Polydivinylbenzene / nickel composite material as well as preparation method and application thereof

Abstract

The invention provides a polydivinylbenzene / nickel composite material as well as a preparation method and application thereof. The polydivinylbenzene / nickel composite material has a relatively high specific surface area, a rich pore structure and good hydrophobicity. According to the preparation method, polyhydric alcohol is adopted as a reaction solvent, nickel acetate is reduced through a solvothermal method, the polydivinylbenzene / nickel composite material with the high specific surface area can be obtained, and the polydivinylbenzene / nickel composite material has wide application prospects in the fields of physical adsorption, chemical adsorption and catalysis. The preparation method is relatively simple and convenient, the polydivinylbenzene / metal nickel composite material can be prepared by only one step, and the yield can be greatly improved.

Description

Technical Field

[0001] The present invention relates to a polydivinylbenzene / nickel composite material, a preparation method thereof and uses thereof, belonging to the technical field of functional materials. Background Art

[0002] Traditional magnetic nanomaterials often aggregate into large aggregates, thus no longer possessing the unique properties of independent nanomagnetic particles. Therefore, researchers usually load them on specific substrate materials for application, loading metal nanoparticles on a polymer matrix to maintain the unique properties of the nanometal particles.

[0003] At present, porous polymer-metal composite materials are mostly prepared by a stepwise method, and its disadvantages are that the steps are cumbersome, the cost is high, and the metal distribution is uneven, which limits its application and development. Summary of the Invention

[0004] It is found through research that polydivinylbenzene has the characteristics of high crosslinking degree, large specific surface area, high temperature resistance, superhydrophobicity, etc., and will not soften even at high temperatures, and is a good metal particle carrier. Single metal particles are prone to agglomeration during use. Loading metal particles on polydivinylbenzene can effectively avoid this problem and greatly broaden the application scenarios of metal particles.

[0005] The purpose of the present invention is to provide a polydivinylbenzene / nickel composite material, a preparation method thereof and uses thereof. The polydivinylbenzene / nickel composite material prepared by the present invention has the characteristics of a high specific surface area and uniform distribution of metal particles, greatly expanding the application scenarios of porous polymer-metal composite materials.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] A preparation method of a polydivinylbenzene / nickel composite material, the method comprising the following steps:

[0008] 1) Dissolve nickel acetate, divinylbenzene and an initiator in a polyol to obtain a mixed solution;

[0009] 2) Transfer the mixed solution in step 1) to a hydrothermal reaction kettle for solvothermal reaction to prepare a gel-like polydivinylbenzene / nickel composite material;

[0010] 3) Immerse the gel-like polydivinylbenzene / nickel in step 2) in absolute ethanol and deionized water in sequence to prepare a polydivinylbenzene / nickel hydrogel;

[0011] 4) Place the polydivinylbenzene / nickel hydrogel obtained in step 3) in liquid nitrogen for rapid freezing. After the polydivinylbenzene hydrogel / nickel is completely frozen, transfer it to a vacuum freeze dryer for vacuum freeze drying to obtain the polydivinylbenzene / nickel composite material.

[0012] According to an embodiment of the present invention, in step 1), the polyol is selected from at least one of ethylene glycol, propylene glycol, and butylene glycol.

[0013] According to an embodiment of the present invention, in step 1), nickel acetate, divinylbenzene, and an initiator are respectively dissolved in the polyol to obtain a mixed solution. Preferably, nickel acetate is first dissolved in the polyol, then the initiator is dissolved in the polyol, and finally divinylbenzene is dissolved in the polyol to obtain a mixed solution.

[0014] According to an embodiment of the present invention, in step 1), the mass ratio of the initiator to divinylbenzene is 1-5:100, such as 1:100, 2:100, 3:100, 4:100, or 5:100.

[0015] According to an embodiment of the present invention, in step 1), the mass ratio of nickel acetate to divinylbenzene is 5-50:100, such as 5:100, 10:100, 15:100, 20:100, 25:100, 30:100, 35:100, 40:100, 45:100, or 50:100.

[0016] According to an embodiment of the present invention, in step 1), the initiator is selected from at least one of azobisisobutyronitrile, di-tert-butyl peroxide, benzoyl peroxide, diisopropylbenzene peroxide, tert-butyl hydroperoxide, potassium persulfate, and ammonium persulfate.

[0017] According to an embodiment of the present invention, in step 1), the dissolution is carried out at room temperature.

[0018] According to an embodiment of the present invention, in step 1), the dissolution is carried out under stirring conditions.

[0019] According to an embodiment of the present invention, it is found that the polyol can not only be used as a solvent in the solvothermal method to prepare polydivinylbenzene, but also be used as a reducing agent to reduce nickel acetate to metallic nickel, which makes it feasible to prepare the polydivinylbenzene / nickel composite material by a one-step synthesis method.

[0020] According to an embodiment of the present invention, in step 2), the temperature of the solvothermal reaction is 180-200 °C, such as 180 °C, 185 °C, 190 °C, 195 °C, or 200 °C.

[0021] According to an embodiment of the present invention, in step 2), the heat preservation time of the solvothermal reaction is 8 - 24 hours, such as 8 hours, 9 hours, 10 hours, 12 hours, 15 hours, 16 hours, 18 hours, 20 hours or 24 hours.

[0022] According to an embodiment of the present invention, in step 2), the mixed solution of step 1) is transferred into a hydrothermal reaction kettle, and the hydrothermal reaction kettle is placed in an oven. After heat preservation at 180 - 200 °C for 8 - 24 hours, it is taken out to obtain gel-like polydivinylbenzene / nickel.

[0023] According to an embodiment of the present invention, in step 3), the gel-like polydivinylbenzene / nickel contains unreacted divinylbenzene, unreacted initiator, polyol and nickel acetate. By sequentially soaking the gel-like polydivinylbenzene / nickel in absolute ethanol and deionized water, the unreacted divinylbenzene, unreacted initiator, polyol and nickel acetate in the gel-like polydivinylbenzene / nickel can be completely replaced with deionized water to obtain a polydivinylbenzene / nickel hydrogel.

[0024] According to an embodiment of the present invention, in step 3), first soak the gel-like polydivinylbenzene / nickel in absolute ethanol for multiple times (such as 2 - 3 times) until the unreacted divinylbenzene, unreacted initiator, polyol and nickel acetate in the gel-like polydivinylbenzene / nickel are completely replaced with absolute ethanol. Then soak the gel-like polydivinylbenzene / nickel in deionized water for multiple times (such as 2 - 3 times) until the absolute ethanol in the gel-like polydivinylbenzene / nickel is completely replaced with deionized water, that is, a polydivinylbenzene / nickel hydrogel is prepared.

[0025] According to an embodiment of the present invention, in step 4), it is found that the drying method will affect the specific surface area of the final product. Traditional oven drying will cause the pore structure to collapse, thereby resulting in a decrease in the specific surface area. When liquid nitrogen is used to rapidly freeze the polydivinylbenzene / nickel hydrogel and then combined with vacuum freeze-drying, the water in the polydivinylbenzene / nickel hydrogel can be directly sublimated from the ice crystal state into water vapor, which can avoid the collapse of the pore structure and further increase the specific surface area of the polydivinylbenzene / nickel.

[0026] According to an embodiment of the present invention, in step 4), the polydivinylbenzene / nickel hydrogel of step 3) is immersed in liquid nitrogen to ensure that the polydivinylbenzene / nickel hydrogel is quickly frozen and at the same time ensure the uniform freezing of the polydivinylbenzene hydrogel / nickel.

[0027] According to an embodiment of the present invention, in step 4), the complete freezing means that all the water in the divinylbenzene / nickel hydrogel is frozen into ice. Under conventional operating conditions, placing the divinylbenzene / nickel hydrogel obtained in step 3) in liquid nitrogen for 5 - 10 minutes or more can achieve the complete freezing of the divinylbenzene / nickel hydrogel.

[0028] According to an embodiment of the present invention, in step 4), the vacuum degree of the vacuum freeze-drying is 5 - 20 Pa, and the time of the vacuum freeze-drying is 24 - 48 h.

[0029] The present invention also provides a divinylbenzene / nickel composite material, which is prepared by the above method.

[0030] According to an embodiment of the present invention, the divinylbenzene / nickel composite material includes divinylbenzene and nickel particles. The divinylbenzene resin is the continuous phase, and the nickel particles with nanoscale size are the dispersed phase. The nickel particles are uniformly dispersed on the surface and in the internal pores of the divinylbenzene.

[0031] According to an embodiment of the present invention, the specific surface area of the divinylbenzene / nickel composite material is 20 - 200 m 2 / g.

[0032] According to an embodiment of the present invention, in the divinylbenzene / nickel composite material, the mass ratio of the nickel particles is 5 - 15%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, and the mass ratio of the divinylbenzene is 85 - 95%, such as 85%, 86%, 87%, 88%, 89%, 90%, 91%, 91.2%, 92%, 93%, 94% or 95%.

[0033] The present invention also provides a use of the divinylbenzene / nickel composite material, which is used in the fields of physical adsorption, chemical adsorption and catalysis.

[0034] The beneficial effects of the present invention:

[0035] The present invention provides a polydivinylbenzene / nickel composite material, a preparation method thereof, and uses thereof. The polydivinylbenzene / nickel composite material has a high specific surface area, a rich pore structure, and good hydrophobicity. In the preparation method, a polyol is used as a reaction solvent, and nickel acetate is reduced by a solvothermal method, so that a polydivinylbenzene / nickel composite material with a high specific surface area can be obtained, which has broad application prospects in the fields of physical adsorption, chemical adsorption, and catalysis. The preparation method is relatively simple and only requires one step to prepare the polydivinylbenzene / metal nickel composite material, which can greatly improve the yield. Specifically, the one-step synthesis method of the present invention is to simultaneously dissolve a divinylbenzene monomer, an initiator, and a metal salt in a polyol solvent, and through a solvothermal method, the monomer polymerization reaction and the reduction of the metal salt are carried out simultaneously, so as to achieve the one-step synthesis of the polydivinylbenzene / nickel composite material. Compared with the polydivinylbenzene / nickel composite material prepared by a stepwise synthesis method, the polydivinylbenzene / nickel composite material prepared by the one-step synthesis method of the present invention has the advantages of more uniform distribution of metal particles and a simple process. Description of the Drawings

[0036] Figure 1 is of a), in Example 1 ( Figure 1 b), in Example 2 ( Figure 1 and c), in Example 3 ( Figure 1 scanning electron microscope images of the polydivinylbenzene / nickel composite material.

[0037] Figure 2 is of a), in Example 1 ( Figure 2 b), in Example 2 ( Figure 2 and c), in Example 3 ( Figure 2 energy dispersive spectroscopy images of nickel element of the polydivinylbenzene / nickel composite material.

[0038] Figure 3 is the XRD spectrum of the polydivinylbenzene / nickel composite material of Examples 1-3. Detailed Embodiments

[0039] The following will further elaborate on the preparation method of the present invention with specific examples. It should be understood that the following examples are only for illustrative and explanatory purposes of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0040] The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples can all be obtained from commercial sources unless otherwise specified.

[0041] Example 1

[0042] First, dissolve 1 g of nickel acetate in 30 ml of ethylene glycol. After the nickel acetate is completely dissolved, dissolve 0.02 g of azobisisobutyronitrile (AIBN) in the mixed solution, and then add 2 g of divinylbenzene to the mixed solution. After AIBN and divinylbenzene are completely dissolved, transfer the mixed solution to a 50-ml polytetrafluoroethylene liner, place the liner in a hydrothermal reactor, and tighten it. Set the oven temperature to 180 °C, transfer the hydrothermal reactor to the oven, and keep it warm for 16 h. After the hydrothermal reactor is completely cooled, take it out to obtain a gel-like polydivinylbenzene / nickel composite material. Soak the polydivinylbenzene / nickel gel three times with anhydrous ethanol and distilled water respectively to remove the residual monomers and initiators, and completely replace the solvent to obtain a polydivinylbenzene / nickel hydrogel. Then, quickly freeze the polydivinylbenzene / nickel hydrogel in liquid nitrogen, and then transfer it to a vacuum freeze dryer. The vacuum degree is 20 Pa, and the drying time is 48 h. After the sample is completely dried, take it out to obtain a polydivinylbenzene / nickel composite material.

[0043] The test results show that the BET specific surface area of the polydivinylbenzene / nickel composite material prepared by this method is 159 m 2 / g.

[0044] Example 2

[0045] First, dissolve 1 g of nickel acetate in 30 ml of propylene glycol. After the nickel acetate is completely dissolved, dissolve 0.02 g of azobisisobutyronitrile (AIBN) in the mixed solution, and then add 2 g of divinylbenzene to the mixed solution. After AIBN and divinylbenzene are completely dissolved, transfer the mixed solution to a 50-ml polytetrafluoroethylene liner, place the liner in a hydrothermal reactor, and tighten it. Set the oven temperature to 180 °C, transfer the hydrothermal reactor to the oven, and keep it warm for 16 h. After the hydrothermal reactor is completely cooled, take it out to obtain a gel-like polydivinylbenzene / nickel composite material. Soak the polydivinylbenzene / nickel gel three times with anhydrous ethanol and distilled water respectively to remove the residual monomers and initiators, and completely replace the solvent to obtain a polydivinylbenzene / nickel hydrogel. Then, quickly freeze the polydivinylbenzene / nickel hydrogel in liquid nitrogen, and then transfer it to a vacuum freeze dryer. The vacuum degree is 20 Pa, and the drying time is 48 h. After the sample is completely dried, take it out to obtain a polydivinylbenzene / nickel composite material.

[0046] The test results show that the BET specific surface area of the polydivinylbenzene / nickel composite material prepared by this method is 97.5 m 2 / g.

[0047] Example 3

[0048] First, 1 g of nickel acetate was dissolved in 30 ml of butanediol. After the nickel acetate was completely dissolved, 0.02 g of azobisisobutyronitrile (AIBN) was dissolved in the mixed solution, and then 2 g of divinylbenzene was added to the mixed solution. After AIBN and divinylbenzene were completely dissolved, the mixed solution was transferred to a 50-ml polytetrafluoroethylene liner, and the liner was placed in a hydrothermal reactor and tightened. The oven temperature was set at 180 °C, and the hydrothermal reactor was transferred to the oven and kept warm for 16 h. After the hydrothermal reactor was completely cooled, it was taken out to obtain a gel-like polydivinylbenzene / nickel composite material. The polydivinylbenzene / nickel gel was soaked in absolute ethanol and distilled water three times respectively to remove the residual monomers and initiators, and the solvent was completely replaced to obtain a polydivinylbenzene / nickel hydrogel. Then the polydivinylbenzene / nickel hydrogel was quickly frozen in liquid nitrogen and then transferred to a vacuum freeze dryer. The vacuum degree was 20 Pa and the drying time was 48 h. After the sample was completely dried, it was taken out to obtain a polydivinylbenzene / nickel composite material.

[0049] The test results showed that the BET specific surface area of the polydivinylbenzene / nickel composite material prepared by this method was 22 m 2 / g.

[0050] It can be seen from Figure 1 that in the composite material prepared by the method of the present invention, nickel particles were successfully loaded on the surface and pores of polydivinylbenzene. It can be seen from Figure 2 that the nickel particles were evenly distributed and no agglomeration occurred. It can be seen from Figure 3 that nano-sized nickel particles could be obtained in the prepared composite material, that is, nickel acetate was reduced to elemental nickel particles by polyol during the solvothermal reaction process.

[0051] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a polydivinylbenzene / nickel composite material, the method comprising the following steps: 1) Dissolve nickel acetate, divinylbenzene and an initiator in a polyol to obtain a mixed solution; 2) Transfer the mixed solution of step 1) to a hydrothermal reaction kettle for solvothermal reaction to prepare a gel-like polydivinylbenzene / nickel composite material; 3) Immerse the gel-like polydivinylbenzene / nickel of step 2) in absolute ethanol and deionized water in sequence to prepare a polydivinylbenzene / nickel hydrogel; 4) Place the polydivinylbenzene / nickel hydrogel of step 3) in liquid nitrogen for rapid freezing. After the polydivinylbenzene hydrogel / nickel is completely frozen, transfer it to a vacuum freeze dryer for vacuum freeze drying to obtain the polydivinylbenzene / nickel composite material.

2. The preparation method according to claim 1, wherein In step 1), the polyol is selected from at least one of ethylene glycol, propylene glycol and butylene glycol. Preferably, in step 1), nickel acetate, divinylbenzene and an initiator are respectively dissolved in a polyol to obtain a mixed solution. Preferably, first dissolve nickel acetate in a polyol, then dissolve the initiator in the polyol, and finally dissolve divinylbenzene in the polyol to obtain a mixed solution.

3. The preparation method according to claim 1, wherein, In step 1), the mass ratio of the initiator to divinylbenzene is 1-5:100; And / or, in step 1), the mass ratio of nickel acetate to divinylbenzene is 5-50:

100.

4. The preparation method according to claim 1, wherein, In step 2), the temperature of the solvothermal reaction is 180-200 °C; the heat preservation time of the solvothermal reaction is 8-24 hours.

5. The preparation method according to claim 1, wherein, In step 3), first immerse the gel-like polydivinylbenzene / nickel in absolute ethanol and repeat multiple times until the unreacted divinylbenzene, unreacted initiator, polyol and nickel acetate in the gel-like polydivinylbenzene / nickel are all replaced by absolute ethanol, and then immerse the gel-like polydivinylbenzene / nickel in deionized water and repeat multiple times until the absolute ethanol in the gel-like polydivinylbenzene / nickel is all replaced by deionized water, that is, a polydivinylbenzene / nickel hydrogel is prepared.

6. The preparation method according to claim 1, wherein In step 4), the vacuum degree of the vacuum freeze drying is 5-20 Pa, and the time of the vacuum freeze drying is 24-48 h.

7. A polydivinylbenzene / nickel composite material, the polydivinylbenzene / nickel composite material is prepared by the method according to any one of claims 1-6.

8. The polydivinylbenzene / nickel composite material according to claim 7, wherein, The polydivinylbenzene / nickel composite material includes polydivinylbenzene and nickel particles. The polydivinylbenzene resin is the continuous phase, and the nickel particles with nanoscale size are the dispersed phase. The nickel particles are uniformly dispersed on the surface and in the internal pores of the polydivinylbenzene.

9. The polydivinylbenzene / nickel composite material according to claim 7 or 8, wherein, In the polydivinylbenzene / nickel composite material, the mass ratio of the nickel particles is 5-15%, and the mass ratio of the polydivinylbenzene is 85-95%.

10. Use of the polydivinylbenzene / nickel composite material according to any one of claims 7-9, which is used in the fields of physical adsorption, chemical adsorption and catalysis.

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