Composite resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of aerogel flame-retardant materials, in particular to composite resin as well as a preparation method and application thereof. The composite resin comprises resin and aerogel containing a carbon nano tube, and the aerogel containing the carbon nano tube comprises the carbon nano tube and nano cellulose. The method for preparing the composite resin comprises the following steps: (1) treating dispersion liquid containing carbon nanotubes and nanocellulose to obtain hydrogel containing the carbon nanotubes; (2) carrying out freeze drying on the hydrogel containing the carbon nanotubes prepared in the step (1) to obtain aerogel containing the carbon nanotubes; and (3) mixing the aerogel containing the carbon nanotubes prepared in the step (2) with resin. When the composite resin is applied to some harsh high-temperature and high-pressure environments such as aviation and spaceflight, the composite resin has relatively good flame retardance and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of aerogel flame retardant materials, and particularly to a composite resin, a preparation method thereof, and an application thereof. Background Art

[0002] Polyetheretherketone (PEEK) is a semi-crystalline high-performance thermoplastic polymer resin with excellent mechanical properties, high-temperature resistance properties, and solvent resistance properties. It is a thermoplastic polymer with relatively good thermal stability and has been widely used in the fields of aviation, aerospace, machinery, medical treatment, etc. Pure polyetheretherketone has been difficult to meet the usage requirements in some harsh high-temperature and high-pressure environments.

[0003] In order to improve the flame retardant performance of polyetheretherketone and make it have a wider application range at high temperatures, it is very necessary to carry out flame retardant modification on it. However, among many methods, the method of directly carrying out structural modification on polyetheretherketone to improve the flame retardant performance has a complex process and uses more chemicals; directly adding an inorganic flame retardant will reduce the mechanical properties of polyetheretherketone. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems that existing pure resin materials have poor mechanical properties and flame retardant properties in high-temperature and high-pressure environments, and to provide a composite resin, a preparation method thereof, and an application thereof. When the composite resin is applied to a high-temperature and high-pressure environment, it not only has high flame retardant performance but also can maintain good mechanical properties.

[0005] In order to achieve the above purpose, in the first aspect of the present invention, a composite resin is provided. The composite resin includes a resin and an aerogel containing carbon nanotubes, wherein the aerogel containing carbon nanotubes includes carbon nanotubes and nanocellulose.

[0006] Preferably, the resin is polyetheretherketone.

[0007] In the second aspect of the present invention, a method for preparing a composite resin is provided, wherein the method includes:

[0008] (1) Treating a dispersion liquid of carbon nanotubes and nanocellulose to obtain a hydrogel containing carbon nanotubes;

[0009] (2) Freeze-drying the hydrogel containing carbon nanotubes prepared in step (1) to obtain an aerogel containing carbon nanotubes;

[0010] (3) Mixing the aerogel containing carbon nanotubes prepared in step (2) with a resin to obtain the composite resin.

[0011] In the third aspect of the present invention, an application of the composite resin described in the first aspect or the composite resin prepared by the preparation method described in the second aspect in a flame retardant material is provided.

[0012] Through the above technical solution, the present invention composes a carbon nanotube-containing aerogel as a filler with a resin. The carbon nanotubes have high strength, elasticity, and fatigue resistance, enabling the carbon nanotubes to act as a reinforcing material in the composite resin material to improve the strength of the composite resin. The carbon nanotube-containing aerogel has characteristics such as low thermal conductivity, high porosity, high specific surface area, and corrosion resistance, and can significantly improve the flame retardancy of the composite resin. Performance parameter tests were conducted on the composite resin material prepared by the present invention. As can be seen from the test results (see Table 1), compared with the comparative example, the peak value of the heat release rate of the composite resin material doped with carbon nanotube aerogel in the present invention is lower. At the same time, the flexural strength of the composite material also increases accordingly. Thus, it can be seen that adding the carbon nanotube-containing aerogel to the resin matrix can not only improve the flame retardancy of the composite resin material but also improve the mechanical properties of the composite material. In addition, the preparation method of the composite resin of the present invention has low cost and a convenient process. Detailed Embodiments

[0013] In the ranges disclosed herein, the endpoints and any value are not limited to the exact range or value. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0014] The following provides a detailed description of the specific embodiments of the present invention. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not used to limit the present invention.

[0015] In the first aspect of the present invention, a composite resin is provided. The composite resin includes a resin and a carbon nanotube-containing aerogel, wherein the carbon nanotube-containing aerogel includes carbon nanotubes and nanocellulose.

[0016] The present invention composes a carbon nanotube-containing aerogel as a filler with a resin. While maintaining the strength of the composite resin material, it can significantly improve the flame retardancy of the composite resin material. Cellulose can be directly prepared into an aerogel. Due to its excellent heat insulation performance, it has a certain flame retardant effect. However, after being added as a filler to the resin matrix, it will reduce the mechanical properties of the resin matrix. After preparing a composite aerogel from carbon nanotubes and cellulose, this problem is improved, and the flame retardancy of the matrix resin can be improved without affecting the mechanical properties.

[0017] In the present invention, the carbon nanotubes are preferably multi-walled carbon nanotubes.

[0018] In the present invention, preferably, the resin is selected from at least one of polyether ether ketone, nylon, polyethylene, and polypropylene, and more preferably polyether ether ketone.

[0019] Further preferably, the weight-average molecular weight of the polyether ether ketone is 30,000-50,000 g / mol.

[0020] According to the present invention, in order to improve the mechanical properties and flame retardancy of the composite resin, when controlling the content of the carbon nanotube-containing aerogel in the composite resin, it is necessary not only to ensure that the carbon nanotube-containing aerogel has good dispersion in the resin, but also to prevent the aggregation between the aerogels caused by the excessive content of the carbon nanotube-containing aerogel, thereby leading to the decline of the mechanical properties and flame retardancy of the composite resin material. Preferably, in the composite resin of the present invention, the mass ratio of the carbon nanotube-containing aerogel to the resin is 0.01-0.1:1. Further preferably, the mass ratio of the carbon nanotube-containing aerogel to the resin is 0.05-0.1:1.

[0021] According to the present invention, preferably, the mass ratio of the carbon nanotubes to the nanofibrillated cellulose is 0.5-2.5:1.

[0022] Preferably, the molecular weight of the nanofibrillated cellulose has a diameter of 3-5 nm and a length of 15-40 μm.

[0023] According to the present invention, in order to improve the dispersion of the carbon nanotube-containing aerogel in the composite resin, thereby better improving the mechanical properties and flame retardancy of the composite resin, preferably, the particle size of the carbon nanotube-containing aerogel is 1000-2000 mesh.

[0024] In the present invention, the particle size of the carbon nanotube-containing aerogel is obtained by sieve test.

[0025] In the present invention, preferably, the flexural strength of the composite resin is 150-300 MPa, and the peak heat release rate is 400-600 KW / m 2 .

[0026] In the present invention, the flexural strength of the composite resin is tested on a composite resin material using a microcomputer-controlled electronic universal testing machine in accordance with GB 3356-82; the peak heat release rate of the composite resin is obtained by testing the composite resin material under the condition of a heat flux radiation intensity of 50 kW / m 2 according to the ISO5660-1 cone calorimetry standard.

[0027] In the present invention, a flame retardant material of an aerogel containing carbon nanotubes and nanofibrillated cellulose is mixed into PEEK as a filler to prepare a composite material. Compared with other additive flame retardants, it avoids the problem of the influence of the poor interfacial performance of the flame retardant on the mechanical properties, and improves the flame retardancy while ensuring the mechanical properties.

[0028] The composition of the composite resin of the present invention is obtained by calculating the feeding amount.

[0029] The present invention does not particularly limit the preparation method of the composite resin, as long as the composite resin with the above composition can be obtained. According to a preferred embodiment of the present invention, a second aspect of the present invention provides a method for preparing a composite resin, wherein the method comprises the following steps:

[0030] (1) Treat the dispersion liquid containing carbon nanotubes and nanocellulose to obtain a hydrogel containing carbon nanotubes;

[0031] (2) Freeze-dry the hydrogel containing carbon nanotubes prepared in step (1) to obtain an aerogel containing carbon nanotubes;

[0032] (3) Mix the aerogel containing carbon nanotubes prepared in step (2) with a resin to obtain the composite resin.

[0033] In the preparation method of the present invention, all raw materials used can be commercially available products or prepared by any existing method.

[0034] According to the preparation method of the present invention, in order to improve the dispersion degree of the obtained aerogel containing carbon nanotubes in the composite resin, so as to better improve the mechanical properties and flame retardancy of the composite resin, preferably, in step (1), the treatment method includes: placing the dispersion liquid containing carbon nanotubes and nanocellulose in a hydrochloric acid atmosphere for 4-8 h at 20-30 °C to form a hydrogel containing carbon nanotubes. Specifically, the dispersion liquid containing carbon nanotubes and nanocellulose can be put into a mold and then placed in a hydrochloric acid atmosphere. Preferably, the method provided by the present invention further includes washing the formed hydrogel with deionized water. There is no particular limitation on the washing conditions and methods, for example, washing until its pH value is neutral.

[0035] In the present invention, the solvent in the dispersion liquid containing carbon nanotubes and nanocellulose is ethanol, methanol, deionized water, preferably deionized water.

[0036] Preferably, the dispersion liquid containing carbon nanotubes and nanocellulose is prepared by the following steps:

[0037] (a) Mix carbon nanotubes with deionized water, stir magnetically, and then ultrasonically disperse in an ice-water bath to obtain an aqueous dispersion of carbon nanotubes;

[0038] (b) Add nanocellulose to the aqueous dispersion obtained in step (a), stir magnetically, and then ultrasonically disperse in an ice-water bath to obtain the dispersion liquid containing carbon nanotubes and nanocellulose.

[0039] Preferably, in step (a), the ratio of the carbon nanotubes to deionized water is 0.1 - 0.5:100, the magnetic stirring time is 5 - 15 min, and the ultrasonic time is 5 - 15 min.

[0040] Preferably, in step (b), the ratio of the nanocellulose to the water in the aqueous dispersion obtained in step (a) is 0.1 - 0.3:100, the magnetic stirring time is 5 - 15 min, and the ultrasonic time is 5 - 15 min.

[0041] According to the preparation method of the present invention, in order to improve the dispersibility of carbon nanotubes in the composite resin material and improve the compatibility between the carbon nanotubes and the resin, preferably, in step (1), the mass ratio of the carbon nanotubes to the nanocellulose in the dispersion containing carbon nanotubes and nanocellulose is 0.5 - 2.5:1.

[0042] According to the method provided by the present invention, the types, sources, and the selection range of the molecular weights of the carbon nanotubes, nanocellulose, and resin can be the same as those described in the first aspect of the present invention, and will not be elaborated herein.

[0043] According to the preparation method of the present invention, in order to maintain the structural characteristics of the hydrogel and give full play to the advantages of the obtained aerogel as a flame retardant in the composite resin material: low thermal conductivity, high porosity, high specific surface area, corrosion resistance, etc., the above-prepared hydrogel is freeze-dried to obtain the corresponding aerogel. Preferably, the conditions of the freeze-drying include: the temperature is -70 to -40 °C, the vacuum degree is 0 to -0.1 MPa, and the time is 24 - 48 h.

[0044] According to the preparation method of the present invention, in order to improve the dispersion degree of the obtained carbon nanotube-containing aerogel in the composite resin, and thus better improve the mechanical properties and flame retardant properties of the composite resin, preferably, in step (2), after the freeze-drying, cryogenic milling is further included.

[0045] Further preferably, the temperature of the cryogenic milling is -70 to -40 °C.

[0046] Further preferably, after the above cryogenic milling, the particle size of the obtained carbon nanotube-containing aerogel is 1000 - 2000 mesh.

[0047] The method provided by the present invention has no particular limitation on the manner of mixing the aerogel containing carbon nanotubes prepared in step (2) with the resin in step (3), as long as the two can be effectively compounded. Preferably, the aerogel containing carbon nanotubes is introduced in the form of a dispersion of the aerogel containing carbon nanotubes. The present invention has no particular limitation on the solvent in the dispersion of the aerogel containing carbon nanotubes, and for example, it can be ethanol. In the present invention, preferably, the dispersion of the aerogel containing carbon nanotubes is obtained by adding the aerogel containing carbon nanotubes into the solvent and then performing ultrasonic dispersion.

[0048] According to the preparation method of the present invention, in order to mix evenly, preferably, in step (3), the manner of mixing includes: adding the dispersion of the aerogel containing carbon nanotubes into the resin suspension.

[0049] According to the preparation method of the present invention, preferably, it further includes drying at 60 - 80 °C to remove the solvent in the dispersion.

[0050] The present invention has no particular limitation on the manner of adding the dispersion of the aerogel containing carbon nanotubes into the resin suspension. Preferably, the dispersion of the aerogel containing carbon nanotubes is added dropwise into the resin suspension. Further preferably, relative to 100 mL of the dispersion of the aerogel containing carbon nanotubes, the addition rate of the dispersion of the aerogel containing carbon nanotubes is 1 - 2 mL / min.

[0051] In the present invention, the resin suspension can be obtained by mixing the resin and a dispersant and then stirring. There is no particular limitation on the solvent, and preferably, it is ethanol.

[0052] According to the preparation method of the present invention, in order to improve the mechanical properties and flame retardancy of the prepared composite resin, when controlling the content of the aerogel containing carbon nanotubes in the composite resin, it is necessary not only to ensure that the aerogel containing carbon nanotubes has a good dispersion degree in the resin, but also to prevent the aggregation between the aerogels caused by too high a content of the aerogel containing carbon nanotubes, thereby resulting in a decrease in the mechanical properties and flame retardancy of the composite resin material. Preferably, in step (3), the mass ratio of the aerogel containing carbon nanotubes to the resin is 0.01 - 0.1:1, and further preferably 0.05 - 0.1:1.

[0053] In the present invention, according to the actual application needs, preferably, in step (3), after the mixing, it further includes molding.

[0054] Further preferably, the conditions of the molding include: the temperature is 380 - 420 °C, the pressure is 8 - 12 MPa, and the time is 5 - 15 min.

[0055] Preferably, after the compression molding, the mold is cooled at room temperature, demolded, and the composite material is obtained.

[0056] In the present invention, the room temperature condition refers to a temperature in the range of 25 - 35 °C.

[0057] The third aspect of the present invention provides an application of the composite resin according to the first aspect or the composite resin prepared by the preparation method according to the second aspect in flame retardant materials.

[0058] Preferably, the composite resin material can be applied in reinforced modified plastics, the construction field, the electrothermal field, or the heat insulation and thermal insulation material field.

[0059] The present invention will be described in detail below through examples. In the present invention, room temperature refers to 25 - 35 °C.

[0060] Multi-walled carbon nanotubes, with an outer diameter of 4 - 6 nm and a length of 10 - 30 μm, were purchased from Adamas Company.

[0061] Nanocellulose, with a diameter of 3 - 5 nm and a length of 15 - 40 μm, was purchased from Adamas Company, and the product number is 89135DA.

[0062] Polyetheretherketone (PEEK), with a weight average molecular weight of 40000 g / mol, was purchased from a company with the product number 770P.

[0063] Example 1

[0064] (1) 0.1 g of multi-walled carbon nanotubes was mixed with 100 g of deionized water, magnetically stirred for 10 min, then ultrasonically dispersed in an ice-water bath for 10 min. Then 0.2 g of nanocellulose was added, magnetically stirred for 10 min, and then ultrasonically dispersed in an ice-water bath for 10 min to obtain an aqueous dispersion containing multi-walled carbon nanotubes. The aqueous dispersion containing multi-walled carbon nanotubes was placed in a mold and placed in a hydrochloric acid atmosphere at 25 °C for 6 h to obtain a hydrogel containing multi-walled carbon nanotubes;

[0065] (2) Under the conditions of a cold trap temperature of -50 °C and a vacuum degree of -0.1 MPa, the hydrogel containing multi-walled carbon nanotubes prepared in step (1) was dried by freeze-drying for 24 h to obtain an aerogel containing multi-walled carbon nanotubes. At -50 °C, the aerogel containing multi-walled carbon nanotubes was cryo-milled to obtain an aerogel powder containing multi-walled carbon nanotubes with a particle size of 1000 mesh;

[0066] (3) Mix 0.2 g of the aerogel powder containing multi-walled carbon nanotubes obtained in step (2) with 100 mL of absolute ethanol, and ultrasonically disperse for 30 min to obtain a dispersion of the aerogel containing multi-walled carbon nanotubes. Drop the dispersion of the aerogel containing multi-walled carbon nanotubes into a PEEK suspension containing 10 g, stir, and then dry at 80 °C to remove the solvent in the solution; Use the high-temperature molding method to prepare a composite material of the aerogel containing carbon nanotubes and polyether ether ketone. Among them, during the high-temperature molding process, the melting temperature is 400 °C, the pressure is 10 MPa, and the pressure holding time is 10 min. Then cool at room temperature and demold to obtain composite resin material 1.

[0067] Test the flame retardancy and mechanical properties of composite resin material 1, and the test results are shown in Table 1.

[0068] Example 2

[0069] (1) Mix 0.2 g of multi-walled carbon nanotubes with 100 g of deionized water, magnetically stir for 10 min, then ultrasonically disperse in an ice-water bath for 10 min, add 0.2 g of nanocellulose, magnetically stir for 10 min, and then ultrasonically disperse in an ice-water bath for 10 min to obtain an aqueous dispersion of multi-walled carbon nanotubes; Put the aqueous dispersion of multi-walled carbon nanotubes into a mold and place it in a hydrochloric acid atmosphere at 25 °C for 6 h to obtain a hydrogel containing multi-walled carbon nanotubes;

[0070] (2) Under the conditions of a cold trap temperature of -50 °C and a vacuum degree of -0.1 MPa, use the freeze-drying method to dry the hydrogel containing multi-walled carbon nanotubes prepared in step (1) for 24 h to obtain an aerogel containing multi-walled carbon nanotubes; At -50 °C, freeze-grind the aerogel containing multi-walled carbon nanotubes to obtain an aerogel powder containing multi-walled carbon nanotubes with a particle size of 1000 mesh;

[0071] (3) Mix 0.4 g of the aerogel powder containing multi-walled carbon nanotubes obtained in step (2) with 100 mL of absolute ethanol, and ultrasonically disperse for 30 min to obtain a dispersion of the aerogel containing multi-walled carbon nanotubes. Drop the dispersion of the aerogel containing multi-walled carbon nanotubes into a PEEK suspension containing 10 g, stir, and then dry at 80 °C to remove the solvent in the solution; Use the high-temperature molding method to prepare a composite material of the aerogel containing carbon nanotubes and polyether ether ketone. Among them, during the high-temperature molding process, the melting temperature is 400 °C, the pressure is 10 MPa, and the pressure holding time is 10 min. Then cool at room temperature and demold to obtain composite resin material 2.

[0072] Test the flame retardancy and mechanical properties of composite resin material 2, and the test results are shown in Table 1.

[0073] Example 3

[0074] (1) Mix 0.6 g of multi-walled carbon nanotubes with 200 g of deionized water, stir magnetically for 10 min, then ultrasonically disperse in an ice-water bath for 10 min. Then add 0.4 g of nanocellulose, stir magnetically for 10 min, and ultrasonically disperse in an ice-water bath for 10 min to obtain an aqueous dispersion containing multi-walled carbon nanotubes. Place the aqueous dispersion containing multi-walled carbon nanotubes in a mold, and place it in a hydrochloric acid atmosphere at 25 °C for 6 h to obtain a hydrogel containing multi-walled carbon nanotubes;

[0075] (2) Under the conditions of a cold trap temperature of -50 °C and a vacuum degree of -0.1 MPa, use the freeze-drying method to dry the hydrogel containing multi-walled carbon nanotubes prepared in step (1) for 24 h to obtain an aerogel containing multi-walled carbon nanotubes. At -50 °C, perform cryogenic grinding on the aerogel containing multi-walled carbon nanotubes to obtain an aerogel powder containing multi-walled carbon nanotubes with a particle size of 1000 mesh;

[0076] (3) Mix 0.6 g of the aerogel powder containing multi-walled carbon nanotubes obtained in step (2) with 100 mL of absolute ethanol, ultrasonically disperse for 30 min to obtain a dispersion of the aerogel containing multi-walled carbon nanotubes. Drop the dispersion of the aerogel containing multi-walled carbon nanotubes into a suspension containing 10 g of PEEK, stir, and then dry at 80 °C to remove the solvent in the solution. Use the high-temperature compression molding method to prepare a composite material containing the aerogel containing carbon nanotubes and polyether ether ketone. Among them, during the high-temperature compression molding process, the melting temperature is 400 °C, the pressure is 10 MPa, and the pressure holding time is 10 min. Then cool at room temperature and demold to obtain composite resin material 3.

[0077] Perform flame retardancy and mechanical property tests on composite resin material 3, and the test results are shown in Table 1.

[0078] Example 4

[0079] (1) Mix 0.8 g of multi-walled carbon nanotubes with 200 g of deionized water, stir magnetically for 10 min, then ultrasonically disperse in an ice-water bath for 10 min. Then add 0.4 g of nanocellulose, stir magnetically for 10 min, and ultrasonically disperse in an ice-water bath for 10 min to obtain an aqueous dispersion containing multi-walled carbon nanotubes. Place the aqueous dispersion containing multi-walled carbon nanotubes in a mold, and place it in a hydrochloric acid atmosphere at 25 °C for 6 h to obtain a hydrogel containing multi-walled carbon nanotubes;

[0080] (2) Under the conditions that the cold trap temperature is -50 °C and the vacuum degree is -0.1 MPa, the hydrogel containing multi-walled carbon nanotubes prepared in step (1) is dried by freeze-drying for 24 h to obtain an aerogel containing multi-walled carbon nanotubes; under the condition of -50 °C, the aerogel containing multi-walled carbon nanotubes is cryo-milled to obtain an aerogel powder containing multi-walled carbon nanotubes with a particle size of 1000 mesh;

[0081] (3) 0.8 g of the aerogel powder containing multi-walled carbon nanotubes obtained in step (2) is mixed with 100 mL of absolute ethanol and ultrasonically dispersed for 30 min to obtain a dispersion of the aerogel containing multi-walled carbon nanotubes. The dispersion of the aerogel containing multi-walled carbon nanotubes is dropped into a PEEK suspension containing 10 g, stirred, and then dried at 80 °C to remove the solvent in the solution; a composite material containing the aerogel containing carbon nanotubes and polyether ether ketone is prepared by the method of high-temperature molding. Among them, during the high-temperature molding process, the melting temperature is 400 °C, the pressure is 10 MPa, and the pressure holding time is 10 min. Then it is cooled at room temperature and demolded to obtain the composite resin material 4.

[0082] The flame retardancy and mechanical properties of the composite resin material 4 are tested, and the test results are shown in Table 1.

[0083] Example 5

[0084] (1) 1.0 g of multi-walled carbon nanotubes is mixed with 200 g of deionized water, magnetically stirred for 10 min, then ultrasonically dispersed in an ice-water bath for 10 min, 0.4 g of nanocellulose is added, magnetically stirred for 10 min, and then ultrasonically dispersed in an ice-water bath for 10 min to obtain an aqueous dispersion containing multi-walled carbon nanotubes; the aqueous dispersion containing multi-walled carbon nanotubes is put into a mold and placed in a hydrochloric acid atmosphere at 25 °C for 6 h to obtain a hydrogel containing multi-walled carbon nanotubes;

[0085] (2) Under the conditions that the cold trap temperature is -50 °C and the vacuum degree is -0.1 MPa, the hydrogel containing multi-walled carbon nanotubes prepared in step (1) is dried by freeze-drying for 24 h to obtain an aerogel containing multi-walled carbon nanotubes; under the condition of -50 °C, the aerogel containing multi-walled carbon nanotubes is cryo-milled to obtain an aerogel powder containing multi-walled carbon nanotubes with a particle size of 1000 mesh;

[0086] (3) Mix 1.0 g of the aerogel powder containing multi-walled carbon nanotubes obtained in step (2) with 100 mL of absolute ethanol, and ultrasonically disperse for 30 min to obtain a dispersion of the aerogel containing multi-walled carbon nanotubes. Drop the dispersion of the aerogel containing multi-walled carbon nanotubes into a PEEK suspension containing 10 g, stir, and then dry at 80 °C to remove the solvent in the solution; use the method of high-temperature molding to prepare a composite material of the aerogel containing carbon nanotubes and polyether ether ketone. Among them, during the high-temperature molding process, the melting temperature is 400 °C, the pressure is 10 MPa, and the pressure holding time is 10 min. Then cool at room temperature and demold to obtain the composite resin material 5.

[0087] Test the flame retardancy and mechanical properties of the composite resin material 5, and the test results are shown in Table 1.

[0088] Comparative Example 1

[0089] According to the preparation step (3) of Example 1, the difference is that the aerogel containing multi-walled carbon nanotubes is not added during the high-temperature molding process to obtain the resin material 6.

[0090] Comparative Example 2

[0091] According to the preparation step (1) of Example 1, the difference is that multi-walled carbon nanotubes are not added during the preparation of the aerogel to obtain the resin material 7.

[0092] Test the flame retardancy and mechanical properties of the composite resin material 6, and the test results are shown in Table 1:

[0093] Table 1

[0094] Index <![CDATA[Peak heat release rate (KW / m 2 )]]> Flexural strength (MPa) Example 1 478.5 192.6 Example 2 432.6 230.8 Example 3 400.2 265.4 Example 4 412.3 243.2 Example 5 426.5 240.5 Comparative Example 1 560 150.8 Comparative Example 2 554 142.6

[0095] As can be seen from Table 1, compared with the comparative examples, in the composite resin material prepared in the example, the added aerogel containing multi-walled carbon nanotubes improves the bending performance and the peak value of the heat release rate of the resin material, indicating that the aerogel containing multi-walled carbon nanotubes can improve the mechanical properties and flame retardancy of the resin matrix. When the resin matrix burns, on the one hand, the aerogel containing multi-walled carbon nanotubes has excellent heat insulation performance as an aerogel, which can prevent the further transfer of heat. On the other hand, during the combustion process, an organic carbon layer is formed on the surface of the composite resin material. The aerogel containing multi-walled carbon nanotubes, as a nano-filler, can enhance the organic carbon layer as a heat and mass transfer barrier to block the propagation of heat.

[0096] As can be seen from the data of Examples 1-5, with the further increase in the addition amount of the aerogel containing multi-walled carbon nanotubes, the aerogel begins to agglomerate, resulting in a decrease in the mechanical properties and flame retardancy of the composite resin material.

[0097] As can be seen from the above examples and comparative examples, by adding the aerogel containing carbon nanotubes to the resin matrix, not only the flame retardancy of the composite resin material can be improved, but also the mechanical properties of the composite material can be improved.

[0098] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A composite resin, characterized in that, The composite resin includes a resin and an aerogel containing carbon nanotubes, wherein the aerogel containing carbon nanotubes includes carbon nanotubes and nanocellulose.

2. The composite resin according to claim 1, wherein The resin is selected from at least one of polyetheretherketone, nylon, polyethylene, and polypropylene, and is preferably polyetheretherketone; Preferably, the weight-average molecular weight of the polyetheretherketone is 30,000 - 50,000 g / mol.

3. The composite resin according to claim 1 or 2, wherein, The mass ratio of the aerogel containing carbon nanotubes to the resin is 0.01 - 0.1:1; Preferably, the mass ratio of the carbon nanotubes to the nanocellulose is 0.5 - 2.5:1; Preferably, the diameter of the nanocellulose is 3 - 5 nm, and the length is 15 - 40 nm.

4. The composite resin according to any one of claims 1 to 3, wherein, The particle size of the aerogel containing carbon nanotubes is 1000 - 2000 mesh.

5. The composite resin according to any one of claims 1-4, wherein, The flexural strength of the composite resin is 150 - 300 MPa, and the peak heat release rate is 400 - 600 KW / m 2 .

6. A method for preparing a composite resin, characterized in that, The method includes the following steps: (1) Treat the dispersion liquid of carbon nanotubes and nanocellulose to obtain a hydrogel containing carbon nanotubes; (2) Freeze-dry the hydrogel containing carbon nanotubes prepared in step (1) to obtain an aerogel containing carbon nanotubes; (3) Mix the aerogel containing carbon nanotubes prepared in step (2) with the resin to obtain the composite resin.

7. The method according to claim 6, wherein, In step (1), the treatment method includes: placing the dispersion liquid of carbon nanotubes and nanocellulose in a hydrochloric acid atmosphere at 20 - 30 °C for 4 - 8 h to form a hydrogel containing carbon nanotubes, and preferably further includes washing the hydrogel containing carbon nanotubes.

8. The method according to claim 6 or 7, wherein In step (1), the mass ratio of carbon nanotubes to nanocellulose in the dispersion liquid of carbon nanotubes and nanocellulose is 0.5 - 2.5:1; Preferably, the diameter of the nanocellulose is 3 - 5 nm, and the length is 15 - 40 μm.

9. The method according to any one of claims 6-8, wherein, In step (2), the conditions for freeze-drying include: the temperature is -70 to -40 °C, the vacuum degree is 0 to -0.1 MPa, and the time is 24 - 48 h; Preferably, in step (2), freeze-grinding is further included after freeze-drying; Preferably, the particle size of the aerogel containing carbon nanotubes is 1000 - 2000 mesh.

10. The method according to any one of claims 6-9, wherein, In step (3), the mixing method includes: adding the dispersion liquid of the aerogel containing carbon nanotubes to the resin suspension; Preferably, relative to 100 mL of the dispersion liquid of the aerogel containing carbon nanotubes, the addition speed of the dispersion liquid of the aerogel containing carbon nanotubes is 1 - 2 mL / min.

11. The method according to any one of claims 6-10, wherein, In step (3), the mass ratio of the aerogel containing carbon nanotubes to the resin is 0.01 - 0.1:1; Preferably, the resin is selected from at least one of polyetheretherketone, nylon, polyethylene, and polypropylene, and is preferably polyetheretherketone; Further preferably, the weight-average molecular weight of the polyetheretherketone is 30,000 - 50,000 g / mol.

12. The composite resin according to any one of claims 6-11, wherein, In step (3), molding is further included after mixing; Preferably, the conditions for molding include: the temperature is 380 - 420 °C, the pressure is 8 - 12 MPa, and the time is 5 - 15 min.

13. Application of the composite resin according to any one of claims 1 - 5 or the composite resin prepared by the method according to any one of claims 6 - 12 in a flame retardant material.