CN110591145B - Multi-time interpenetrating network structure nano composite material and preparation method thereof - Google Patents
Multi-time interpenetrating network structure nano composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110591145B CN110591145B CN201910972728.3A CN201910972728A CN110591145B CN 110591145 B CN110591145 B CN 110591145B CN 201910972728 A CN201910972728 A CN 201910972728A CN 110591145 B CN110591145 B CN 110591145B
- Authority
- CN
- China
- Prior art keywords
- foam
- polyurethane
- polyurethane foam
- graphene oxide
- network structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a multi-time interpenetrating network structure nano composite material and a preparation method thereof, belonging to the field of composite material preparation. The nano composite material prepared by the method of dip coating, drying and curing for multiple times has a multilayer sandwich structure and a reticular structure, the nano material under the sandwich structure is used as a concentrated functional area, and the network structure connects the functional areas together in a reticular form in a matrix, so that the functional advantages of the nano carbon material can be exerted to the maximum extent under the condition of low content, and the integrity and the connectivity of the matrix material are not damaged.
Description
Technical Field
The invention relates to a multi-time interpenetrating network structure nano composite material and a preparation method thereof, belonging to the field of composite materials.
Background
The nano material is a novel material with at least one dimension in a nano scale, shows various excellent performances due to the nano size effect, and has been a key point in the field of material research since the discovery of the 20 th century and the 70 th era. The nano material is added into the polymer as an additive to form the multifunctional composite material, and the method is also an effective method for expanding the performance and application of the polymer material. The traditional preparation method of the nano composite material is a blending method, namely, a nano additive and a polymer precursor are mixed, stirred and solidified to form the composite material. However, the method has the phenomena that the nano-filler is difficult to disperse and easy to maliciously agglomerate, and greatly limits the exertion of excellent performance of the nano-filler, particularly the characteristic of high specific surface area; meanwhile, the special spatial distribution of the filler in the matrix is difficult to control and design; moreover, the amount of nanofiller is often high in order to perform a certain function. Therefore, there is a need to develop a novel method for preparing a composite material to design and prepare a nanocomposite material with a specific structure. In recent years, newly created template methods, gradient methods, and the like are still in the research stage of researching and exploring how to prepare nano composite materials with certain structures, particularly the preparation and performance research of composite materials based on a net distribution structure.
Disclosure of Invention
The invention aims to provide a preparation method of a multi-time interpenetrating network structure nano composite material, which is simple in process, easy to control and expected to be industrially generated, aiming at overcoming the defects of the prior art. The method is based on the view point of non-uniform network structure distribution of the nano particles in the matrix, solves the problems that the traditional blending method is difficult to overcome, such as easy malignant agglomeration, difficult control of distribution, high content and the like of the nano material particles in the matrix, and realizes the material preparation method by efficiently utilizing the nano filler under the condition of low content.
The technical scheme adopted by the invention is as follows:
a preparation method of a multi-time interpenetrating network structure nano composite material comprises the following steps:
s1: after carrying out oxygen plasma treatment on polyurethane foam with a network skeleton structure, immediately immersing the polyurethane foam into carbon material ink containing graphene oxide, vacuumizing to assist the ink to be immersed into foam pore channels, and maintaining pressure to carry out degassing; after standing, taking out the foam, carrying out low-speed centrifugation to recover redundant ink immersed in the pore channel, then uniformly mixing carbon material ink loaded on the surface of the foam framework, simultaneously carrying out high-speed centrifugation to remove residual liquid, and drying to obtain polyurethane foam with a graphene oxide layer attached to the surface of the framework;
s2: performing oxygen plasma treatment on the polyurethane foam obtained in the step S1 again, immediately soaking the polyurethane foam into the aqueous polyurethane solution, and vacuumizing to assist the aqueous polyurethane to be soaked into foam pore channels; after standing, taking out the foam, carrying out low-speed centrifugation to recover excessive waterborne polyurethane immersed in the pore channel, then uniformly mixing the waterborne polyurethane loaded on the surface of the foam framework, simultaneously carrying out high-speed centrifugation to remove residual liquid, drying and curing to obtain polyurethane foam with a sandwich structure as the framework;
s3: repeatedly coating the polyurethane foam obtained by one-time coating in the S2 for multiple times continuously according to S1 and S2 to obtain the polyurethane foam with a multi-layer sandwich structure;
s4: and finally, directly filling and curing the polyurethane foam obtained from the S3 by using aqueous polyurethane to obtain the polyurethane-based nano composite material with a multi-time interpenetrating network structure.
Preferably, in step S1, after the polyurethane foam having the graphene oxide layer attached to the surface of the skeleton is obtained, it is further required to perform a reduction reaction in a hydroiodic acid reducing agent so that the graphene oxide attached to the surface of the polyurethane foam skeleton is reduced to reduced graphene oxide. The method of the reduction reaction may adopt the following steps: the polyurethane foam was placed in a reducing agent of hydroiodic acid at 80 ℃ for 1 minute.
Based on the above two schemes, the present invention can further provide the following preferred schemes.
Preferably, in step S1, the polyurethane foam is polyurethane foam with PPI value of 60-80, and is subjected to ultrasonic washing twice by alternately using deionized water and ethanol in advance, and is dried for 5 hours at 50 ℃ for standby.
Preferably, in step S1, the carbon material ink is a graphene oxide glycol ink solution, and the preparation method includes: adding graphene oxide powder into ethylene glycol, stirring for 12 hours, and performing ultrasonic treatment for 2.5 hours alternately; and then adding acetic acid to enable the pH value of the solution to be 4, then adding a silane coupling agent KH550, and ultrasonically mixing uniformly to obtain the graphene oxide glycol ink, wherein the mass fraction of the graphene oxide is 0.4wt%, and the mass fraction of the silane coupling agent is 1.0 wt%.
In the mode, the solvent of the ink is ethylene glycol which is a good solvent of graphene oxide, and meanwhile, the high viscosity of the solvent is beneficial to the vacuumizing treatment process and the formation of a uniform liquid film of the ink on the surface of the foam framework. The control of the pH value is beneficial to the reaction of the coupling agent and the graphene oxide, the stability of the ink solution is maintained, and meanwhile, the subsequent graphene oxide nanosheet is beneficial to being attached to the surface of the foam framework.
Preferably, in step S1, the standing time is 15 minutes, and the standing is performed at normal temperature and normal pressure; the low-speed centrifugation is carried out on a spin coater at the rotating speed of 500 rpm, the high-speed centrifugation is carried out on a planetary mixer at the rotating speed of 1200 rpm, the drying temperature is 50 ℃, and the drying time is 40 hours.
The spin coater can be modified to have only centrifugal force. In the step, the spin coating instrument is used for low-speed centrifugal recovery of ink and waterborne polyurethane, so that the dip coating step can be repeated for a plurality of times; and the coating layer on the surface of the foam framework can be integrally and continuously uniform by using a planetary mixer (with autorotation in the process of cavity centrifugation) to perform high-speed mixing, and comprises the graphene oxide and the waterborne polyurethane coating.
Preferably, in step S2, the standing time is 15 minutes, and the standing is performed at normal temperature and normal pressure; the low-speed centrifugation is carried out on a spin coater at the rotating speed of 500 rpm, the high-speed centrifugation is carried out on a planetary mixer at the rotating speed of 1200 rpm, the drying temperature is 50 ℃, and the drying and curing time is 5 hours.
Preferably, in step S4, the method of directly filling and curing the polyurethane foam with the aqueous polyurethane is as follows: and (3) putting the polyurethane foam obtained in the step (S3) into an aqueous polyurethane solution, filling the aqueous polyurethane into foam pores under the assistance of vacuum, taking out the polyurethane foam filled with the aqueous polyurethane, and curing for 24 hours at 50 ℃.
It is another object of the present invention to provide a multiple interpenetrating network structure nanocomposite prepared by the method according to any one of the above embodiments.
The invention has the beneficial effects that: the nano composite material prepared by the method of dip coating, drying and curing for many times has a multilayer sandwich structure and a reticular structure, the nano material under the sandwich structure is taken as a concentrated functional area, and the network structure connects the functional areas together in a reticular form in a matrix, so that the functional advantages of the nano carbon material can be exerted to the maximum extent under the condition of low content, and the integrity and the connectivity of the matrix material are not damaged.
Drawings
FIG. 1 is a scanning electron micrograph of a raw polyurethane foam prepared in example 1.
Fig. 2 is a scanning electron microscope picture of a layer of graphene oxide uniformly attached to the surface of the polyurethane foam skeleton prepared in example 1.
Fig. 3 is a scanning electron microscope image of the 5-time interpenetrating network structure polyurethane-based graphene composite material prepared in example 1.
FIG. 4 shows the damping performance exhibited by the composites prepared in examples 1, 2 and 1.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
Example 1
1) Selecting industrial grade polyurethane foam with PPI value of 60-80, alternately ultrasonically washing twice with deionized water and ethanol, and drying for 5 hours at 50 ℃ for later use.
2) Preparing graphene oxide by using a chemical oxidation synthesis method, adding 0.4 g of graphene oxide powder into 100 ml of ethylene glycol, stirring for 12 hours, performing ultrasonic treatment for 2.5 hours alternately, adding acetic acid to adjust the pH value of the solution to 4, adding a silane coupling agent KH550 to the mass fraction of 1.0wt%, and finally preparing the graphene oxide ethylene glycol ink with the mass fraction of 0.4 wt%.
3) And (2) carrying out oxygen plasma treatment on the polyurethane foam obtained in the step 1) for 4 minutes to enable the surface of the polyurethane foam to be in better contact with the polyurethane foam in a soaking mode, then immediately soaking the polyurethane foam into the ink prepared in the step 2), vacuumizing to assist the ink to be soaked into foam pore channels, and keeping the pressure for 3 minutes to carry out degassing. And standing for 15 minutes in a normal-temperature and normal-pressure environment to enable the ink to be better immersed into the contact framework cavity, taking out the foam, carrying out low-speed centrifugation (500 revolutions per minute) on a spin coater to recover the redundant ink immersed into the pore channel, uniformly mixing the graphene oxide ink loaded on the surface of the foam framework on a planetary mixer at a high speed, and centrifuging to remove the residual liquid (1200 revolutions per minute). Drying for 40 hours at 50 ℃ to obtain the polyurethane foam with the framework surface attached with a layer of graphene oxide.
4) Carrying out oxygen plasma treatment on the composite foam obtained in the step 3) for 4 minutes, immediately immersing the composite foam into an aqueous polyurethane solution with the solid content of 35% and the viscosity of 75cps, and fully immersing the aqueous polyurethane into foam pore channels under the assistance of certain vacuum pumping. Standing for 15 minutes in a normal temperature and pressure environment, taking out the foam, and recovering excessive waterborne polyurethane through low-speed centrifugation in the step 3), and then uniformly mixing the waterborne polyurethane coated foam skeleton layer at a high speed. Drying and curing for 5 hours at 50 ℃ to obtain the polyurethane foam with a sandwich structure of the framework.
5) And (4) repeating the steps 3) and 4) to obtain the polyurethane foam with the multi-time coated lower skeleton in the multilayer sandwich structure. After 5 times of repeated coating, the obtained polyurethane foam is placed in aqueous polyurethane solution, the aqueous polyurethane is filled into foam pore channels under the assistance of vacuum negative pressure, and then the polyurethane foam filled with the aqueous polyurethane is taken out and cured for 24 hours at 50 ℃. Finally obtaining the polyurethane-based nano composite material with a multi-time interpenetrating network structure.
In the present embodiment, the scanning electron microscope picture of the original polyurethane foam in step 1) is shown in fig. 1, and it can be seen that the foam frameworks are interconnected to form a network structure, and the surface of the frameworks is smooth. As shown in fig. 2, the scanning electron microscope picture after the layer of graphene oxide is correspondingly coated in step 3) shows that the surface of the whole skeleton becomes rough, which indicates that the whole polyurethane skeleton is uniformly coated with the graphene oxide and the graphene oxide sheet is in an unfolded shape. And 5) repeating the step of coating for 5 times, wherein the scanning electron microscope picture of the polyurethane-based nanocomposite after the polyurethane is filled in the whole cavity is shown in figure 3, so that a refined 5-layer sandwich structure and a network structure formed by the sandwich structure can be clearly seen. The graphene oxide nano material under the sandwich structure is used as a concentrated functional area, and the functional areas are connected together in a matrix in a net shape by the network structure, so that the functional advantages of the nano carbon material can be exerted to the maximum extent under the condition of low content, and the integrity and connectivity of the matrix material are not damaged.
Example 2
1) Selecting industrial grade polyurethane foam with PPI value of 60-80, alternately ultrasonically washing twice with deionized water and ethanol, and drying for 5 hours at 50 ℃ for later use.
2) Preparing graphene oxide by using a chemical oxidation synthesis method, adding 0.4 g of graphene oxide powder into 100 ml of ethylene glycol, stirring for 12 hours, performing ultrasonic treatment for 2.5 hours alternately, adding acetic acid to adjust the pH value of the solution to 4, adding a silane coupling agent KH550 to the mass fraction of 1.0wt%, and finally preparing the graphene oxide ethylene glycol ink with the mass fraction of 0.4 wt%.
3) And (2) carrying out oxygen plasma treatment on the polyurethane foam obtained in the step 1) for 4 minutes, immediately immersing the polyurethane foam into the ink prepared in the step 2), vacuumizing to assist the ink to be immersed into foam pore channels, and maintaining the pressure for 3 minutes to carry out degassing. And standing for 15 minutes in a normal-temperature and normal-pressure environment, taking out the foam, performing low-speed centrifugation (500 revolutions per minute) on a spin coater to recover the redundant ink immersed in the pore channel, uniformly mixing the graphene oxide ink loaded on the surface of the foam framework on a planetary mixer at a high speed, and centrifuging to remove the residual liquid (1200 revolutions per minute). Drying for 40 hours at 50 ℃ to obtain the polyurethane foam with the framework surface attached with a layer of graphene oxide.
Then, the reduction process of graphene oxide is introduced: and (3) putting the polyurethane foam with the graphene oxide layer attached to the surface of the skeleton prepared in the step into hydroiodic acid, and reacting for 1 minute at 80 ℃, wherein the hydroiodic acid is used as a reducing agent to reduce the graphene oxide attached to the surface of the polyurethane foam skeleton into reduced graphene oxide.
4) Carrying out oxygen plasma treatment on the composite foam obtained in the step 3) for 4 minutes, immediately immersing the composite foam into an aqueous polyurethane solution with the solid content of 35% and the viscosity of 75cps, and fully immersing the aqueous polyurethane into foam pore channels under the assistance of certain vacuum pumping. Standing for 15 minutes in a normal temperature and pressure environment, taking out the foam, and recovering excessive waterborne polyurethane through low-speed centrifugation in the step 3), and then uniformly mixing the waterborne polyurethane coated foam skeleton layer at a high speed. Drying and curing for 5 hours at 50 ℃ to obtain the polyurethane foam with a sandwich structure of the framework.
5) And (4) repeating the steps 3) and 4) to obtain the polyurethane foam with the multi-time coated lower skeleton in the multilayer sandwich structure. After 5 times of repeated coating, the obtained polyurethane foam is placed in aqueous polyurethane solution, the aqueous polyurethane is filled into foam pore channels under the assistance of vacuum negative pressure, and then the polyurethane foam filled with the aqueous polyurethane is taken out and cured for 24 hours at 50 ℃. Finally obtaining the polyurethane-based nano composite material with a multi-time interpenetrating network structure.
The basic structure of the polyurethane-based nanocomposite obtained in this example is similar to that of example 1, but the graphene layer is reduced graphene oxide, so that the material is a nanocomposite material with a reduced graphene network distribution structure.
Comparative example 1
1) Selecting industrial grade polyurethane foam with PPI value of 60-80, alternately ultrasonically washing twice with deionized water and ethanol, and drying for 5 hours at 50 ℃ for later use.
2) And (2) placing the dried polyurethane foam into an aqueous polyurethane solution with the solid content of 35% and the viscosity of 75cps, filling the aqueous polyurethane into foam pore channels under the assistance of vacuum negative pressure, taking out the polyurethane foam filled with the aqueous polyurethane, and curing for 24 hours at 50 ℃. Finally obtaining the nano composite material filled and solidified by the waterborne polyurethane.
In order to verify the performance of the nanocomposite obtained by the preparation method of the invention, the damping performance of the materials in each example was determined by using a dynamic mechanical property analyzer, wherein the nanocomposite prepared in examples 1, 2 and comparative example 1 was respectively denoted as D-5(PU + GO + PUD), D-5(PU + RGO + PUD) and D-5(PU + PUD). The test result is shown in fig. 4, and it is found that after the graphene oxide GO and the reduced graphene RGO are added, the damping performance of the material is greatly improved, and particularly, compared with the nanocomposite material obtained by adding the reduced graphene in example 2, the damping performance of the nanocomposite material is improved by 90%.
In addition, in the present invention, the specific parameters and materials of each step can be reasonably adjusted according to the needs. For example, the composite material matrix may be other materials, but it is desirable to have foamable or easily prepared open-cell foam characteristics so as to serve as a framework template for the network structure, such as polyurethane, melamine, etc. When the subsequent dip coating process is carried out under the ideal framework structure, foams with different porosities (PPI values) have different framework structure densities, so that the internal network structure of the subsequent material can be adjusted. In addition, the concentration of the carbon material ink can be adjusted, so that the network distribution continuity of the carbon material in the composite material can be adjusted, and meanwhile, other nano carbon materials, such as carbon nano tubes, can be added to the specific carbon material besides the graphene oxide. Other implementations of the present invention are illustrated by some of the following examples.
Example 3
1) Selecting industrial grade polyurethane foam with PPI value of 60-80, alternately ultrasonically washing twice with deionized water and ethanol, and drying for 5 hours at 50 ℃ for later use.
2) Preparing graphene oxide powder by using a chemical oxidation synthesis method, adding 0.2 g of graphene oxide powder into 100 ml of ethylene glycol, stirring for 12 hours, performing ultrasonic treatment for 2.5 hours alternately, adding acetic acid to enable the pH value of the solution to be 4, adding a silane coupling agent until the mass fraction of the silane coupling agent is 1.0wt%, and finally preparing the graphene oxide ethylene glycol ink with the mass fraction of 0.2 wt%.
3) And (2) carrying out oxygen plasma treatment on the polyurethane foam obtained in the step 1) for 4 minutes, immediately immersing the polyurethane foam into the ink prepared in the step 2), vacuumizing to assist the ink to be immersed into foam pore channels, and maintaining the pressure for 3 minutes to carry out degassing. And standing for 15 minutes in a normal-temperature and normal-pressure environment, taking out the foam, performing low-speed centrifugation (500 revolutions per minute) on a spin coater to recover the redundant ink immersed in the pore channel, uniformly mixing the graphene oxide ink loaded on the surface of the foam framework on a planetary mixer at a high speed, and centrifuging to remove the residual liquid (1200 revolutions per minute). Drying for 40 hours at 50 ℃ to obtain the polyurethane foam with a layer of graphene oxide distributed in island shape attached to the surface of the framework.
4) Carrying out oxygen plasma treatment on the composite foam obtained in the step 3) for 4 minutes, immediately immersing the composite foam into an aqueous polyurethane solution with the solid content of 35% and the viscosity of 75cps, and fully immersing the aqueous polyurethane into foam pore channels under the assistance of certain vacuum pumping. Standing for 15 minutes in a normal temperature and pressure environment, taking out the foam, and recovering excessive waterborne polyurethane through low-speed centrifugation in the step 3), and then uniformly mixing the waterborne polyurethane coated foam skeleton layer at a high speed. Drying and curing for 5 hours at 50 ℃ to obtain the polyurethane foam with a sandwich structure of the framework.
5) And (4) repeating the steps 3) and 4) to obtain the polyurethane foam with the multi-time coated lower skeleton in the multilayer sandwich structure. After 5 times of repeated coating, the obtained polyurethane foam is placed in aqueous polyurethane solution, the aqueous polyurethane is filled into foam pore channels under the assistance of vacuum negative pressure, and then the polyurethane foam filled with the aqueous polyurethane is taken out and cured for 24 hours at 50 ℃. Finally, the polyurethane-based nanocomposite with a multi-time interpenetrating network structure in the overall macroscopic view and discontinuous graphene distribution in the microscopic view is obtained.
Example 4
1) Selecting industrial grade polyurethane foam with PPI value of 60-80, alternately ultrasonically washing twice with deionized water and ethanol, and drying for 5 hours at 50 ℃ for later use.
2) Preparing graphene oxide powder by using a chemical oxidation synthesis method, adding 0.4 g of graphene oxide powder and 0.1 g of multi-walled carbon nano tube into 100 ml of ethylene glycol, stirring for 12 hours, performing ultrasonic treatment for 2.5 hours alternately, adding acetic acid to enable the pH value of the solution to be 4, adding a silane coupling agent to enable the mass fraction of the silane coupling agent to be 1.0wt%, and finally preparing the ethylene glycol ink with the mass fraction of 0.5 wt% and the mixed graphene oxide and carbon nano tube.
3) And (2) carrying out oxygen plasma treatment on the polyurethane foam obtained in the step 1) for 4 minutes, immediately immersing the polyurethane foam into the ink prepared in the step 2), vacuumizing to assist the ink to be immersed into foam pore channels, and maintaining the pressure for 3 minutes to carry out degassing. And standing for 15 minutes in a normal-temperature and normal-pressure environment, taking out the foam, performing low-speed centrifugation (500 revolutions per minute) on a self-modified spin coater to recover the redundant ink immersed in the pore channel, uniformly mixing the graphene oxide loaded on the surface of the foam framework and the ethylene glycol ink mixed with the carbon nano tubes on a planetary mixer at a high speed, and centrifuging to remove the residual liquid (1200 revolutions per minute). And drying the mixture for 40 hours at the temperature of 50 ℃ to obtain the polyurethane foam with the framework surface attached with a layer of the mixture of the graphene oxide and the carbon nano tube.
4) Carrying out oxygen plasma treatment on the composite foam obtained in the step 3) for 4 minutes, immediately immersing the composite foam into an aqueous polyurethane solution with the solid content of 35% and the viscosity of 75cps, and fully immersing the aqueous polyurethane into foam pore channels under the assistance of certain vacuum pumping. Standing for 15 minutes in a normal temperature and pressure environment, taking out the foam, and recovering excessive waterborne polyurethane through low-speed centrifugation in the step 3), and then uniformly mixing the waterborne polyurethane coated foam skeleton layer at a high speed. Drying and curing for 5 hours at 50 ℃ to obtain the polyurethane foam with a sandwich structure of the framework.
5) And (4) repeating the steps 3) and 4) to obtain the polyurethane foam with the multi-time coated lower skeleton in the multilayer sandwich structure. After 5 times of repeated coating, the obtained polyurethane foam is placed in aqueous polyurethane solution, the aqueous polyurethane is filled into foam pore channels under the assistance of vacuum negative pressure, and then the polyurethane foam filled with the aqueous polyurethane is taken out and cured for 24 hours at 50 ℃. Finally obtaining the polyurethane-based nano composite material with a multi-time interpenetrating network structure.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (10)
1. A preparation method of a multi-time interpenetrating network structure nano composite material is characterized by comprising the following steps:
s1: after carrying out oxygen plasma treatment on polyurethane foam with a network skeleton structure, immediately immersing the polyurethane foam into acid carbon material ink containing graphene oxide and a silane coupling agent, vacuumizing to assist the ink to be immersed into foam pore channels, and maintaining pressure to remove gas; after standing, taking out the foam, carrying out low-speed centrifugation to recover redundant ink immersed in the pore channel, then uniformly mixing carbon material ink loaded on the surface of the foam framework, simultaneously carrying out high-speed centrifugation to remove residual liquid, and drying to obtain polyurethane foam with a graphene oxide layer attached to the surface of the framework;
s2: performing oxygen plasma treatment on the polyurethane foam obtained in the step S1 again, immediately soaking the polyurethane foam into the aqueous polyurethane solution, and vacuumizing to assist the aqueous polyurethane to be soaked into foam pore channels; after standing, taking out the foam, carrying out low-speed centrifugation to recover excessive waterborne polyurethane immersed in the pore channel, then uniformly mixing the waterborne polyurethane loaded on the surface of the foam framework, simultaneously carrying out high-speed centrifugation to remove residual liquid, drying and curing to obtain polyurethane foam with a sandwich structure as the framework;
s3: repeatedly coating the polyurethane foam obtained by one-time coating in the S2 for multiple times continuously according to S1 and S2 to obtain the polyurethane foam with a multi-layer sandwich structure;
s4: and finally, directly filling and curing the polyurethane foam obtained from the S3 by using aqueous polyurethane to obtain the polyurethane-based nano composite material with a multi-time interpenetrating network structure.
2. The method for preparing the multiple interpenetrating network structure nanocomposite as claimed in claim 1, wherein in step S1, after the polyurethane foam with the graphene oxide layer attached to the surface of the skeleton is obtained, the polyurethane foam is further subjected to a reduction reaction in a hydroiodic acid reducing agent, so that the graphene oxide attached to the surface of the polyurethane foam skeleton is reduced to reduced graphene oxide.
3. The method for preparing the multiple interpenetrating network structure nanocomposite as claimed in claim 1 or 2, wherein in step S1, the polyurethane foam is a polyurethane foam having a PPI value of 60 to 80, and is ultrasonically washed twice with deionized water and ethanol alternately in advance, and dried at 50 ℃ for 5 hours for use.
4. The method for preparing a multiple interpenetrating network structure nanocomposite as claimed in claim 1 or 2, wherein in step S2, the aqueous polyurethane is an aqueous polyurethane solution having a solid content of 35% and a viscosity of 75 cps.
5. The method according to claim 1 or 2, wherein in step S1, the carbon material ink is a graphene oxide glycol ink solution, and the method comprises: adding graphene oxide powder into ethylene glycol, stirring for 12 hours, and performing ultrasonic treatment for 2.5 hours alternately; and then adding acetic acid to enable the pH value of the solution to be 4, then adding a silane coupling agent KH550, and ultrasonically mixing uniformly to obtain the graphene oxide glycol ink, wherein the mass fraction of the graphene oxide is 0.4wt%, and the mass fraction of the silane coupling agent is 1.0 wt%.
6. The method for preparing a multiple interpenetrating network structure nanocomposite as claimed in claim 1 or 2, wherein in step S1, the standing time is 15 minutes, and the standing is performed at normal temperature and pressure; the low-speed centrifugation is carried out on a spin coater at the rotating speed of 500 rpm, the high-speed centrifugation is carried out on a planetary mixer at the rotating speed of 1200 rpm, the drying temperature is 50 ℃, and the drying time is 40 hours.
7. The method for preparing a multiple interpenetrating network structure nanocomposite as claimed in claim 2, wherein in step S1, the reduction reaction is performed by: the polyurethane foam was placed in a reducing agent of hydroiodic acid at 80 ℃ for 1 minute.
8. The method for preparing a multiple interpenetrating network structure nanocomposite as claimed in claim 1 or 2, wherein in step S2, the standing time is 15 minutes, and the standing is performed at normal temperature and pressure; the low-speed centrifugation is carried out on a spin coater at the rotating speed of 500 rpm, the high-speed centrifugation is carried out on a planetary mixer at the rotating speed of 1200 rpm, the drying temperature is 50 ℃, and the drying and curing time is 5 hours.
9. The method for preparing the multiple interpenetrating network structure nanocomposite as claimed in claim 1 or 2, wherein in step S4, the polyurethane foam is directly filled and cured with the aqueous polyurethane by: and (3) putting the polyurethane foam obtained in the step (S3) into an aqueous polyurethane solution, filling the aqueous polyurethane into foam pores under the assistance of vacuumizing, taking out the polyurethane foam filled with the aqueous polyurethane, and curing for 24 hours at 50 ℃.
10. A multiple interpenetrating network structure nanocomposite prepared according to the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910972728.3A CN110591145B (en) | 2019-10-14 | 2019-10-14 | Multi-time interpenetrating network structure nano composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910972728.3A CN110591145B (en) | 2019-10-14 | 2019-10-14 | Multi-time interpenetrating network structure nano composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110591145A CN110591145A (en) | 2019-12-20 |
| CN110591145B true CN110591145B (en) | 2020-08-25 |
Family
ID=68867071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910972728.3A Active CN110591145B (en) | 2019-10-14 | 2019-10-14 | Multi-time interpenetrating network structure nano composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110591145B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852159B (en) * | 2021-01-11 | 2022-09-09 | 常州富烯科技股份有限公司 | Graphene composite foam film and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022106B (en) * | 2017-03-23 | 2021-01-19 | 华南理工大学 | Multi-dimensional nanoparticle modified super-hydrophobic oil-absorbing foam material and preparation method thereof |
-
2019
- 2019-10-14 CN CN201910972728.3A patent/CN110591145B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110591145A (en) | 2019-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | One-pot synthesis of robust superhydrophobic, functionalized graphene/polyurethane sponge for effective continuous oil–water separation | |
| CN106520040B (en) | A kind of modified graphene oxide, MGO-SiO2Nano-hybrid material and MGO-SiO2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film | |
| CN106902778A (en) | A kind of chitosan/oxidized Graphene/polyvinyl alcohol cellular composite adsorbing material and preparation method thereof | |
| CN105502342A (en) | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source | |
| CN103030974A (en) | Light flexible graphene/polymer foam electromagnetic shielding material, preparation method and application thereof | |
| CN110591145B (en) | Multi-time interpenetrating network structure nano composite material and preparation method thereof | |
| CN103599705B (en) | The method of organic/inorganic hybrid membrane is prepared in a kind of ultrasonic immersing | |
| CN105252015B (en) | Yolk-eggshell structure Au@ hollow carbon nanosphere composite material and preparation and application thereof | |
| CN105131607A (en) | Point, line, surface three-dimensional carbon material composite heat-conduction silica gel and preparation method thereof | |
| CN103223309A (en) | Carbon nanotube filling composite membrane with alcohol penetration priority and preparation method thereof | |
| CN107746052A (en) | A kind of preparation method of the graphene aerogel of N doping | |
| CN106543478A (en) | A kind of preparation and flame retardance of polymer application of graphene-supported fullerene hybrid | |
| CN111073033A (en) | Super-hydrophobic, conductive and swelling-resistant fluorine-containing silicone rubber foam composite material and preparation method thereof | |
| CN105116030B (en) | A kind of Cu2Nuclear-shell structured nano-composite materials of O@CuO half and preparation method thereof | |
| WO2021135378A1 (en) | Graphene-based polyurethane porous nanometer material and preparation method therefor | |
| CN105273216A (en) | Three-dimensional wrinkle polylactic acid microballoons and preparation method and uses thereof | |
| CN107353026A (en) | A kind of composite material of silicon carbide and preparation method | |
| CN108439373B (en) | Amphiphilic Janus structure graphene-based aerogel and preparation method thereof | |
| CN107674236B (en) | Super-amphiphilic polyurethane foam material and preparation method thereof | |
| CN110452480B (en) | Preparation method of ultra-light heat-insulating flexible aerogel | |
| CN114316380B (en) | Honeycomb light high-toughness elastomer resin-based material and preparation method thereof | |
| Ji et al. | Porous hollow carbon nanotube composite cages | |
| CN106752098A (en) | A kind of nano-calcium carbonate powder of ferrocene polyethyleneimine cross-linked polymer coating modification and preparation method thereof | |
| CN108328620B (en) | Preparation method of hydrophobic foaming cement composite silicon aerogel material | |
| CN113394029B (en) | MXene electrode preparation method based on 3D printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |