CN114316380A - Honeycomb light high-toughness elastomer resin-based material and preparation method thereof - Google Patents
Honeycomb light high-toughness elastomer resin-based material and preparation method thereof Download PDFInfo
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Abstract
The invention provides an elastomer resin-based material, which comprises rubber and a resin material; the rubber is a continuous phase, and the resin material is a dispersed phase; the elastomer resin-based material has a porous channel structure. The elastomer resin-based material with a specific structure and composition provided by the invention has the advantages of small density of the honeycomb material with oval honeycomb holes, no contraction cracking phenomenon, good toughness, excellent elasticity, excellent fatigue resistance, repeated bending and compression, excellent shape memory and elasticity, capability of being bent and twisted for 180 degrees in any direction without plastic deformation, higher specific strength and wear resistance compared with the traditional heat insulation material, and good heat insulation performance. The preparation method provided by the invention is simple to operate, mild in condition and good in controllability, can be used for large-scale preparation, and can regulate and control the structure, density, mechanical property and the like of the obtained polymer composite material by regulating and controlling freezing temperature, rubber emulsion content, resin content, curing temperature and the like.
Description
Technical Field
The invention belongs to the technical field of flexible resin composite materials, relates to an elastomer resin-based material and a preparation method thereof, and particularly relates to a honeycomb-shaped light high-toughness elastomer resin-based material and a preparation method thereof.
Background
The polymer porous material has important characteristics of light weight, heat insulation, temperature resistance, moisture resistance and the like, and has wide application prospects in various fields of national defense and military industry, aerospace, transportation, biomedicine, building engineering and the like. Meanwhile, lightweight, high strength and durable materials have been the basic attributes of many advanced scientific and engineering demanding materials that can effectively meet the requirements for materials under extreme conditions. Meanwhile, the high-molecular porous material has high-efficiency heat-insulating performance, so that the electric power cost brought by building energy can be greatly reduced, and the future energy shortage can be effectively relieved. At present, mechanical toughness and thermal insulation performance of Advanced porous Materials are difficult to be considered (Advanced Functional Materials, page 1636/26/2016), which is mainly due to the difficulty in achieving/achieving coordination of molecular structure and microporous structure. The rigid molecule has high mechanical strength, but the intrinsic thermal conductivity of the molecular network is high, and brittle failure is easy to occur, so that the application is not favorable (such as the phenolic foam plate is easy to slag off). The flexible molecular network has low thermal conductivity, but is not strong enough and has poor stability, and cannot meet the safety requirement of engineering materials. To achieve this goal, scientists have conducted a series of studies. For example: german applied chemistry (Angewandte Chemie,2019, 131: 14290) reports that a honeycomb-shaped fibroin-silver sulfide double-network structure material is prepared by using fibroin as a framework and utilizing an in-situ liquid phase synthesis technology and can be used in the field of water evaporation. For example, germany Advanced Functional Materials (2018, page 51 28) reports that nano sodium chloride particles are used as a sacrificial template, and the template is removed after a conductive composite material of PGS and carbon nanotubes is prepared by using a 3D printing technology, so as to obtain the nano friction power generation material.
However, the materials prepared by the above methods all have the following problems that the preparation method is complicated, the technical cost and the economic cost are high, the large-scale preparation is not suitable, and the prepared materials can not realize functionalization, such as: fire prevention, heat insulation, sound insulation, and the like. Similarly, the template method, Science (2013, 341, 530) in the united states of america, reported that a porous polymer skeleton material having hierarchical pores was prepared by using a polyethylene oxide monomer as a template, a polyethylene oxide-polystyrene block copolymer as a matrix, and xylene as a solvent, inducing phase separation by a solvent evaporation process, and washing to remove the template. This material can be used to grow the framework of calcite crystals. However, the material has various problems mentioned above, and the problem of volume of the material in practical application is ignored.
The oriented freezing technology is a self-assembly technology widely applied to the fields of bionic science, bioengineering and the like. In recent years, this technology has enabled the production of a variety of high-performance anisotropic thermal insulation materials by incorporating various new materials of nanostructure units, polymers, inorganic ceramics, and the like. The material has excellent heat insulation and fire resistance, and has great engineering and scientific development prospects. In 2017, the U.S. Nature Communications (page 14425 of 8 of 2017) reports that a chemically modified graphene solution is subjected to oriented freeze-drying by utilizing an oriented freezing technology to prepare a three-dimensional oriented framework structure. And then, ceramic precursor polymethylsiloxane is used for permeating into the graphene framework and is sintered at 1000 ℃ in a nitrogen atmosphere to convert siloxane polymer into silicon carbide ceramic, so that the graphene-ceramic composite block is obtained, but the process is complicated, high-temperature sintering is involved, the energy consumption is high, the environment is not protected, and meanwhile, the shrinkage rate of the obtained graphene framework in the sintering process is up to 20%, and the problem is large in the practical application process.
In conclusion, the existing materials still have the defects of weak performance, poor practicability, complex preparation process, high cost and the like.
Therefore, how to design a porous material with good elasticity, good toughness, high durability and good heat insulation performance by using nanotechnology has become a problem to be solved in the field of novel porous materials, and is one of the focuses of extensive attention of prospective researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an elastomer resin-based material and a preparation method thereof, and particularly to a honeycomb-shaped light high-toughness elastomer resin-based material, which has good toughness, excellent elasticity, excellent fatigue resistance, repeated bending and compression, higher strength and wear resistance than commercial insulation board materials, and good heat insulation performance. And the method is simple to operate, good in controllability and capable of realizing large-scale preparation.
The invention provides an elastomer resin-based material, which comprises rubber and a resin material;
the rubber is a continuous phase, and the resin material is a dispersed phase;
the elastomer resin-based material has a porous channel structure.
Preferably, the elastomeric resin-based material has a sea-island structure;
in the elastomer resin-based material, the mass content of the resin material is 25-50%;
in the elastomer resin-based material, the mass content of rubber is 50-75%;
the porous cell structures comprise honeycomb cell structures;
the honeycomb holes of the honeycomb comprise oval honeycomb holes;
the elastomeric resin-based material has a vertical channel orientation structure.
Preferably, the radial dimension of the pore channel is 5-50 μm;
the wall thickness of the pore channel is 1-5 mu m;
the elastomer resin-based material further comprises a thickening agent;
the thickening agent is a supporting template made of elastomer resin-based material;
in the elastomer resin-based material, a rubber molecular chain and a resin molecular chain form a charge action and a hydrogen bond action through a thickening agent;
in the elastomer resin-based material, the mass content of the thickening agent is 2-4%.
Preferably, in the elastomer resin-based material, the longitudinal channel structure penetrates through the elastomer resin-based material;
the elastomer resin-based material also comprises a nano filler;
the nano filler is compounded in the pore channel structure;
in the elastomer resin-based material, the mass content of the nano filler is 5-15%;
the elastomer resin-based material has longitudinal texture-like appearance macroscopically along the direction of the pore channel;
the elastomer resin-based material is a heat insulating material and/or a cushioning material.
Preferably, the rubber comprises one or more of natural rubber, isoprene rubber, nitrile rubber, styrene butadiene rubber and butyl rubber;
the resin comprises one or more of polyurethane, epoxy resin, phenolic resin and silicone-acrylate resin;
the elastomer resin-based material is a bendable material and/or a compressible material;
the bending strength of the elastomer resin-based material is 4-11 MPa;
the elastomer resin-based material is prepared by an oriented freezing method;
the density of the elastomer resin-based material is 100-300 mg/cm3。
The invention provides a preparation method of an elastomer resin-based material, which comprises the following steps:
1) mixing the water-based rubber emulsion, the water-based resin and water to obtain a mixed solution;
2) adding a mixed glue solution of a thickening agent and a catalyst into the mixed solution obtained in the step, mixing again to obtain a mixed sol, placing the mixed sol into a mold, performing oriented freezing, taking out, placing on a substrate, and performing freeze drying to obtain a freeze-dried material;
3) and heating and curing the freeze-dried material obtained in the step to obtain the elastomer resin-based material.
Preferably, the ratio of the water-based rubber emulsion to the water is (3-9) g: 10 mL;
the ratio of the water-based resin to the water is (1-3) g: 10 mL;
the catalyst comprises one or more of formic acid, glacial acetic acid, oxalic acid, tartaric acid and hydrochloric acid;
the thickening agent comprises one or more of chitosan, sodium alginate, agar, starch and sodium carboxymethyl cellulose;
the raw materials in the step 1) also comprise nano-fillers.
Preferably, the ratio of the nanofiller to the water is (0.5-1.5) g: 10 mL;
the nano filler comprises one or more of silicon carbide, montmorillonite, silicon dioxide, carbon nano tubes, graphene, magnesium salt whiskers, calcium sulfate whiskers and hydroxyapatite;
the mixed glue solution of the thickening agent and the catalyst comprises the thickening agent, the catalyst and a water solvent;
the ratio of the thickening agent to the aqueous solvent is (2-4) g: 100 ml;
the volume ratio of the catalyst to the water solvent is (2-4) to 100;
the volume ratio of water in the mixed solution to the mixed glue solution of the thickening agent and the catalyst is 1: 1.
preferably, the temperature of the orientation freezing is-10 to-80 ℃;
the orientation freezing time is 10-30 min;
the substrate comprises a low surface energy substrate;
the material of the substrate comprises one or more of polytetrafluoroethylene, perfluoroethylene propylene copolymer, fluorocarbon resin and organic silicon rubber;
the manner of placement includes vertical placement along the orientation direction.
Preferably, the temperature of the freeze drying is-20 to-50 ℃;
the freeze drying time is 24-72 hours;
the temperature of the heating and curing is 100-180 ℃;
the heating and curing time is 0.5-2 h;
the heating and curing process also comprises a carbonization step;
the carbonization temperature is 300-800 ℃;
the carbonization time is 1-4 h.
The invention provides an elastomer resin-based material, which comprises rubber and a resin material; the rubber is a continuous phase, and the resin material is a dispersed phase; the elastomer resin-based material has a porous channel structure. Compared with the prior art, the elastomer resin-based material with a specific structure and composition is obtained, and the specific honeycomb material with the oval honeycomb holes is small in density (100-300 mg/cm)3) The heat-insulating material has the advantages of no shrinkage cracking phenomenon, good toughness, excellent elasticity, excellent fatigue resistance, repeated bending and compression, excellent shape memory and elasticity, capability of being bent and twisted for 180 degrees in any direction without plastic deformation, higher specific strength and wear resistance (without powder falling) compared with the traditional commercial heat-insulating material, and good heat-insulating property. In addition, the invention can regulate and control the structure, density, mechanical property and the like of the obtained polymer composite material by regulating and controlling the freezing temperature, the content of the rubber emulsion, the content of resin, the curing temperature and the like.
The porous elastomer resin-based material with good elasticity, good toughness, high durability and good heat-insulating property is prepared based on an orientation freezing method, and the structure, density, mechanical strength and the like of the material can be regulated and controlled by regulating and controlling parameters and curing temperature in the orientation freezing process. Furthermore, by adding the conductive nano filler, the anisotropic flexible sensing performance can be achieved. The regulation and control process is simple and feasible, and can meet the requirements of different densities and strengths. The raw materials adopted by the invention are aqueous rubber emulsion, aqueous resin and natural thickening agent. The synthesis technology of the rubber emulsion and the water-based resin is mature, simple and easy to obtain, and high in industrialization degree; the natural thickening agent such as chitosan and sodium alginate is used as an important marine product, has wide source and is green and environment-friendly. The three components are low in price, can effectively reduce the production cost and is very suitable for commercial production. Meanwhile, the invention is prepared by a wet method, can combine different requirements and compound different materials, and is convenient to obtain various light high-strength materials with different functions. Meanwhile, the material matrix is rubber emulsion and water-based resin, and different rubber emulsion raw materials are adopted, so that the porous material with excellent elasticity and good weather resistance can be obtained, and the porous material is suitable for extreme working environments in various fields.
The method for preparing the elastomer resin-based material by adopting the oriented freezing method has the advantages of simple process, mature technology, controllable cellular structure, density and mechanical strength of the material, simple operation, mild conditions, good controllability, large-scale preparation and suitability for industrial development and application, and the cellular rubber resin material has low cost and excellent performance.
Experimental results show that the elastomer resin-based material prepared by the invention has small density (100-300 mg/cm)3) The thermal insulation material has no shrinkage cracking phenomenon, has excellent shape memory and elasticity (permanent deformation is not generated after 40% of maximum deformation compression cycle is 1000 times in the direction perpendicular to the pore channel, and permanent deformation is not generated after 20% of maximum deformation compression cycle is 1000 times in the direction parallel to the pore channel), can be bent and twisted for 180 degrees in any direction without generating plastic deformation, has higher specific strength and wear resistance (no powder falling) compared with the traditional commercial thermal insulation material, and has good thermal insulation performance.
Drawings
FIG. 1 is a scanning electron microscope image of a transverse cross section of a cured cellular rubber resin material prepared in example 1 of the present invention;
FIG. 2 is a longitudinal cross-sectional scanning electron microscope image of the cured cellular rubber resin material prepared in example 1 of the present invention;
FIG. 3 is a photograph of a physical sample of a cured cellular rubber resin material prepared in example 1 of the present invention;
FIG. 4 is a curved display photograph of a cellular rubber resin material prepared in example 1 of the present invention;
FIG. 5 is a photograph showing a twist of the cellular rubber resin material prepared in example 1 of the present invention;
FIG. 6 is a stress-strain curve of a compression cycle test of a cellular rubber resin material prepared in example 1 of the present invention;
FIG. 7 is a three-point bending stress-strain curve of cellular rubber resin materials of different ratios prepared in example 2 of the present invention;
FIG. 8 is a stress-strain curve of compression cycle test of the cellular rubber resin material (formulation: 600mg rubber, 200mg resin) prepared in example 2 of the present invention;
FIG. 9 is a photograph of a physical embodiment of cellular rubber resin material (CMN) of varying rubber/resin content prepared in example 2 of the present invention;
FIG. 10 is a graph showing the thermal insulation performance (longitudinal and transverse) of honeycomb rubber resin materials of different rubber/resin contents prepared in example 2 of the present invention;
fig. 11 shows the conductivity of the honeycomb rubber resin material with different carbon tube contents prepared in example 3 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs a purity commonly used in the field of analytical materials or resin-based composite materials.
The invention provides an elastomer resin-based material, which comprises rubber and a resin material;
the rubber is a continuous phase, and the resin material is a dispersed phase;
the elastomer resin-based material has a porous channel structure.
In the present invention, the elastomer resin-based material preferably has an island-in-sea structure.
In the present invention, the porous cell structure preferably includes a honeycomb-like cell structure. Specifically, the cell holes of the honeycomb preferably include oval cell holes.
In the present invention, the elastomeric resin-based material preferably has a vertical cell orientation.
In the invention, the radial dimension of the pore channel is preferably 5-50 μm, more preferably 15-40 μm, and more preferably 25-30 μm.
In the invention, the wall thickness of the pore channel is preferably 1-5 μm, more preferably 1.5-4.5 μm, more preferably 2-4 μm, and more preferably 2.5-3.5 μm.
In the present invention, a thickener is preferably included in the elastomer resin-based material.
In the present invention, the thickener is preferably a supporting template of an elastomeric resin-based material.
In the present invention, in the elastomer resin-based material, the rubber molecular chain and the resin molecular chain form a charge action and a hydrogen bond action, preferably by a thickener.
In the present invention, the mass content of the thickener in the elastomer resin-based material is preferably 2% to 4%, more preferably 2.4% to 3.6%, and still more preferably 2.8% to 3.2%.
In the present invention, in the elastomer resin-based material, the longitudinal channel structure preferably penetrates the elastomer resin-based material.
In the present invention, the elastomeric resin-based material preferably includes a nanofiller therein.
In the present invention, the nanofiller is preferably compounded in the channel structure. Specifically, the composite mode is an embedded network structure.
In the present invention, the mass content of the nanofiller in the elastomer resin-based material is preferably 5% to 15%, more preferably 7% to 13%, and still more preferably 9% to 11%.
In the present invention, the elastomeric resin-based material preferably has a longitudinal, textural morphology on a macroscopic scale along the direction of the channels.
In the present invention, the elastomer resin-based material is preferably a heat insulating material and/or a cushioning material, more preferably a heat insulating material and a cushioning material.
In the present invention, the mass content of the resin material in the elastomer resin-based material is preferably 25% to 50%, more preferably 30% to 45%, and still more preferably 35% to 40%.
In the present invention, the resin preferably includes one or more of polyurethane, epoxy resin, phenol resin, and silicone-acrylate resin, and more preferably polyurethane, epoxy resin, phenol resin, or silicone-acrylate resin.
In the present invention, the mass content of the rubber in the elastomer resin-based material is preferably 50% to 75%, more preferably 55% to 70%, and still more preferably 60% to 65%.
In the present invention, the elastomeric resin-based material is preferably a bendable material and/or a compressible material, more preferably a bendable material or a compressible material.
In the present invention, the elastomeric resin-based material is preferably prepared by an orientation freezing method.
In the invention, the preferable range of the elastomer resin-based material is 100-300 mg/cm3More preferably 140 to 260mg/cm3More preferably 180 to 220mg/cm3。
The invention provides a preparation method of an elastomer resin-based material, which comprises the following steps:
1) mixing the water-based rubber emulsion, the water-based resin and water to obtain a mixed solution;
2) adding a mixed glue solution of a thickening agent and a catalyst into the mixed solution obtained in the step, mixing again to obtain a mixed sol, placing the mixed sol into a mold, performing oriented freezing, taking out, placing on a substrate, and performing freeze drying to obtain a freeze-dried material;
3) and heating and curing the freeze-dried material obtained in the step to obtain the elastomer resin-based material.
The invention firstly mixes the water-based rubber latex, the water-based resin and the water to obtain the mixed solution.
In the invention, the ratio of the water-based rubber emulsion to the water is preferably (3-9) g: 10mL, more preferably (4-8) g: 10mL, more preferably (5-7) g: 10 mL.
In the present invention, the ratio of the aqueous resin to the water is preferably (1 to 3) g: 10mL, more preferably (1.4-2.6) g: 10mL, more preferably (1.8-2.2) g: 10 mL.
In the present invention, the raw material in the step 1) preferably includes a nano filler.
In the present invention, the nanofiller preferably comprises one or more of silicon carbide, montmorillonite, silica, carbon nanotubes, graphene, magnesium salt whiskers, calcium sulfate whiskers, and hydroxyapatite, and more preferably silicon carbide, montmorillonite, silica, carbon nanotubes, graphene, magnesium salt whiskers, calcium sulfate whiskers, or hydroxyapatite.
In the present invention, the ratio of the nanofiller to the water is preferably (0.5 to 1.5) g: 10mL, more preferably (0.7 to 1.3) g: 10mL, more preferably (0.9 to 1.1) g: 10 mL.
Adding the mixed glue solution of the thickening agent and the catalyst into the mixed solution obtained in the step, mixing again to obtain mixed sol, placing the mixed sol into a mold, performing oriented freezing, taking out, placing on a substrate, and performing freeze drying to obtain the freeze-dried material.
In the present invention, the mixed glue solution of the thickener and the catalyst preferably comprises the thickener, the catalyst and an aqueous solvent
In the present invention, the ratio of the thickener to the water solvent is preferably (2 to 4) g: 100ml, more preferably (2.4 to 3.6) g: 100ml, more preferably (2.8 to 3.2) g: 100 ml.
In the invention, the volume ratio of the catalyst to the water solvent is preferably (2-4): 100, more preferably (2.4-3.6): 100, and more preferably (2.8-3.2): 100.
In the present invention, the volume ratio of the water in the mixed solution to the mixed glue solution of the thickener and the catalyst is preferably 1: 1.
in the present invention, the temperature of the orientation freezing is preferably-10 to-80 deg.C, more preferably-20 to-50 deg.C, and still more preferably-30 to-40 deg.C.
In the invention, the time for orientation freezing is preferably 10-30 min, more preferably 14-26 min, and more preferably 18-22 min.
In the present invention, the substrate preferably comprises a low surface energy substrate.
In the present invention, the material of the substrate preferably includes one or more of polytetrafluoroethylene, perfluoroethylene propylene copolymer, fluorocarbon resin and silicone rubber, and more preferably polytetrafluoroethylene, perfluoroethylene propylene copolymer, fluorocarbon resin or silicone rubber.
In the present invention, the manner of placement preferably includes vertical placement along the orientation direction.
In the present invention, the temperature of the freeze-drying is preferably-20 to-50 ℃, more preferably-30 to-50 ℃, and still more preferably-40 to-50 ℃.
In the invention, the freeze drying time is preferably 24-72 h, more preferably 34-62 h, and more preferably 44-52 h.
Finally, heating and curing the freeze-dried material obtained in the step to obtain the elastomer resin-based material.
In the invention, the heating and curing temperature is preferably 100-180 ℃, more preferably 110-150 ℃, and more preferably 120-140 ℃.
In the invention, the time for heating and curing is preferably 0.5-2 h, more preferably 0.8-1.7 h, and more preferably 1.1-1.4 h.
In the present invention, the heating and curing preferably includes a carbonization step.
In the invention, the carbonization temperature is preferably 300-800 ℃, more preferably 400-700 ℃, and more preferably 500-600 ℃.
In the invention, the carbonization time is preferably 1-4 h, more preferably 1.5-3.5 h, and more preferably 2-3 h.
The invention is a complete and refined integral preparation process, better ensures the structure, the appearance and the parameters of the elastomer resin-based material, and improves the integral comprehensive performance of the elastomer resin-based material, and the preparation method of the elastomer resin-based material can specifically comprise the following steps:
a. dispersing the nano filler, the water-based rubber emulsion and the water-based resin in water, and stirring to obtain a mixed solution;
b. mixing the mixed solution, the thickening agent and the catalyst solution in different proportions to obtain mixed sol, slowly adding the mixed sol into a mold (the bottom surface is a smooth and flat copper block), and adding liquid nitrogen to cool and perform oriented freezing. And finally, after the sample is completely frozen, placing the sample on a low-surface-energy substrate, and storing the sample in a refrigerator. Finally, putting the mixture into a freeze dryer for freeze drying;
c. and c, placing the block material obtained in the step b into an oven for curing to obtain the honeycomb elastomer resin matrix material.
Specifically, the aqueous rubber emulsion in step a is preferably selected from one of natural rubber, isoprene rubber, nitrile rubber, styrene butadiene rubber, butyl rubber and the like, and more preferably styrene butadiene rubber and nitrile butadiene rubber. The aqueous resin is preferably one selected from polyurethane, epoxy resin, phenol resin, melamine resin, and the like, and more preferably epoxy resin or phenol resin.
The ratio of the mass of the rubber emulsion, the mass of the water-based resin and the water in the mixed solution in the step a is (3 g-9 g):1 g-3 g):10 ml.
Specifically, the nano-filler is an inorganic material, such as one or more of silicon carbide, montmorillonite, silica, carbon nanotubes, graphene, magnesium salt whiskers, calcium sulfate whiskers, hydroxyapatite and the like in any proportion. In the step a, the ratio of the mass of the nano filler to the water in the mixed solution is (0.5-1.5) g: 10 ml. The filler (nano filler) is only used for assisting the three-dimensional structure of the supporting material and endowing the material with more functionality, and can be selectively added or not added.
Specifically, the thickener in the step b is chitosan, sodium alginate, agar, starch, sodium carboxymethylcellulose and the like. The catalyst is one or more of formic acid, glacial acetic acid, oxalic acid, tartaric acid and hydrochloric acid in any proportion, and formic acid, acetic acid and hydrochloric acid are more preferable. The mass of the thickening agent, the volume of the catalyst and the proportion of the thickening agent to the water in the catalyst solution are (2 g-4 g): 0.5 ml-1 ml):100 ml.
Specifically, in the step b, the orientation freezing temperature is-10 to-80 ℃, the block material obtained by freezing is placed on a low surface energy substrate (polytetrafluoroethylene, perfluoroethylene propylene copolymer, fluorocarbon resin and organic silicon rubber) and is placed in a freeze dryer, and the duration time of the freeze-drying process is 24 to 72 hours.
Specifically, in the step c, the curing temperature is 100-180 ℃, and the curing time is 0.5-2 h; the carbonization temperature is 300-800 ℃, and the carbonization time is 1-4 h.
The method takes an oriented freezing method as a preparation basis, takes rubber emulsion, mixed sol, various fillers and water-based resin as raw materials, ensures that the resin is supported enough without collapsing in the freeze drying process by the interaction of charges and hydrogen bonds between a thickening agent and molecular chains of rubber and resin, takes the thickening agent as a supporting template and is assisted by various fillers, so that a sample keeps a honeycomb structure in the oriented freezing process; then the freeze-dried material is solidified in an oven to obtain enough mechanical strength; the material can be further carbonized at low temperature, so that the density of the material is further reduced.
The rubber and the resin adopted in the invention are water-based rubber emulsion and water-soluble water-based resin, and simultaneously, the invention adopts a natural thickening agent which is green, environment-friendly and low in price as a main supporting template. The filler is added into the sol, so that the low molecular weight rubber can be further supported, and the resin can not collapse due to creep action in the freeze drying process.
In the invention, in order to realize orientation freezing, the bottom surface of the metal platform is immersed into a liquid nitrogen tank, a thermocouple is bonded on the surface of the metal platform, and the surface temperature of the metal platform is controlled by changing the addition of liquid nitrogen. The method can control the error of the surface temperature of the metal platform within 3 ℃. In the invention, the size and the shape of the prepared material are controlled by molds with different sizes and shapes, the material of the mold is preferably silicone rubber, polydimethylsiloxane and polytetrafluoroethylene, and more preferably silicone rubber and polydimethylsiloxane.
In the orientation freezing process, the temperature of the metal platform is controlled at the required freezing temperature, the metal platform is placed on a mould, and the mixed sol is poured. The freezing temperature is preferably-10 ℃ to-80 ℃, and more preferably-20 ℃ to-40 ℃. The invention particularly adopts the substrate with low surface energy, because the resin is not completely solidified in the freeze drying process after the orientation freezing, the material has certain viscosity, in order to ensure the quality of the material, the sample after the orientation freezing is placed on the substrate with low surface energy, and then the sample and the substrate are placed into a freeze dryer together for freeze drying, thereby better improving the quality of the final material.
The low surface energy substrate is preferably one of polytetrafluoroethylene, a perfluoroethylene propylene copolymer, fluorocarbon resin and organic silicon rubber, and more preferably polytetrafluoroethylene; the duration of the freeze drying process is preferably 24 to 72 hours, and more preferably 36 to 48 hours.
The sample after freeze drying is off-white or light yellow in color, intact in structure but low in strength, and needs further curing treatment or carbonization treatment after curing. Specifically, the curing temperature is preferably 100-180 ℃, and more preferably 120-160 ℃; the curing time is preferably 0.5h to 2h, more preferably 0.5h to 1 h; the carbonization temperature is preferably 300-800 ℃, and the carbonization time is preferably 1-4 h.
The invention provides a honeycomb light high-toughness elastomer resin-based material and a preparation method thereof, the elastomer resin-based material with a specific structure and composition has small density (100-300 mg/cm) of the specific honeycomb material with oval honeycomb holes3) The heat-insulating material has the advantages of no shrinkage cracking phenomenon, good toughness, excellent elasticity, excellent fatigue resistance, repeated bending and compression, excellent shape memory and elasticity, capability of being bent and twisted for 180 degrees in any direction without plastic deformation, higher specific strength and wear resistance (without powder falling) compared with the traditional commercial heat-insulating material, and good heat-insulating property. In addition, the invention can regulate and control the structure, density, mechanical property and the like of the obtained polymer composite material by regulating and controlling the freezing temperature, the content of the rubber emulsion, the content of resin, the curing temperature and the like.
The porous elastomer resin-based material with good elasticity, good toughness, high durability and good heat-insulating property is prepared based on an orientation freezing method, and the structure, density, mechanical strength and the like of the material can be regulated and controlled by regulating and controlling parameters and curing temperature in the orientation freezing process. Furthermore, by adding the conductive nano filler, the anisotropic flexible sensing performance can be achieved. The regulation and control process is simple and feasible, and can meet the requirements of different densities and strengths. The raw materials adopted by the invention are aqueous rubber emulsion, aqueous resin and natural thickening agent. The synthesis technology of the rubber emulsion and the water-based resin is mature, simple and easy to obtain, and high in industrialization degree; the natural thickening agent such as chitosan and sodium alginate is used as an important marine product, has wide source and is green and environment-friendly. The three components are low in price, can effectively reduce the production cost and is very suitable for commercial production. Meanwhile, the invention is prepared by a wet method, can combine different requirements and compound different materials, and is convenient to obtain various light high-strength materials with different functions. Meanwhile, the material matrix is rubber emulsion and water-based resin, and different rubber emulsion raw materials are adopted, so that the porous material with excellent elasticity and good weather resistance can be obtained, and the porous material is suitable for extreme working environments in various fields.
The method for preparing the elastomer resin-based material by adopting the oriented freezing method has the advantages of simple process, mature technology, controllable cellular structure, density and mechanical strength of the material, simple operation, mild conditions, good controllability, large-scale preparation and suitability for industrial development and application, and the cellular rubber resin material has low cost and excellent performance.
Experimental results show that the elastomer resin-based material prepared by the invention has small density (100-300 mg/cm)3) The thermal insulation material has no shrinkage cracking phenomenon, has excellent shape memory and elasticity (permanent deformation is not generated after 40% of maximum deformation compression cycle is 1000 times in the direction perpendicular to the pore channel, and permanent deformation is not generated after 20% of maximum deformation compression cycle is 1000 times in the direction parallel to the pore channel), can be bent and twisted for 180 degrees in any direction without generating plastic deformation, has higher specific strength and wear resistance (no powder falling) compared with the traditional commercial thermal insulation material, and has good thermal insulation performance.
For further illustration of the present invention, the following will describe in detail an elastomer resin-based material and a method for preparing the same with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Dispersing 4g of chitosan (Shanghai pharmaceutical group) in 100ml of deionized water, adding 4ml of acetic acid, and stirring overnight to obtain a light yellow transparent acetic acid chitosan mixed sol for later use.
Adding 1ml of deionized water into a centrifugal tube, adding 900mg of nitrile-butadiene rubber emulsion and 300mg of commercial melamine resin, and fully shaking and mixing;
and (3) putting 1ml of the acetic acid chitosan mixed sol into a centrifugal tube, fully shaking and mixing, and putting the centrifugal tube into a vacuum oven for vacuumizing to remove air bubbles in the sol for later use.
Placing a metal platform connected with a thermocouple in a plastic foam container, pouring liquid nitrogen into the plastic foam container, and controlling the pouring amount of the liquid nitrogen to stabilize the temperature of the metal platform at-10 ℃; cutting a through small block with the bottom surface of about 1.5cm x 1.5cm from the middle of a silica gel plate with the thickness of 1.5cm as a template, and flatly placing the small block on the surface of a low-temperature metal platform; and pouring the mixed sol into a template, controlling the temperature of a metal platform to be stabilized at about-10 ℃ by adding the amount of liquid nitrogen, and completely freezing the sample block after about 20 minutes. And taking the sample block out of the template, vertically placing the sample block on a flat polytetrafluoroethylene substrate in the orientation direction, and then putting the sample together with the substrate into a freeze dryer for freeze drying for 48 hours. Taking out after drying, and curing in an oven at 100 ℃ for 0.5 h.
The elastomeric resin-based material prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is a scanning electron microscope image of a transverse cross section of a cured cellular rubber resin material prepared in example 1 of the present invention.
Referring to fig. 2, fig. 2 is a scanning electron microscope image of a longitudinal section of the cured cellular rubber resin material prepared in example 1 of the present invention.
Referring to fig. 3, fig. 3 is a photograph of a physical sample of the cured cellular rubber resin material prepared in example 1 of the present invention.
The elastomer resin-based material prepared in example 1 of the present invention was examined.
The density of the sample was about 240mg/cm3The compressive yield strength in the orientation direction was about 1.0MPa, the tensile strength was 1.5MPa, and the Young's modulus was 13.5 MPa.
Referring to fig. 4, fig. 4 is a curved display photograph of the cellular rubber resin material prepared in example 1 of the present invention.
Referring to fig. 5, fig. 5 is a twist display photograph of the cellular rubber resin material prepared in example 1 of the present invention.
Referring to fig. 6, fig. 6 is a compression cycle test stress-strain curve of the cellular rubber resin material prepared in example 1 of the present invention.
Example 2
Dispersing 4g of chitosan (Shanghai pharmaceutical group) in 100ml of deionized water, adding 4ml of acetic acid, and stirring overnight to obtain a light yellow transparent acetic acid chitosan mixed sol for later use.
3 centrifuge tubes are respectively filled with 1ml of deionized water, 900mg, 600mg and 300mg of nitrile rubber emulsion and 300mg, 200mg and 100mg of commercial melamine resin are added into the centrifuge tubes in sequence and are fully shaken and mixed.
And (3) respectively adding 1ml of the chitosan sol into a centrifugal tube, fully shaking and mixing, and placing in a vacuum oven for vacuumizing to remove air bubbles in the sol for later use.
The metal platform temperature was stabilized at-10 ℃ using the same preparation method as in example 1; flatly placing the silica gel template on the surface of the low-temperature metal platform; and pouring the mixed sol into a template, controlling the temperature of a metal platform to be stabilized at about-10 ℃ by adding the amount of liquid nitrogen, and completely freezing the sample block after about 20 minutes. The sample block is taken out from the template, the orientation direction is vertically placed on a flat plate substrate made of polytetrafluoroethylene, and then all samples and the substrate are placed into a freeze dryer together for freeze drying, and the drying time is 48 hours. Taking out after drying, and curing in an oven at 100 ℃ for 0.5 h.
Elastomer resin-based materials of different ratios prepared in example 2 of the present invention were tested.
Referring to fig. 7, fig. 7 is a three-point bending stress-strain curve of cellular rubber resin materials with different formulations prepared in example 2 of the present invention. Wherein, the sample is named as CMN-X-Y, X represents the content of the water-based resin, and Y represents the content of the rubber emulsion; the sample was CMN-3-9 as in example 1, i.e., 300mg resin, 900mg rubber; CMF is a control sample containing only 900mg of melamine resin (MF) and no rubber component.
Referring to fig. 8, fig. 8 is a stress-strain curve of compression cycle test of the honeycomb rubber resin material (compounding ratio: 600mg rubber, 200mg resin) prepared in example 2 of the present invention.
Referring to fig. 9, fig. 9 is a photograph of cellular rubber resin material (CMN) of varying rubber/resin content prepared in example 2 of the present invention. Wherein, the sample is named as CMN-X-Y, X represents the content of the water-based resin, and Y represents the content of the rubber emulsion.
Referring to fig. 10, fig. 10 is a graph showing the thermal insulation performance (longitudinal and transverse) of the honeycomb rubber resin materials of different rubber/resin contents prepared in example 2 of the present invention. Wherein, the sample is named as CMN-X-Y, X represents the content of the water-based resin, and Y represents the content of the rubber emulsion. The heat insulation performance adopts a transient plane heat source method.
Example 3
4g of chitosan (Shanghai pharmaceutical group) was dispersed in 100ml of deionized water, and 4ml of acetic acid was added thereto, followed by stirring overnight to obtain a pale yellow transparent chitosan sol for use.
And (3) putting 1ml of deionized water into each centrifuge tube, adding 900mg, 600mg and 300mg of nitrile rubber emulsion, 150mg, 100mg and 50mg of multi-wall carbon nano tube and 300mg, 200mg and 100mg of commercial melamine resin into the centrifuge tubes in sequence, and fully shaking and mixing.
And (3) respectively adding 1ml of the acetic acid chitosan mixed sol into a centrifuge tube, fully shaking and mixing, and then placing in a vacuum oven for vacuumizing to remove air bubbles in the sol for later use.
The metal platform temperature was stabilized at-10 ℃ using the same preparation method as in example 1; flatly placing the silica gel template on the surface of the low-temperature metal platform; and pouring the mixed sol into a template, controlling the temperature of a metal platform to be stabilized at about-10 ℃ by adding the amount of liquid nitrogen, and completely freezing the sample block after about 20 minutes. The sample block is taken out from the template, the orientation direction is vertically placed on a flat plate substrate made of polytetrafluoroethylene, and then all samples and the substrate are placed into a freeze dryer together for freeze drying, and the drying time is 48 hours. Taking out after drying, and curing in an oven at 100 ℃ for 0.5 h.
The elastomer resin-based materials with different carbon nanotube contents prepared in example 3 of the present invention were subjected to performance testing.
Connecting wires at two ends of the material, coating silver glue for packaging, and testing the resistance of the material by using a universal meter.
Referring to fig. 11, fig. 11 shows the conductivity of the honeycomb rubber resin material with different carbon tube contents prepared in example 3 of the present invention.
Wherein, the resin content of the upper pattern product is 300mg, the rubber content is 900mg, and the carbon nano tube content is 150 mg; the resin content of the lower pattern product is 100mg, the rubber content is 300mg, and the carbon nanotube content is 50 mg. The results show that the conductivity of the material increases with increasing carbon nanotube content.
While the present invention has been described in detail with respect to a cellular lightweight high toughness elastomeric resin based material and method of making the same, the principles and embodiments of the present invention are described herein using specific examples, which are set forth only to facilitate an understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. An elastomeric resin-based material, comprising a rubber and a resin material;
the rubber is a continuous phase, and the resin material is a dispersed phase;
the elastomer resin-based material has a porous channel structure.
2. The elastomeric resin-based material of claim 1, wherein the elastomeric resin-based material has a sea-island structure;
in the elastomer resin-based material, the mass content of the resin material is 25-50%;
in the elastomer resin-based material, the mass content of rubber is 50-75%;
the porous cell structures comprise honeycomb cell structures;
the honeycomb holes of the honeycomb comprise oval honeycomb holes;
the elastomeric resin-based material has a vertical channel orientation structure.
3. The elastomeric resin-based material of claim 1, wherein the channels have a radial dimension of 5 to 50 μ ι η;
the wall thickness of the pore channel is 1-5 mu m;
the elastomer resin-based material further comprises a thickening agent;
the thickening agent is a supporting template made of elastomer resin-based material;
in the elastomer resin-based material, a rubber molecular chain and a resin molecular chain form a charge action and a hydrogen bond action through a thickening agent;
in the elastomer resin-based material, the mass content of the thickening agent is 2-4%.
4. The elastomeric resin-based material of claim 1, wherein the elastomeric resin-based material has longitudinal cell structures extending through the elastomeric resin-based material;
the elastomer resin-based material also comprises a nano filler;
the nano filler is compounded in the pore channel structure;
in the elastomer resin-based material, the mass content of the nano filler is 5-15%;
the elastomer resin-based material has longitudinal texture-like appearance macroscopically along the direction of the pore channel;
the elastomer resin-based material is a heat insulating material and/or a cushioning material.
5. The elastomeric resin-based material of claim 1, wherein the rubber comprises one or more of natural rubber, isoprene rubber, nitrile rubber, styrene butadiene rubber, and butyl rubber;
the resin comprises one or more of polyurethane, epoxy resin, phenolic resin and silicone-acrylate resin;
the elastomer resin-based material is a bendable material and/or a compressible material;
the bending strength of the elastomer resin-based material is 4-11 MPa;
the elastomer resin-based material is prepared by an oriented freezing method;
the density of the elastomer resin-based material is 100-300 mg/cm3。
6. A method of preparing an elastomeric resin-based material, comprising the steps of:
1) mixing the water-based rubber emulsion, the water-based resin and water to obtain a mixed solution;
2) adding a mixed glue solution of a thickening agent and a catalyst into the mixed solution obtained in the step, mixing again to obtain a mixed sol, placing the mixed sol into a mold, performing oriented freezing, taking out, placing on a substrate, and performing freeze drying to obtain a freeze-dried material;
3) and heating and curing the freeze-dried material obtained in the step to obtain the elastomer resin-based material.
7. The method according to claim 6, wherein the ratio of the aqueous rubber emulsion to the water is (3-9) g: 10 mL;
the ratio of the water-based resin to the water is (1-3) g: 10 mL;
the catalyst comprises one or more of formic acid, glacial acetic acid, oxalic acid, tartaric acid and hydrochloric acid;
the thickening agent comprises one or more of chitosan, sodium alginate, agar, starch and sodium carboxymethyl cellulose;
the raw materials in the step 1) also comprise nano-fillers.
8. The method according to claim 7, wherein the ratio of the nanofiller to the water is (0.5-1.5) g: 10 mL;
the nano filler comprises one or more of silicon carbide, montmorillonite, silicon dioxide, carbon nano tubes, graphene, magnesium salt whiskers, calcium sulfate whiskers and hydroxyapatite;
the mixed glue solution of the thickening agent and the catalyst comprises the thickening agent, the catalyst and a water solvent;
the ratio of the thickening agent to the aqueous solvent is (2-4) g: 100 ml;
the volume ratio of the catalyst to the water solvent is (2-4) to 100;
the volume ratio of water in the mixed solution to the mixed glue solution of the thickening agent and the catalyst is 1: 1.
9. the method of claim 6, wherein the temperature of the oriented freezing is from-10 ℃ to-80 ℃;
the orientation freezing time is 10-30 min;
the substrate comprises a low surface energy substrate;
the material of the substrate comprises one or more of polytetrafluoroethylene, perfluoroethylene propylene copolymer, fluorocarbon resin and organic silicon rubber;
the manner of placement includes vertical placement along the orientation direction.
10. The method according to claim 6, wherein the temperature of the freeze-drying is-20 to-50 ℃;
the freeze drying time is 24-72 hours;
the temperature of the heating and curing is 100-180 ℃;
the heating and curing time is 0.5-2 h;
the heating and curing process also comprises a carbonization step;
the carbonization temperature is 300-800 ℃;
the carbonization time is 1-4 h.
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