Crosslinking poly(organophosphazenes) microsphere and preparation method thereof

[0020] Example 1:

[0021] Add 0.1 g (0.29 mmol) of hexachlorocyclotriphosphazene, 0.22 g (0.86 mmol) of 4,4'-dihydroxydiphenyl sulfone and 0.17 g (1.73 mmol) of triethylamine into a 150 ml flask, and then Add 90 ml of acetone and stir to dissolve. Under 25℃, magnetically stir the reaction for 2 hours. After the reaction, the solid is separated by centrifugation. The crude product is washed three times with acetone, then three times with deionized water, and finally in a vacuum oven. After drying for 24 hours, 0.52 g of crosslinked polyphosphazene microspheres were obtained, and the yield based on hexachlorocyclotriphosphazene was 47%.

[0022] figure 1 Is the transmission electron micrograph of the crosslinked polyphosphazene microspheres, figure 2 Is a scanning electron micrograph of cross-linked polyphosphazene microspheres, image 3 It is a field emission scanning electron microscope photo of cross-linked polyphosphazene microspheres. It can be seen from the photo that the diameter of the microspheres is 0.5-5 microns, and the surface of the microspheres is flat and solid.

[0023] Figure 4 It is the X-ray energy spectrum (EDAX) spectrum of cross-linked polyphosphazene microspheres. It is known that the cross-linked polyphosphazene microspheres contain carbon, nitrogen, phosphorus, sulfur, oxygen and chlorine.

[0024] Figure 5 It is the nuclear magnetic resonance phosphorus spectrum and carbon spectrum of the cross-linked polyphosphazene microspheres. The corresponding attributions of signals 1, 2, 3, and 4 in the carbon spectrum and signals 5 and 6 in the phosphorus spectrum have been marked in the figure.

[0025] Figure 6 It is the Fourier transform infrared spectrum of crosslinked polyphosphazene microspheres. Bands 2 and 3 are the resonance absorption of the benzene ring, bands 4 and 6 are the resonance absorption of the sulfone group, and band 5 is the resonance absorption of the P=N bond. , Band 7 is the resonance absorption of the PO-Ar bond. Nuclear magnetic and infrared spectroscopy analysis showed that its structure is a cross-linked condensation structure of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenylsulfone.

[0026] Figure 7 It is the thermogravimetric curve (TGA) of cross-linked polyphosphazene microspheres in a nitrogen atmosphere. It is known from the figure that the decomposition temperature under a nitrogen atmosphere is 542°C.

[0027] Example 2:

[0028] Add 1 g (2.9 mmol) of hexachlorocyclotriphosphazene, 2.2 g (8.6 mmol) of 4,4'-dihydroxydiphenylsulfone and 34 g (346 mmol) of triethylamine to a 500 ml flask, and then Add 250ml of acetone, stir to dissolve, at 25℃, magnetically stir the reaction for 1 hour, after the reaction, the solid is separated by centrifugation, the crude product is washed with acetone three times, then washed with deionized water three times, and finally in a vacuum oven After drying for 24 hours, 1.17 g of cross-linked polyphosphazene microspheres were obtained, and the yield based on hexachlorocyclotriphosphazene was 64%. The electron microscope photos show that the diameter of the microspheres is 0.4-4.5 microns, and the surface of the microspheres is flat and solid. Spectroscopic analysis shows that the structure is a cross-linked condensation structure of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenylsulfone .

[0029] Example 3:

[0030] The equipment and preparation process described in Example 1 were used, except that the reaction temperature was carried out at the reflux temperature of acetone, and the yield was 55% based on hexachlorocyclotriphosphazene. The analysis of the experimental results shows that the diameter of the microspheres is 0.5-4.5 microns, and the surface of the microspheres is flat and solid, and the structure is a cross-linked condensation structure of hexachlorocyclotriphosphazene and 4,4'-dihydroxydiphenylsulfone.