gamma-aminopropyl triethoxysilane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(2) Stirring and dissolving polyamide in a monomer mixed solution to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, the polyamide concentration in the polyamide mixed solution is 3.5wt%, and the mass ratio of aniline monomer to polyamide is 0.48:1;
(3) Dropwise adding an ammonium persulfate initiator into the polyamide mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.8:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
Comparative example 2
The preparation method of the antistatic aerogel for 3D printing comprises the following steps:
(1) Stirring and dissolving polyamide in a formic acid solvent to obtain a polyamide mixed solution, wherein the polyamide is polyamide 66, and the concentration of the polyamide in the polyamide mixed solution is 3.5wt%;
(2) Stirring and dispersing inorganic nano particles modified by an epoxy group-containing silane coupling agent and an aniline monomer in a polyamide mixed solution, and standing for 1.5h to obtain a monomer mixed solution, wherein the mass ratio of the inorganic nano particles modified by the epoxy group-containing silane coupling agent to the aniline monomer is 0.2:1, and the mass ratio of the aniline monomer to the polyamide is 0.48:1;
The specific preparation process of the inorganic nano-particles modified by the epoxy group-containing silane coupling agent comprises the steps of uniformly dispersing the epoxy group-containing silane coupling agent and the inorganic nano-particles in a mixed solvent of ethanol and deionized water, stirring and reacting for 1.6 hours at 50 ℃, filtering, washing and drying to obtain the inorganic nano-particles modified by the epoxy group-containing silane coupling agent, wherein the mass ratio of the epoxy group-containing silane coupling agent to the inorganic nano-particles is 0.8:1, the epoxy group-containing silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, the inorganic nano-particles are nano-silica, and the volume average particle diameter D50 of the inorganic nano-particles is 40nm;
(3) And dropwise adding an ammonium persulfate initiator into the monomer mixed solution, and stirring and reacting for a certain time to obtain a polyaniline modified polyamide solution, wherein the molar ratio of the initiator to the aniline monomer is 0.8:1, the reaction temperature is 0 ℃, and the reaction time is 17 hours.
(4) And freeze-drying the polyaniline modified polyamide solution to obtain the antistatic aerogel for 3D printing.
The aerogel materials prepared in the above examples and comparative examples were tested for their performance under the same conditions, and the antistatic aerogels for 3D printing prepared in examples 1 to 10 and comparative examples 1 to 2 were tested for their effect on the performance of 3D printed polyurethane products.
Specifically, the 3D printing polyurethane material comprises 100 parts of thermoplastic polyurethane, 15 parts of antistatic aerogel for 3D printing and 3 parts of zinc stearate. Printing the 3D printing polyurethane material into a spline, and testing the conductivity by adopting a conductivity tester according to the tensile strength of the spline tested by referring to GB/T528-2009 determination of the tensile stress and strain properties of vulcanized rubber or thermoplastic rubber. The results are shown in Table 1.
TABLE 1 Properties of 3D printed polyurethane products corresponding to examples 1-10 and comparative examples 1-2
Table 1, below
Fig. 1 is a scanning electron microscope image of the antistatic aerogel for 3D printing prepared in example 10. As can be seen from the figure, the aerogel has a rich pore structure, has a relatively uniform pore diameter, is beneficial to the melt impregnation of thermoplastic resin such as polyurethane and the like, and improves the compatibility and interfacial force of the aerogel and 3D printing matrix resin.
Fig. 2 is a particle transmission electron microscope image obtained by acid dissolution of the antistatic aerogel for 3D printing prepared in example 10. From the figure, polyaniline is uniformly coated on the surface of compact silicon dioxide particles, so that the polyaniline not only has a conductive effect, but also can serve as a surface modifier of inorganic nano particles, so that the compatibility of the inorganic nano particles and organic polyamide resin is improved, and the stability of the air-curing agent and the mechanical property of the 3D printing material are improved.
Fig. 3 is a particle transmission electron microscope image of the antistatic aerogel for 3D printing prepared in comparative example 1 obtained by acid dissolution. As can be seen from fig. 3, the surface of the inorganic nanoparticle is smoother, and no obvious coating layer exists, which indicates that polyaniline does not undergo polymerization reaction on the surface of the inorganic nanoparticle, and no core-shell structure is formed.
At the same time, it can be seen in combination with the data of table 1. The invention polymerizes polyaniline in situ in polyamide acid solution, skillfully and directly utilizes the acid solvent in the polyamide solution to dope polyaniline, not only simplifies the production process, but also ensures that the acid doped polyaniline is uniformly dispersed in the polyamide matrix. The invention introduces inorganic nano particles modified by the epoxy group-containing silane coupling agent as a nucleating agent for polyaniline and a rigid particle reinforcing agent for polyamide aerogel powder. The inorganic nano particles modified by the epoxy group-containing silane coupling agent are used as nucleating agents of aniline monomers, the polyaniline nano particles with core-shell structures are formed in situ in the polyamide solution, the dispersion performance of polyaniline is improved, the formation of conductive paths is promoted, and the conductivity of aerogel is greatly improved under the condition of adding less conductive fillers. By controlling the agglomeration of modified polyaniline nano particles and the distribution of nano particles in a polyamide matrix resin material, a good conductive path is formed with a small polyaniline addition amount, and the antistatic performance of the antistatic aerogel for 3D printing is improved.
Specifically, in comparison with example 10, comparative example 1 modified nanosilica with an amino group-containing silane coupling agent. In formic acid solution, amino groups on the silane coupling agent cannot form strong bonding effect with aniline monomers, inorganic nano particles cannot play a role of a nucleating agent, and only play a role of an inorganic filler, but polyaniline also serves as a conductive filler, so that the polyaniline and the inorganic nano particles cannot play a role of synergistic enhancement and antistatic.
In comparison with example 10, comparative example 2 in which polyamide was dissolved in an acidic solvent in advance, and then inorganic nanoparticles modified with an epoxy group-containing silane coupling agent and aniline monomer were added to the acidic solution of polyamide, the inorganic nanoparticles modified with an epoxy group-containing silane coupling agent are unfavorable for nucleation due to the nitrogen group in the polyamide and the influence of high viscosity of the polymer, resulting in poor dispersibility of the inorganic nanoparticles, failure of polyaniline to form a stable conductive network, and reduced conductivity and mechanical properties of the 3D printed product.
The foregoing description is merely illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Equivalent changes and modifications are intended to be within the scope of the present invention as defined in the appended claims.
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