CN107501494B - Phosphorus-containing covalent organic framework nanosheet and preparation method thereof - Google Patents
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Abstract
The invention discloses a phosphorus-containing covalent organic framework nanosheet and a preparation method thereof, wherein the phosphorus-containing covalent organic framework nanosheet is characterized in that the structural general formula is as follows:wherein Z is a phosphorus-containing structure. According to the invention, the melamine/o-phthalaldehyde COFs nanosheets are organically modified by using the phosphorus-containing compound, so that the COFs nanosheets not only can more efficiently retard the flame of the epoxy resin, but also can improve the mechanical property of the epoxy resin.
Description
Technical Field
The invention relates to a phosphorus-containing covalent organic framework nanosheet and a preparation method thereof, and belongs to the technical field of high polymer materials.
Background
Covalent Organic Frameworks (COFs) are two-or three-dimensional crystalline porous materials formed from Organic building blocks connected by strong Covalent bonds. Because of its structural features distinct from those of conventional organic materials, COFs are widely used in gas storage and separation, catalysis, chemical sensors, electrochemistry, and clean energy. Meanwhile, because the COFs have a graphite-like three-dimensional layered structure, many scholars around the world are dedicated to preparing the COFs nanosheets.
Preparation of COFs nanoplates on highly oriented graphite was published by Xuan-He Liu et al in Small, Vol.10, p.4934-4939, 2014. In 2011, the preparation of COFs Nano-sheets on a gold surface made of self-made single crystals is disclosed by RyotaTanoue et al in ACS Nano 5, 3923 and 3929. However, the preparation process is complex, the yield is low, the raw materials are expensive, and the application of the COFs nanosheets in high polymer plastics is greatly limited. At present, the COFs nano-sheet of melamine and phthaloyl is successfully prepared by a ball milling method, and the problems are solved to a certain extent. However, few reports are available about the preparation of phosphorus-containing COFs nano-sheets with flame retardant properties. Therefore, the search for a simple and cheap preparation method for synthesizing the organic functionalized COFs nano-sheet is urgent.
Disclosure of Invention
The invention aims to provide a phosphorus-containing covalent organic framework nanosheet and a preparation method thereof, and the novel phosphorus-containing organic modified COFs nanosheet is developed on the basis of a melamine/o-phthalaldehyde COFs nanosheet, so that the original advantages of the COFs material are retained, and meanwhile, the flame retardant property is achieved.
The phosphorus-containing covalent organic framework nanosheet has the following structural general formula:
wherein Z is a phosphorus-containing structure, and specifically comprises the following structures:
the preparation method of the phosphorus-containing covalent organic framework nanosheet comprises the following steps:
step 1: adding dimethyl sulfoxide solution (100ml) containing 2.02g of melamine into a single-neck flask with magnetons, then sequentially adding dimethyl sulfoxide solution (10ml) containing 3.22g of o-phthalaldehyde and acetic acid aqueous solution (40ml, 3M), vacuumizing the single-neck flask, and reacting at 135 ℃ and 0.1MPa for 3 days to obtain the COFs material;
step 2: dispersing the COFs material obtained in the step 1 in a solvent, carrying out wet ball milling for 24 hours in a ball mill at the rotating speed of 225rpm, and collecting an upper layer suspension after centrifugal separation, namely the COFs nanosheet suspension;
and step 3: and (3) dropwise adding a phosphorus-containing compound solution into the COFs nanosheet suspension obtained in the step (2), reacting for 12-24 hours at the temperature of 100-180 ℃, and after the reaction is finished, performing centrifugal separation and washing to obtain the phosphorus-containing COFs nanosheets.
In step 2, the solvent is selected from ethanol, chloroform, N Dimethylformamide (DMF), dioxane, tetrahydrofuran, acetone or dimethyl sulfoxide.
In step 2, the rotation speed of the centrifugal separation is 3000-.
In the step 2, the concentration of the COFs nanosheet suspension liquid after ball milling is 0.2-1 wt%.
In the step 3, the mass ratio of the phosphorus-containing compound to the COFs nano-sheets is 1:1-10: 1.
In step 3, the phosphorus-containing compound is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diethyl phosphite, dimethyl phosphite, dibutyl phosphite, diphenyl phosphite, or dialkyl phosphite. The solvent used by the phosphorus compound solution is methanol, ethanol, diethyl ether, chloroform, N dimethylformamide or dioxane. The concentration of the phosphorus-containing compound solution is 0.2-2 mol/L.
In the step 3, the rotation speed of centrifugal separation is 1500-; the solvent used in washing is one or more of methanol, tetrahydrofuran, acetone and dichloromethane.
Compared with the prior art, the invention has the beneficial effects that:
1. if the phosphorus-containing compound is directly added into epoxy resin for in-situ polymerization, the crosslinking density of the epoxy resin is reduced, and the mechanical properties of the epoxy resin are damaged. According to the invention, the phosphorus-containing compound is used for organically modifying the melamine/o-phthalaldehyde COFs nanosheets, so that the COFs nanosheets not only can be used for more efficiently retarding the flame of the epoxy resin, but also can be used for improving the mechanical property of the epoxy resin.
2. The COFs adopted by the invention is easy to prepare, the raw materials are easy to obtain, and the manufacturing cost of the COFs is greatly reduced.
3. The phosphorus-containing COFs nanosheet prepared by the method is simple in synthesis process, and the phosphorus content of the prepared modified COFs material can be effectively adjusted by adjusting the content and the type of the phosphorus-containing compound participating in the reaction, so that the possibility is provided for further organic modification.
Drawings
FIG. 1 is an infrared spectrum of DOPO-COFs nanosheets in example 1.
FIG. 2 is an X-ray photoelectron spectrum of DOPO-COFs nanosheet in example 1.
FIG. 3 is a transmission electron micrograph of DOPO-COFs nanosheets in example 1.
FIG. 4 is a graph of the heat release rate of epoxy resin and its nanocomposites in example 6.
FIG. 5 is a dynamic mechanical analysis curve of the epoxy resin and its nanocomposite in example 6.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1: preparation of COFs nanosheets
1. Adding 100ml of dimethyl sulfoxide solution containing 2.02g of melamine into a single-neck flask with magnetons, then sequentially adding 10ml of dimethyl sulfoxide solution containing 3.22g of o-phthalaldehyde and acetic acid aqueous solution (40ml, 3M), vacuumizing the single-neck flask, and reacting at 135 ℃ and 0.1MPa for 3 days to obtain the COFs material;
2. and (3) dispersing the COFs material obtained in the step (1) in N, N dimethylformamide, carrying out wet ball milling for 24 hours in a ball mill at the rotating speed of 225rpm, and collecting an upper layer suspension after centrifugal separation, namely the COFs nanosheet suspension.
Example 2: preparation of DOPO-COFs nano-sheet
Dissolving 4.6g of DOPO in N, N-dimethylformamide, then dropwise adding into 200g of 0.2 wt% COFs nanosheet suspension at 130 ℃, and reacting for 12 hours after dropwise adding is finished; and after the reaction is finished, centrifuging the reaction solution at 1500rpm for 10 minutes, carrying out suction filtration on the upper layer liquid, and sequentially washing the obtained product with acetone, chloroform and methanol to obtain the DOPO-COFs nanosheet.
FIG. 1 is an infrared spectrum of DOPO-COFs nanosheets in example 1. In the infrared spectrum of COFs, at 3401,1726 and 1350cm-1The peaks at (A) are respectively aromatic ring stretching vibration, unreacted aldehyde group stretching vibration and-NH-stretching vibration. COFs are 1209 and 810cm-1The bond at (A) is an aromatic stretching vibration of the C-N bond. In the infrared spectrum of DOPO, at 2437,1143 and 1117cm-1The peaks at (b) correspond to the stretching vibration of the P-H bond, P ═ O stretching vibration and P-O-Ph stretching vibration, respectively. In the infrared spectrogram of the DOPO-COFs nano-sheet, P-H disappears, which indicates that the DOPO and the COFs nano-sheet react. Meanwhile, P ═ O bond and P-O-Ph bond are found in the infrared spectrum of the DOPO-COFs nano sheet, which indicates that the DOPO-COFs nano sheet is successfully synthesized.
FIG. 2 is an X-ray photoelectron spectrum of DOPO-COFs nanosheet in example 1. The phosphorus content of the DOPO-COFs nano-sheet is measured to be 0.69 at%, and the loaded DOPO accounts for 11.6 wt% of the total DOPO-COFs nano-sheet mass. Meanwhile, the successful synthesis of the DOPO-COFs nano-sheet is also demonstrated.
FIG. 3 is a transmission electron micrograph of DOPO-COFs nanosheets in example 1. As can be seen from the figure, the size of the DOPO-COFs nano-sheet is about several hundred nanometers to several micrometers.
Example 3: preparation of phosphorus-containing COFs nanosheets
Dissolving 0.4g of diethyl phosphite in dioxane, dropwise adding the solution into 200g of 0.5 wt% COFs nanosheet suspension at 180 ℃, and reacting for 18 hours after the dropwise adding is finished; and after the reaction is finished, centrifuging the reaction solution at 3000rpm for 10 minutes, carrying out suction filtration on the upper layer liquid, and sequentially washing the obtained product with acetone, chloroform and methanol to obtain the phosphorus-containing COFs nanosheet.
Example 4: preparation of phosphorus-containing COFs nanosheets
Dissolving 20g of dibutyl phosphite in N, N-dimethylformamide, then dropwise adding the dibutyl phosphite into 200g of 0.1 wt% COFs nanosheet suspension at 100 ℃, and reacting for 24 hours after dropwise adding is finished; and after the reaction is finished, centrifuging the reaction solution at 8000rpm for 10 minutes, carrying out suction filtration on the upper layer liquid, and sequentially washing the obtained product with acetone, chloroform and methanol to obtain the phosphorus-containing COFs nanosheet.
Example 5: preparation of phosphorus-containing COFs nanosheets
2g of diphenyl phosphite is dissolved in N, N-dimethylformamide, and then is dropwise added into 200g of 0.5 wt% COFs nanosheet suspension at 160 ℃, and the reaction lasts for 12 hours after the dropwise addition is finished; and after the reaction is finished, centrifuging the reaction solution at 4000rpm for 10 minutes, carrying out suction filtration on the upper layer liquid, and sequentially washing the obtained product with acetone, chloroform and methanol to obtain the phosphorus-containing COFs nanosheet.
Example 6: preparation of phosphorus-containing COFs nanosheets
6g of DOPO is dissolved in dioxane, and then the DOPO is dripped into 200g of 0.5 wt% COFs nanosheet suspension at 145 ℃, and the reaction lasts 15 hours after the dripping is finished; and after the reaction is finished, centrifuging the reaction solution at 3000rpm for 10 minutes, carrying out suction filtration on the upper layer liquid, and sequentially washing the obtained product with acetone, chloroform and methanol to obtain the phosphorus-containing COFs nanosheet.
Example 7: performance comparison
1.6g of DOPO-COFs nano-sheet, 0.186g of DOPO and 1.414g of COFs (DOPO: COFs is 11.6: 88.4), 1.6g of COFs nano-sheet are respectively ultrasonically dispersed in 50ml of tetrahydrofuran solution, then respectively added into 40g of epoxy resin, mechanically stirred at 80 ℃ for 8 hours to remove tetrahydrofuran, finally respectively added with 8.4g of diaminodiphenylmethane, and respectively insulated at 100 ℃ and 150 ℃ for 2 hours. The prepared epoxy resin nano composite is subjected to cone calorimetry and dynamic mechanical analysis tests to research the combustion behavior and mechanical property of the epoxy resin nano composite.
FIG. 4 is a graph of the heat release rate of epoxy resin and its nanocomposites in example 6. After 3.2 wt% of DOPO-COFs nano-sheet is added, the peak value of the heat release rate of the epoxy resin is reduced by 18.4%. The peak heat release rate was also significantly reduced compared to the control. The prepared DOPO-COFs nano-sheet has flame retardant property.
FIG. 5 shows the results of dynamic mechanical analysis of the epoxy resin and its nanocomposite in example 6. Obviously, after the DOPO-COFs nano-sheet is added, the mechanical capacity of the epoxy resin is obviously improved.
Claims (8)
1. A phosphorus-containing covalent organic framework nanosheet is characterized in that the structural general formula is as follows:
wherein Z is a phosphorus-containing structure, and specifically comprises the following structures:
2. a process for the preparation of covalent organic framework nanoplatelets containing phosphorus according to claim 1, characterized in that it comprises the following steps:
step 1: adding a dimethyl sulfoxide solution containing 2.02g of melamine into a single-neck flask with magnetons, then sequentially adding 40ml of a dimethyl sulfoxide solution containing 3.22g of o-phthalaldehyde and 40ml of an acetic acid aqueous solution with the concentration of 3M, vacuumizing the single-neck flask, and reacting at 135 ℃ and 0.1MPa for 3 days to obtain the COFs material;
step 2: dispersing the COFs material obtained in the step 1 in a solvent, carrying out wet ball milling for 24 hours in a ball mill at the rotating speed of 225rpm, and collecting an upper layer suspension after centrifugal separation, namely the COFs nanosheet suspension;
and step 3: dropwise adding a phosphorus-containing compound solution into the COFs nanosheet suspension obtained in the step 2, reacting at 100-180 ℃ for 12-24 hours, and after the reaction is finished, performing centrifugal separation and washing to obtain phosphorus-containing COFs nanosheets; the phosphorus-containing compound is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diethyl phosphite, dimethyl phosphite, dibutyl phosphite or diphenyl phosphite.
3. The method of claim 2, wherein:
in step 2, the solvent is selected from ethanol, chloroform, N-dimethylformamide, dioxane, tetrahydrofuran, acetone or dimethyl sulfoxide.
4. The method of claim 2, wherein:
in step 2, the rotation speed of the centrifugal separation is 3000-.
5. The method of claim 2, wherein:
in the step 2, the concentration of the COFs nanosheet suspension liquid after ball milling is 0.2-1 wt%.
6. The method of claim 2, wherein:
in the step 3, the mass ratio of the phosphorus-containing compound to the COFs nanosheets is 1:1-10: 1.
7. The method of claim 2, wherein:
in step 3, the solvent used by the phosphorus compound-containing solution is methanol, ethanol, diethyl ether, chloroform, N dimethylformamide or dioxane; the concentration of the phosphorus-containing compound solution is 0.2-2 mol/L.
8. The method of claim 2, wherein:
in the step 3, the rotation speed of centrifugal separation is 1500-; the solvent used in washing is one or more of methanol, tetrahydrofuran, acetone and dichloromethane.
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| CN109294506A (en) * | 2018-10-15 | 2019-02-01 | 山东腾熙新材料有限公司 | A kind of conductive adhesive film and preparation method thereof |
| CN110698620B (en) * | 2019-08-30 | 2020-09-11 | 厦门大学 | Vanillyl Schiff base-containing covalent organic framework flame retardant and preparation method thereof |
| CN111100303B (en) * | 2019-12-02 | 2020-11-17 | 厦门大学 | Preparation method and application of organic phosphine grafted hollow metal organic framework material |
| CN111318266B (en) * | 2020-02-14 | 2022-01-28 | 南京师范大学 | Two-dimensional covalent organic framework modified ion exchange resin and preparation method and application thereof |
| CN111320872B (en) * | 2020-04-15 | 2023-04-25 | 盐城申源塑胶有限公司 | Red phosphorus/polyimide covalent organic framework composite material with excellent flame retardant property and preparation method thereof |
| CN113801463B (en) * | 2021-09-06 | 2022-11-22 | 浙江葆润应用材料有限公司 | Anti-condensation material and preparation method thereof |
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| Novel Melamine/o-Phthalaldehyde Covalent Organic Frameworks anosheets: Enhancement Flame Retardantand Mechanical Performances of Thermoplastic Polyurethanes;Xiaowei Mu et al.;《Appl. Mater. Interfaces》;20170721;第9卷(第27期);23017-23026 * |
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