Explosion-proof resin composite material and preparation method thereof

Abstract

The invention discloses an explosion-proof resin composite material and a preparation method thereof, belonging to the technical field of compositions of polymer compounds. The composite material comprises the following components, measured by mass: 80-100 parts of epoxy resin, 10-15 parts of wave-absorbing modified glass fiber, 5-8 parts of flame retardant, 0.3-0.4 parts of zinc stearate, and 0.2-0.3 parts of antioxidant; the raw materials are added into a mixer, stirred and mixed, and then added into a mold, and hot-pressed to obtain the explosion-proof resin composite material; the explosion-proof resin composite material prepared by the invention is prepared by compounding a porous nickel-based carbon material and graphene nanosheets to obtain composite MOF graphene powder, and fixing the dispersed composite MOF graphene powder on the surface of high-silica glass fiber through high-temperature carbonization to obtain wave-absorbing modified glass fiber with wave-absorbing ability, thereby making the explosion-proof resin composite material have wave-absorbing performance, and the doping of the graphene nanosheets also improves the mechanical properties of the explosion-proof resin material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer compound compositions, and particularly relates to a blast-resistant resin composite material and a preparation method thereof. BACKGROUND

[0002] Resin materials are widely used in building materials in various industries. In the application of building materials in chemical, petroleum and other industries, the building materials need to have certain blast-resistant performance. The blast-resistant modified resin has excellent heat resistance, durability, barrier performance and good mechanical strength, and is widely used in blast-resistant buildings, storage facilities, chemical equipment and other fields. The high molecular structure of the blast-resistant modified resin can effectively isolate the fire source, prevent gas leakage and explosion. The existing technology usually uses glass fiber modified resin with high strength to obtain blast-resistant resin material with excellent blast-resistant performance.

[0003] The Chinese patent application with the publication number CN118290958A discloses a glass fiber modified blast-resistant wear-resistant corrosion-resistant composite resin well lid and a preparation method thereof. Polyethyleneimine is added as a flexible protective layer and reacts with dopamine. The glass fiber is dispersed in the resin due to the good compatibility of polyethyleneimine with the resin. The prepared composite resin well lid has high compression and bending strength, high flame resistance and other advantages, and good blast-resistant performance.

[0004] However, with the development of intelligent factories, more and more factories use electric control and automatic intelligent production. In the automatic control process, a large amount of electromagnetic signals are generated, causing electromagnetic pollution and affecting the intelligent production of the entire factory. Therefore, it is necessary to dope wave-absorbing materials in the building materials to reduce the influence of electromagnetic pollution.

[0005] The Chinese patent application with the publication number CN108045060A discloses a blast-resistant wideband wave-absorbing composite material and a preparation method thereof. A blast-resistant skin is prepared from quartz fiber and unsaturated resin. The wideband sandwich wave-absorbing material and the blast-resistant skin are sequentially attached to the reflective bottom plate to obtain the blast-resistant wideband wave-absorbing composite material, which has both blast-resistant function and wideband wave-absorbing function. However, the blast-resistant resin and the wave-absorbing material are physically attached in this scheme, and the performance difference between the two materials is large, which reduces the physical performance of the composite material and has low practicability. SUMMARY

[0006] The present application aims to improve the wave-absorbing performance of blast-resistant resin and provides a blast-resistant resin composite material and a preparation method thereof.

[0007] The application composites the graphene oxide nanosheet and the Ni-MOF through the phosphorylated lignin, carbonizes the phosphorylated lignin through high-temperature carbonization, fixes the graphene oxide nanosheet and the Ni-MOF on the surface of the glass fiber, and forms the nickel-based carbon material, which cooperates with the graphene oxide nanosheet to improve the wave absorption capacity of the explosion-proof resin.

[0008] The object of the application can be achieved by the following technical solutions.

[0009] An explosion-proof resin composite material contains the following components in parts by mass:

[0010] 80-100 parts of epoxy resin, 10-15 parts of wave-absorbing modified glass fiber, 5-8 parts of flame retardant, 0.3-0.4 parts of zinc stearate and 0.2-0.3 parts of antioxidant.

[0011] The flame retardant is one of aluminum hydroxide and magnesium hydroxide.

[0012] The antioxidant is one of hindered phenolic antioxidant and phosphite antioxidant.

[0013] Further, the wave-absorbing modified glass fiber is prepared by the following steps:

[0014] The high-silica glass fiber, the composite MOF graphene powder and the deionized water are ultrasonically mixed in a reaction kettle for 5-6 h, centrifugal filtration is performed to obtain a precipitate, the precipitate is vacuum dried at 60-70 DEG C, and then placed in a tube furnace, heated to 700-800 DEG C at a rate of 5 DEG C / min under nitrogen protection, and kept for 1.5-2 h, and then cooled to obtain the wave-absorbing modified glass fiber.

[0015] Further, the high-silica glass fiber, the composite MOF graphene powder and the deionized water are used in a ratio of 10-15 g: 0.8-1 g: 100-150 mL.

[0016] Further, the composite MOF graphene powder is prepared by the following steps:

[0017] The nickel nitrate hexahydrate and the 2-amino terephthalic acid are dissolved in DMF and deionized water in a reaction kettle, the lignin / graphene powder is added, heated to 120-130 DEG C and reacted for 20-24 h, the precipitate is separated by centrifugation, the precipitate is washed with DMF and ethanol, and vacuum dried to obtain the composite MOF graphene powder.

[0018] Further, the nickel nitrate hexahydrate, the 2-amino terephthalic acid, the DMF, the deionized water and the lignin / graphene powder are used in a ratio of 3-5 g: 3-4 g: 200-250 mL: 100-150 mL: 0.5-0.6 g.

[0019] Further, the lignin / graphene powder is prepared by the following steps:

[0020] Ultrasonic dispersion of phosphonated lignin in deionized water in a reaction kettle, add graphene oxide nanosheet, stirring reaction 10-12h, centrifugal collection of precipitate, 60-70℃ vacuum drying 10-12h to get lignin / graphene powder.

[0021] Further, the amount of phosphonated lignin, deionized water and graphene oxide nanosheet is 2-2.5g: 200-250mL: 1-1.2g.

[0022] Further, the phosphonated lignin is prepared by the following steps:

[0023] The basic lignin powder is dissolved in tetrahydrofuran in a reaction kettle, 85wt% phosphoric acid solution is added to the reaction kettle, 30-40℃ magnetic stirring 3-4h, after cooling, remove the solvent by distillation under reduced pressure to get the precipitate, wash the precipitate, vacuum drying to get phosphonated lignin.

[0024] Further, the amount of basic lignin powder, tetrahydrofuran and phosphoric acid is 1-2g: 50-60mL: 0.8-1g.

[0025] A preparation method of an explosion-proof resin composite material, comprising the following steps:

[0026] The epoxy resin, wave-absorbing modified glass fiber, flame retardant, zinc stearate and antioxidant are added to the mixing machine to stir and mix to get the premix, the premix is added to the mold, heated to reflux reaction at 150-170℃ for 3-6h, hot-pressed to form, and the explosion-proof resin composite material is obtained after curing for 20-24h.

[0027] The beneficial effects of the present application are:

[0028] (1) The explosion-proof resin composite material prepared by the present application is prepared by compounding porous nickel-based carbon material and graphene nanosheet to prepare composite MOF graphene powder, and the dispersed composite MOF graphene powder is fixed on the surface of high silica glass fiber by high temperature carbonization, so that the wave-absorbing modified glass fiber with wave-absorbing ability is obtained, so that the explosion-proof resin composite material has wave-absorbing performance, and the doping of graphene nanosheet also improves the mechanical properties of the explosion-proof resin material.

[0029] (2) The preparation method of the present application uses phosphonated lignin as a connecting material, and the phosphonated lignin is compounded with graphene oxide nanosheet, and the Ni-MOF is combined on the surface of the graphene oxide nanosheet under the action of the phosphonated cellulose, to form a composite MOF powder with uniform compounding degree, and the carbon structure formed by carbonization of lignin is used to fix the composite MOF powder on the surface of high silica glass fiber, so that the wave-absorbing performance and mechanical properties of the explosion-proof resin composite material are better improved. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0031] Embodiment 1: A preparation method of an explosion-proof resin composite material, comprising the following steps:

[0032] S1, dissolve 1 g of alkaline lignin powder passing through a 100 mesh sieve in 50 mL of tetrahydrofuran in a reaction kettle, add 0.8 g of 85 wt% phosphoric acid solution to the reaction kettle, magnetically stir at 30°C for 3 h, remove the solvent by distillation under reduced pressure after cooling to obtain a precipitate, wash the precipitate with deionized water, and vacuum dry at 90°C for 3 h to obtain phosphated lignin.

[0033] S2, ultrasonically disperse 2 g of phosphated lignin in 200 mL of deionized water in a reaction kettle, add 1 g of graphene oxide nanosheet, stir for 10 h, centrifuge to collect the precipitate, and vacuum dry at 60°C for 10 h to obtain lignin / graphene powder.

[0034] S3, dissolve 3 g of nickel nitrate hexahydrate and 3 g of 2-amino terephthalic acid in 200 mL of DMF and 100 mL of deionized water in a reaction kettle, add 0.5 g of lignin / graphene powder, heat to 120°C and react for 20 h, centrifuge to separate the precipitate, wash the precipitate with DMF and ethanol, and vacuum dry at 60°C for 10 h to obtain composite MOF graphene powder.

[0035] S4, ultrasonically mix 10 g of high-silica glass fiber, 0.8 g of composite MOF graphene powder, and 100 mL of deionized water in a reaction kettle for 5 h, centrifuge to obtain a precipitate, vacuum dry the precipitate at 60°C, and then place it in a tube furnace, heat to 700°C at a rate of 5°C / min under nitrogen protection, and keep the temperature for 1.5 h, and then cool to obtain wave-absorbing modified glass fiber.

[0036] S5, add 80 g of epoxy resin, 10 g of wave-absorbing modified glass fiber, 5 g of aluminum hydroxide, 0.3 g of zinc stearate, and 0.2 g of hindered phenolic antioxidant into a mixing machine and stir to mix to obtain a premix, add the premix into a mold, heat to reflux at 150°C for 3 h, hot-press to form, and then solidify for 20 h to obtain an explosion-proof resin composite material.

[0037] Embodiment 2: A preparation method of an explosion-proof resin composite material, comprising the following steps:

[0038] S1, 1.5 g of alkaline lignin powder sieved through a 100 mesh screen was dissolved in 55 mL of tetrahydrofuran in a reaction kettle, 0.9 g of 85 wt% phosphoric acid solution was added to the reaction kettle, and it was stirred magnetically at 35°C for 3.5 h. After cooling, the solvent was removed by distillation under reduced pressure to obtain a precipitate, which was washed with deionized water and vacuum dried at 92.5°C for 3.5 h to obtain phosphated lignin.

[0039] S2, 2.25 g of phosphated lignin was ultrasonically dispersed in 225 mL of deionized water in a reaction kettle, 1.1 g of graphene oxide nanosheet was added, and the reaction was stirred for 11 h. The precipitate was collected by centrifugation and vacuum dried at 65°C for 11 h to obtain lignin / graphene powder.

[0040] S3, 4 g of nickel nitrate hexahydrate and 3.5 g of 2-amino terephthalic acid were dissolved in 225 mL of DMF and 125 mL of deionized water in a reaction kettle, 0.55 g of lignin / graphene powder was added, and the temperature was raised to 125°C for 22 h. The precipitate was separated by centrifugation, washed with DMF and ethanol, and vacuum dried at 65°C for 11 h to obtain composite MOF graphene powder.

[0041] S4, 12.5 g of high-silica glass fiber, 0.9 g of composite MOF graphene powder, and 125 mL of deionized water were ultrasonically mixed in a reaction kettle for 5.5 h, and the precipitate was obtained by centrifugal filtration. After vacuum drying at 65°C, the precipitate was placed in a tube furnace and heated to 750°C at a rate of 5°C / min under nitrogen protection, and held for 1.75 h. After cooling, the wave-absorbing modified glass fiber was obtained.

[0042] S5, 90 g of epoxy resin, 12.5 g of wave-absorbing modified glass fiber, 6.5 g of aluminum hydroxide, 0.35 g of zinc stearate, and 0.25 g of hindered phenolic antioxidant were added to a mixing machine and stirred to obtain a premix. The premix was added to a mold, heated to reflux at 160°C for 4.5 h, and hot-pressed to form a solidified product. After curing for 22 h, the explosion-proof resin composite material was obtained.

[0043] Example 3: A method for preparing an explosion-proof resin composite material, comprising the following steps:

[0044] S1, 2 g of alkaline lignin powder sieved through a 100 mesh screen was dissolved in 60 mL of tetrahydrofuran in a reaction kettle, 1 g of 85 wt% phosphoric acid solution was added to the reaction kettle, and it was stirred magnetically at 40°C for 4 h. After cooling, the solvent was removed by distillation under reduced pressure to obtain a precipitate, which was washed with deionized water and vacuum dried at 95°C for 4 h to obtain phosphated lignin.

[0045] S2, 2.5 g of phosphated lignin was ultrasonically dispersed in 250 mL of deionized water in a reaction kettle, 1.2 g of graphene oxide nanosheet was added, and the reaction was stirred for 12 h. The precipitate was collected by centrifugation and vacuum dried at 70°C for 12 h to obtain lignin / graphene powder.

[0046] S3, dissolve 5g nickel nitrate hexahydrate and 4g 2-amino terephthalic acid in 250mL DMF and 150mL deionized water in a reaction kettle, add 0.6g lignin / graphene powder, heat to 130℃ for 24h, centrifugal separation of the precipitate, the precipitate is washed with DMF and ethanol, vacuum drying at 70℃ for 12h to obtain composite MOF graphene powder.

[0047] S4, ultrasonic mixing 15g high silica glass fiber, 1g composite MOF graphene powder and 150mL deionized water in a reaction kettle for 6h, centrifugal filtration to obtain the precipitate, the precipitate is vacuum dried at 70℃ and then placed in a tube furnace, heated to 800℃ at a rate of 5℃ / min under nitrogen protection, and kept for 2h, and then cooled to obtain wave-absorbing modified glass fiber.

[0048] S5, add 100g epoxy resin, 15g wave-absorbing modified glass fiber, 8g magnesium hydroxide, 0.4g zinc stearate and 0.3g phosphite antioxidant into a mixing machine to stir and mix to obtain a premix, add the premix into a mold, heat and reflux at 170℃ for 6h to hot-press form, and then solidify for 24h to obtain an explosion-proof resin composite material.

[0049] Invention principle:

[0050] The alkaline lignin is modified by phosphoric acid, the alkaline lignin surface hydroxyl group is beneficial to the grafting modification of phosphoric acid group, the phosphatized lignin reacts with the hydroxyl group on the surface of graphene oxide nanosheet by using the phosphoric acid group, and the lignin surface and graphene oxide nanosheet also have hydrogen bonding, the phosphatized lignin is compounded with graphene oxide nanosheet, then Ni-MOF is generated in situ on the surface of lignin / graphene powder, the amino group in the ligand 2-amino terephthalic acid is used to improve the binding capacity of Ni-MOF on the surface of phosphatized lignin, and finally the composite MOF powder compounded by Ni-MOF, phosphatized lignin and graphene oxide nanosheet is obtained.

[0051] The composite MOF powder is compounded with high-silica glass fiber which has high temperature resistance and high strength, and then high temperature sintering is carried out, so that the phosphatized cellulose in the composite MOF graphene powder is carbonized on the surface of high-silica glass fiber, the binding strength of the composite MOF graphene powder and the high-silica glass fiber is improved, the agglomeration phenomenon of the composite MOF graphene powder when mixed with epoxy resin is avoided, meanwhile, the ligand of Ni-MOF is carbonized and derived into porous nickel-based carbon material under high temperature, which has good electromagnetic wave absorption capacity and is dispersed on the surface of high-silica glass fiber, and the wave-absorbing performance of high-silica glass fiber is improved.

[0052] The high temperature also causes the graphene oxide nanosheet to be reduced to form a graphene nanosheet, the graphene nanosheet has a large specific surface area, can effectively serve as a wave-absorbing material to improve the wave-absorbing capacity of the resin, and has an improvement effect on the mechanical properties of the resin, can effectively improve the impact resistance and tensile strength of the resin, and improve the explosion-proof capacity of the resin, and cooperates with the nickel-based carbon material to jointly improve the wave-absorbing capacity of the resin.

[0053] Comparative Example 1: The difference from Example 1 is that in S2, the alkaline lignin powder is used to replace the phosphorized lignin to prepare the explosion-proof resin composite material.

[0054] Comparative Example 2: The difference from Example 1 is that in S3, the graphene oxide nanosheet is used to replace the lignin / graphene powder to prepare the explosion-proof resin composite material.

[0055] Comparative Example 3: The difference from Example 1 is that in S4, the 0.5 g of lignin / graphene powder and 0.3 g of zirconium dioxide nanometer powder are used to replace the composite MOF graphene powder to prepare the explosion-proof resin composite material.

[0056] The sources of some reagents in the comparative examples and the examples are as follows:

[0057] The alkaline lignin powder has a CAS number of 9005-53-2 and a purity of 99%, and is purchased from Hubei Dalili Chemical Co., Ltd.

[0058] The graphene oxide nanosheet has a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm, and is purchased from Su Xianfeng Nanometer Material Technology Co., Ltd.

[0059] The high-silica glass fiber is a chopped fiber, and has a specification of 9-15 μm, and is purchased from Lianyungang Rongbai New Material Co., Ltd.

[0060] The explosion-proof resin composite materials prepared in Examples 1-3 and Comparative Examples 1-3 are subjected to performance tests, the compressive strength of the samples is tested according to the standard GBJ81-1985, the impact resistance of the samples is tested according to the standard GB / T1043.1-2008, the electromagnetic parameters of the samples are tested according to the coaxial test method, and the model of the testing machine is N5241BPNA-X microwave network analyzer, and the frequency range of the test is 2-18 GHz.

[0061] The results are shown in Table 1:

[0062] Table 1: Performance test results of the explosion-proof resin composite material

[0063] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Compressive strength (MPa) 78 81 82 72 68 63 Impact strength (kJ / m 2 ) 102 103 105 92 90 86 Effective absorption bandwidth (GHz) 5.43 5.28 5.12 5.81 6.72 7.41 Minimum reflectance (dB) -33.6 -33.9 -34.0 -30.1 -27.4 -24.8

[0064] As shown in Table 1, the anti-explosion resin composite prepared by the application has high compressive strength and impact strength, indicating that the anti-explosion performance is good, and the effective absorption bandwidth is low and the minimum reflectivity is small, indicating that the anti-explosion resin composite prepared by the application has good wave absorption capacity.

[0065] In Comparative Example 1, the alkaline lignin powder is not phosphatized and modified, the composite degree of the alkaline lignin powder and the graphene oxide nanosheet is low, and the composite degree of the Ni-MOF and the lignin / graphene powder is also reduced, so that the performance of the prepared anti-explosion resin composite is reduced.

[0066] In Comparative Example 2, the phosphatized lignin is not added, the composite degree and the composite strength of the graphene oxide nanosheet and the Ni-MOF are low, the modification effect on the high silica glass fiber is reduced, and when the prepared wave absorption modified glass fiber is mixed with the epoxy resin, the composite MOF graphene powder is easy to fall off from the surface of the high silica glass fiber, and the mechanical performance and the wave absorption performance of the anti-explosion resin composite are improved to a low degree.

[0067] In Comparative Example 3, the zirconium dioxide nanometer powder is used to replace the Ni-MOF, the formed nickel-based carbon material does not have a porous structure, the wave absorption capacity is improved to a small degree, and the combination degree of the zirconium dioxide nanometer powder and the lignin / graphene powder is low, and the synergistic effect of the zirconium dioxide and the graphene nanosheet is small.

[0068] Although the embodiments of the application have been shown and described, it is understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.

Claims

1. An explosion-proof resin composite material, characterized in that: Calculated by mass, it contains the following components: 80-100 parts of epoxy resin, 10-15 parts of microwave-absorbing modified glass fiber, 5-8 parts of flame retardant, 0.3-0.4 parts of zinc stearate and 0.2-0.3 parts of antioxidant; The flame retardant is one of aluminum hydroxide and magnesium hydroxide; The antioxidant is one of a hindered phenol antioxidant and a phosphite antioxidant; The wave-absorbing modified glass fiber is prepared by the following steps: In a reaction kettle, high silica glass fiber, composite MOF graphene powder and deionized water were ultrasonically mixed for 5-6 hours, centrifuged and filtered to obtain a precipitate, the precipitate was vacuum dried at 60-70°C and placed in a tube furnace, and heated to 700-800°C at a rate of 5°C / min under nitrogen protection, kept warm for 1.5-2 hours, and cooled to obtain the microwave-absorbing modified glass fiber; The composite MOF graphene powder is prepared by the following steps: In a reaction kettle, nickel nitrate hexahydrate and 2-aminoterephthalic acid are dissolved in DMF and deionized water, lignin / graphene powder is added, the temperature is raised to 120-130°C and the reaction is carried out for 20-24 hours, the precipitate is separated by centrifugation, the precipitate is washed with DMF and ethanol, and vacuum dried to obtain a composite MOF graphene powder; The lignin / graphene powder is prepared by the following steps: Phosphorylated lignin was ultrasonically dispersed in deionized water in a reactor, graphene oxide nanosheets were added, and the mixture was stirred for 10-12 hours. The precipitate was collected by centrifugation and vacuum dried at 60-70° C. for 10-12 hours to obtain lignin / graphene powder.

2. The explosion-proof resin composite material according to claim 1, characterized in that: The usage ratio of the high silica glass fiber, the composite MOF graphene powder and the deionized water is 10-15 g: 0.8-1 g: 100-150 mL.

3. The explosion-proof resin composite material according to claim 1, characterized in that: The usage ratio of the nickel nitrate hexahydrate, 2-aminoterephthalic acid, DMF, deionized water and lignin / graphene powder is 3-5 g: 3-4 g: 200-250 mL: 100-150 mL: 0.5-0.6 g.

4. The explosion-proof resin composite material according to claim 1, characterized in that: The usage ratio of the phosphorylated lignin, deionized water and graphene oxide nanosheets is 2-2.5 g: 200-250 mL: 1-1.2 g.

5. The explosion-proof resin composite material according to claim 1, characterized in that: The phosphorylated lignin is prepared by the following steps: Alkaline lignin powder is dissolved in tetrahydrofuran in a reactor, and 85 wt% phosphoric acid solution is added to the reactor, and magnetic stirring is performed at 30-40° C. for 3-4 hours. After cooling, the solvent is removed by vacuum distillation to obtain a precipitate, and the precipitate is washed and vacuum dried to obtain phosphorylated lignin.

6. The explosion-proof resin composite material according to claim 5, characterized in that: The usage ratio of the alkaline lignin powder, tetrahydrofuran and phosphoric acid is 1-2 g: 50-60 mL: 0.8-1 g.

7. The method for preparing an explosion-proof resin composite material according to claim 1, characterized in that: The steps include: Epoxy resin, wave-absorbing modified glass fiber, flame retardant, zinc stearate and antioxidant are added into a mixer and stirred to obtain a premix. The premix is ​​added into a mold, heated to reflux at 150-170° C. for 3-6 hours and hot-pressed to form the mixture. The explosion-proof resin composite material is obtained after curing for 20-24 hours.