CT-(MIO) modified polyphosphazene as well as synthesis method and application thereof

Abstract

The invention discloses CT-(MIO) modified polyphosphazene as well as a synthesis method and application thereof. The CT-(MIO) modified polyphosphazene is obtained by chemically modifying phosphorus atoms in the phosphazene repetition structure unit of a polyphosphazene high-polymer material by CT-(MIO) derivatives, or obtained by chemically modifying the phosphorus atoms of a phosphonitrilic chloride trimer monomer by CT-(MIO) derivatives, and then carrying out a polymerization reaction. According to the CT-(MIO) modified polyphosphazene disclosed by the invention, free radicals with a proper redox potential are fixed to a conducting polyphosphazene side chain in a conjugating manner to form a stable free radical polymer, wherein each free radical unit is capable of participating in an electrode reaction, and reaction electronics can be rapidly transmitted through the main chain of the polymer, so that the CT-(MIO) modified polyphosphazene has excellent electrochemical performance, conductive performance, charge storage density, capacitance retention rate and rapid electrode reaction dynamic performance, and is expected to become a new high-capacity and high-power battery material.

Description

technical field

[0001] The invention belongs to the field of conductive polymer materials, and in particular relates to a kind of polyphosphazene modified by isozaindene nitrogen oxide radical, its synthesis method and application. Background technique

[0002] Polyphosphazene (polyphosphazene) is a kind of elemental organic polymer whose skeleton is alternately arranged with phosphorus and nitrogen single and double bonds, and the side group is composed of organic groups. It mainly includes two types of cyclic and linear polyphosphazenes. Polyphosphazene is widely used in heat-resistant and flame-retardant materials, while linear polyphosphazene is more widely used. In the linear polyphosphazene structure, the flexibility of the main chain formed by alternating single and double bonds of phosphorus and nitrogen is very good. By changing the side groups, polyphosphazene can form different types of polymers such as rubber, plastics, and fibers. Water can also be hydrophobic,...

Examples

Embodiment 1

[0045] Poly(diisozaindene nitroxide radical aminophosphazene)

[0046] In a single-necked flask of 250 mL of sulfamic acid (0.1165 g, 1.2 mmol), calcium sulfate dihydrate (0.1033 g, 0.6 mmol), ammonium chloride (20.0 g, 0.374 mmol), phosphorus pentachloride (66.0 g, 0.317 mmol) mmol) and 1,2,4-trichlorobenzene (23mL), quickly heated up to 210°C for 0.5h, then cooled to 190°C for 3h, cooled to room temperature after the reaction, filtered, reprecipitated with petroleum ether, and then used Tetrahydrofuran was dissolved in petroleum ether to reprecipitate, and the oil pump was vacuum-dried at room temperature to obtain polydichlorophosphazene.

[0047] Under nitrogen protection, polydichlorophosphazene (0.058g, 1mmol), tetrahydrofuran (10mL), triethylamine (0.193mL) were added dropwise with 5-amino-1,1,3,3-tetramethyliso A tetrahydrofuran (3ml) solution of azaindene nitroxide radical (0.218, 1mmol) was added dropwise and reacted at room temperature for 12 hours. After the react...

Embodiment 2

[0051] Poly(isozaindene nitroxide radical amine-anilino-phosphazene)

[0052] In a single-necked flask of 250 mL of sulfamic acid (0.1165 g, 1.2 mmol), calcium sulfate dihydrate (0.1033 g, 0.6 mmol), ammonium chloride (20.0 g, 0.374 mmol), phosphorus pentachloride (66.0 g, 0.317 mmol) mmol) and 1,2,4-trichlorobenzene (23mL), quickly heated up to 210°C for 0.5h, then cooled to 190°C for 3h, cooled to room temperature after the reaction, filtered, reprecipitated with petroleum ether, and then used Tetrahydrofuran was dissolved in petroleum ether to reprecipitate, and the oil pump was vacuum-dried at room temperature to obtain polydichlorophosphazene.

[0053] Under nitrogen protection, polydichlorophosphazene (0.058g, 1mmol), tetrahydrofuran (10mL), triethylamine (0.193mL) were added dropwise with 5-amino-1,1,3,3-tetramethyliso Azaindene nitrogen oxide radical (0.109, 0.5mmol) and aniline (0.047g, 0.5mmol) in tetrahydrofuran (3mL) solution, after the dropwise addition, react at...

Embodiment 3

[0055] Poly(diisozaindene nitroxide radical vinyl phosphazene)

[0056] Put 3g of hexachlorocyclotriphosphazene monomer into a clean polymerization tube that has been dried with an alcohol blowtorch. After the polymerization tube is connected to a vacuum and inert gas device, turn on the pump to pump for 30 minutes, and then pass in nitrogen to pump. vacuum. After repeating three to four times, close the valve. Melt the hexachlorocyclotriphosphazene in the polymerization tube, cool it down to room temperature, re-evacuate for about 3 hours, and then seal the tube with an alcohol torch. Put the sealed polymerization tube into an oil bath at 250°C for polymerization. During the polymerization, observe the situation in the polymerization tube at any time. Take the polymerization tube out of the oil bath, put it in a glove box filled with nitrogen, and break the polymerization tube. The polymer was taken out from the tube, shredded and put into a round bottom flask, and dry pet...

technical field

[0001] The invention belongs to the field of conductive polymer materials, and in particular relates to a kind of polyphosphazene modified by isozaindene nitrogen oxide radical, its synthesis method and application. Background technique

[0002] Polyphosphazene (polyphosphazene) is a kind of elemental organic polymer whose skeleton is alternately arranged with phosphorus and nitrogen single and double bonds, and the side group is composed of organic groups. It mainly includes two types of cyclic and linear polyphosphazenes. Polyphosphazene is widely used in heat-resistant and flame-retardant materials, while linear polyphosphazene is more widely used. In the linear polyphosphazene structure, the flexibility of the main chain formed by alternating single and double bonds of phosphorus and nitrogen is very good. By changing the side groups, polyphosphazene can form different types of polymers such as rubber, plastics, and fibers. Water can also be hydrophobic,...

Examples

Embodiment 1

[0045] Poly(diisozaindene nitroxide radical aminophosphazene)

[0046] In a single-necked flask of 250 mL of sulfamic acid (0.1165 g, 1.2 mmol), calcium sulfate dihydrate (0.1033 g, 0.6 mmol), ammonium chloride (20.0 g, 0.374 mmol), phosphorus pentachloride (66.0 g, 0.317 mmol) mmol) and 1,2,4-trichlorobenzene (23mL), quickly heated up to 210°C for 0.5h, then cooled to 190°C for 3h, cooled to room temperature after the reaction, filtered, reprecipitated with petroleum ether, and then used Tetrahydrofuran was dissolved in petroleum ether to reprecipitate, and the oil pump was vacuum-dried at room temperature to obtain polydichlorophosphazene.

[0047] Under nitrogen protection, polydichlorophosphazene (0.058g, 1mmol), tetrahydrofuran (10mL), triethylamine (0.193mL) were added dropwise with 5-amino-1,1,3,3-tetramethyliso A tetrahydrofuran (3ml) solution of azaindene nitroxide radical (0.218, 1mmol) was added dropwise and reacted at room temperature for 12 hours. After the react...

Embodiment 2

[0051] Poly(isozaindene nitroxide radical amine-anilino-phosphazene)

[0052] In a single-necked flask of 250 mL of sulfamic acid (0.1165 g, 1.2 mmol), calcium sulfate dihydrate (0.1033 g, 0.6 mmol), ammonium chloride (20.0 g, 0.374 mmol), phosphorus pentachloride (66.0 g, 0.317 mmol) mmol) and 1,2,4-trichlorobenzene (23mL), quickly heated up to 210°C for 0.5h, then cooled to 190°C for 3h, cooled to room temperature after the reaction, filtered, reprecipitated with petroleum ether, and then used Tetrahydrofuran was dissolved in petroleum ether to reprecipitate, and the oil pump was vacuum-dried at room temperature to obtain polydichlorophosphazene.

[0053] Under nitrogen protection, polydichlorophosphazene (0.058g, 1mmol), tetrahydrofuran (10mL), triethylamine (0.193mL) were added dropwise with 5-amino-1,1,3,3-tetramethyliso Azaindene nitrogen oxide radical (0.109, 0.5mmol) and aniline (0.047g, 0.5mmol) in tetrahydrofuran (3mL) solution, after the dropwise addition, react at...

Embodiment 3

[0055] Poly(diisozaindene nitroxide radical vinyl phosphazene)

[0056] Put 3g of hexachlorocyclotriphosphazene monomer into a clean polymerization tube that has been dried with an alcohol blowtorch. After the polymerization tube is connected to a vacuum and inert gas device, turn on the pump to pump for 30 minutes, and then pass in nitrogen to pump. vacuum. After repeating three to four times, close the valve. Melt the hexachlorocyclotriphosphazene in the polymerization tube, cool it down to room temperature, re-evacuate for about 3 hours, and then seal the tube with an alcohol torch. Put the sealed polymerization tube into an oil bath at 250°C for polymerization. During the polymerization, observe the situation in the polymerization tube at any time. Take the polymerization tube out of the oil bath, put it in a glove box filled with nitrogen, and break the polymerization tube. The polymer was taken out from the tube, shredded and put into a round bottom flask, and dry pet...

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