1. The phosphorus-containing triazole metal complex is characterized in that the structural formula of the phosphorus-containing triazole metal complex is any one of the following formulas:

wherein M is one of Al, Ca, Zn, Fe, Co, Ni and Ag, and n is the valence of M.

2. The preparation method of the metal complex containing the phosphorus triazole as claimed in claim 1, which is characterized in that:

1) dissolving a phosphopolyazole compound in a solvent to obtain a solution A; dissolving a metal salt in a solvent to obtain a solution B;

2) adding the solution A into a three-neck flask provided with a thermometer and a mechanical stirrer, dropwise adding an alkali metal hydroxide solution into the three-neck flask through a constant-pressure dropping funnel, and reacting at a certain temperature until the pH value is 7;

3) dropwise adding the solution B into the solution obtained in the step 2), stopping the reaction after reacting for several hours, carrying out vacuum filtration to remove the solvent to obtain a crude product, and finally washing the crude product with the solvent for several times to obtain the phosphorus-containing polynitrogen azole metal complex.

3. The preparation method of the metal complex containing phosphorus-containing polyazole according to claim 2, wherein the chemical structure of the compound containing phosphorus-containing polyazole is any one of the following:

4. the process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the metal salt is one of anhydrous calcium chloride, calcium nitrate tetrahydrate, anhydrous calcium sulfate, calcium carbonate, calcium acetate, aluminum trichloride hexahydrate, aluminum nitrate nonahydrate, aluminum sulfate, zinc nitrate hexahydrate, zinc sulfate heptahydrate, zinc acetate, ferric nitrate nonahydrate, ferric chloride, ferric sulfate, cobalt nitrate hexahydrate, cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt dichloride, nickel nitrate hexahydrate, nickel sulfate, nickel chloride hexahydrate, silver nitrate and silver nitrite.

5. The process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the solvent is one or more of deionized water, methanol, absolute ethyl alcohol and N, N-dimethylformamide.

6. The process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the alkali metal hydroxide is one or two of potassium hydroxide and sodium hydroxide.

7. The process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the molar ratio of the metal salt to the phosphorus-containing polynitrogen azole compound is 1: 1-6.

8. The process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the molar use ratio of the alkali metal hydroxide to the phosphorus-containing polynitrogen azole compound is 1: 1-4.

9. The process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the molar use ratio of the phosphorus-containing polynitrogen azole compound to the solvent is 1: 25-50, and the molar using ratio of the metal salt to the solvent is 1: 40-110.

10. The process for preparing a phosphopolyazole metal complex according to claim 2, wherein: the reaction temperature of the step 2) is 5-60 ℃, and the reaction time of the step 3) is 4-15 hours.

Background

The emergence of fire has promoted the development history of human civilization, and the fire brings huge threat to public safety and social development simultaneously. Many daily necessities used in our daily life contain extremely flammable and combustible materials, and once a fire breaks out, the fire can bring harm to our lives and properties, so that the materials are endowed with flame retardant property. At present, due to the requirement of no halogenation, the organic phosphorus flame retardant is a hot point of current research by virtue of the advantages of environmental protection, low toxicity, high flame retardant efficiency and the like. In recent years, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and phosphonochloride and derivatives thereof have been reported to work in relation to flame retardance both at home and abroad, and the flame retardant mainly plays a gas phase flame retardant mechanism.

Disclosure of Invention

The invention aims to provide a phosphorus-containing triazole metal complex compound to solve the problem of flammability of high polymer materials.

The structure of the phosphorus-containing polynitrogen azole metal complex is shown as the following formula:

wherein M is Al, Ca, Zn, Fe, Co, Ni, Ag, and n is the valence of M.

The preparation method of the phosphorus-containing polynitrogen azole metal complex comprises the following steps:

1) dissolving a certain amount of phosphorus-containing triazole compound in a proper amount of solvent to obtain a solution A; dissolving a certain amount of metal salt in a proper amount of solvent to obtain a solution B;

2) adding the solution A into a three-neck flask provided with a thermometer and a mechanical stirrer, dropwise adding an alkali metal hydroxide solution into the three-neck flask through a constant-pressure dropping funnel, and reacting at a certain temperature until the pH is 7.

3) Dropwise adding the solution B into the solution obtained in the step 2), stopping the reaction after reacting for several hours, carrying out vacuum filtration to remove the solvent to obtain a crude product, and washing the crude product for several times by using the solvent to obtain the phosphorus-containing polynitrogen azole metal complex.

The chemical structure of the phosphorus-containing triazole compound is one of the following:

the metal salt is one of anhydrous calcium chloride, calcium nitrate tetrahydrate, anhydrous calcium sulfate, calcium carbonate, calcium acetate, aluminum trichloride hexahydrate, aluminum nitrate nonahydrate, aluminum sulfate, zinc nitrate hexahydrate, zinc sulfate heptahydrate, zinc acetate, ferric nitrate nonahydrate, ferric chloride, ferric sulfate, cobalt nitrate hexahydrate, cobalt sulfate, cobalt carbonate, cobalt acetate, cobalt dichloride, nickel nitrate hexahydrate, nickel sulfate, nickel chloride hexahydrate, silver nitrate and silver nitrite.

The solvent is one or more of deionized water, methanol, absolute ethyl alcohol and N, N-dimethylformamide.

The alkali metal hydroxide is one or two of potassium hydroxide and sodium hydroxide.

The molar use ratio of the metal salt to the phosphorus-containing polynitrogen azole compound is 1: 1-6.

The molar use ratio of the alkali metal hydroxide to the phosphorus-containing polynitrogen azole compound is 1: 1-4.

The molar use ratio of the phosphorus-containing polynitrogen azole compound to the solvent is 1: 25-50, and the molar using ratio of the metal salt to the solvent is 1: 40-110.

The reaction temperature of the step 2) is 5-60 ℃, and the reaction time of the step 3) is 4-15 hours.

The phosphorus-containing triazole metal complex provided by the invention has a gas-phase and condensed-phase flame retardant mechanism, a phosphorus-containing free radical can play a quenching role in the combustion process so as to interrupt and delay combustion, and a nitrogen-containing compound and a sulfur-containing compound can release non-combustible gas so as to play a role in diluting oxygen and taking away heat; meanwhile, the formed phosphoric acid catalyzes the dehydration and carbonization of the matrix, and metal ions catalyze the carbonization to form a compact carbon layer, so that the heat exchange between the matrix and the outside is isolated.

The phosphorus-containing triazole metal complex obtained by the invention has the following advantages:

1. the phosphorus-containing triazole metal complex prepared by the invention contains phosphorus, nitrogen and sulfur flame retardant elements, can play a role in synergistic flame retardance, and simultaneously contains metal elements which can catalyze a substrate to form carbon during combustion, so that the flame retardant efficiency is high.

2. The preparation method of the phosphorus-containing polynitrogen azole metal complex has the advantages of high yield, simple process and environmental protection.

Drawings

FIG. 1 is an infrared spectrum of a phosphorus-containing triazole metal complex flame retardant (synthesized in example 18 and example 22).

FIG. 2 is an XRD spectrum of a phosphorus-containing polynitrogen azole metal complex flame retardant synthesized in example 18 and example 22.

Detailed Description

The preparation method of the phosphorus-containing triazole compound comprises the following steps:

DOPO and CH₂Cl₂Adding into a three-neck flask equipped with a thermometer and a mechanical stirrer, adding a certain amount of acid-binding agent after the raw materials are uniformly mixed, adding an azole compound after the raw materials are completely dissolved, and then adding CCl dropwise₄Reacting at room temperature for a period of time after the dropwise addition is finished, finally carrying out suction filtration on the obtained solution, taking a filter cake, and using CH₂Cl₂Washing for 1 time, then washing for 2 times by deionized water, and drying to obtain the phosphopoly-azazole compound. (D-ATA, D-MBZ, D-ABZ and D-3-ATA are prepared by the method)

Adding an azole compound and acetonitrile into a three-neck flask provided with a thermometer and a mechanical stirrer, adding a certain amount of triethylamine after the raw materials are uniformly mixed, dropwise adding an acetonitrile solution mixed with phosphonyl chloride into the three-neck flask AT normal temperature after the raw materials are completely dissolved, reacting AT normal temperature for a period of time after the dropwise adding is finished, then heating and refluxing for a period of time, cooling to room temperature after the reaction is finished, and carrying out post-treatment to obtain the phosphorus-containing polynitrogen azole compound (prepared by the method) B-ATA, D-AT, D-5-AT, D-2-ABZ, P-3-ATA and D-3-AT). The preparation method of the phosphorus-containing triazole metal complex is shown as the following example:

example 1

0.04mol of D-ATA is dissolved in 80ml of methanol (the resulting solution is denoted A), and 0.02mol of anhydrous calcium chloride is dissolved in 40ml of deionized water (the resulting solution is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 4 hours of reaction. The solvent was removed by suction filtration under reduced pressure to give the crude product, which was washed with deionized water 3 times to give the product D-ATA-Ca in 78% yield.

Example 2

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is denoted A), and 0.02mol of calcium carbonate is dissolved in 40ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Ca with the yield of 83%.

Example 3

0.04mol of B-ATA is dissolved in 80ml of absolute ethanol (the resulting solution is denoted A), and 0.04mol of calcium nitrate tetrahydrate is dissolved in 80ml of absolute ethanol (the resulting solution is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 6 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product B-ATA-Ca with the yield of 82%.

Example 4

0.04mol of B-ATA is dissolved in 80ml of absolute ethyl alcohol (the solution obtained is denoted A), and 0.04mol of anhydrous calcium sulfate is dissolved in 80ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 6 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product B-ATA-Ca with the yield of 84%.

Example 5

0.04mol of D-AT is dissolved in 80ml of methanol (the resulting solution is designated A), and 0.025mol of calcium acetate is dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with methanol for 1 time to obtain a product D-AT-Ca with the yield of 80%.

Example 6

0.04mol of D-AT is dissolved in 80ml of absolute ethanol (the solution obtained is designated A), and 0.02mol of anhydrous calcium sulfate is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 6 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-AT-Ca with the yield of 82%.

Example 7

0.03mol of D-ATA is dissolved in 60ml of absolute ethanol (the solution obtained is designated A), and 0.01mol of aluminum trichloride hexahydrate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 15ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Al, wherein the yield is 80%.

Example 8

0.03mol of D-ATA is dissolved in 60ml of methanol (the resulting solution is designated A), and 0.015mol of aluminum nitrate nonahydrate is dissolved in 25ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 15ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Al, wherein the yield is 83%.

Example 9

0.03mol of D-5-AT is dissolved in 60ml of N' -N-dimethylformamide (the solution obtained is designated A) and 0.015mol of aluminum nitrate nonahydrate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Al, wherein the yield is 84%.

Example 10

0.03mol of D-5-AT is dissolved in 60ml of N' -N-dimethylformamide (the solution obtained is designated A), and 0.015mol of aluminum sulfate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Al, wherein the yield is 84%.

Example 11

0.03mol of D-5-AT is dissolved in 60ml of N' -N-dimethylformamide (the solution obtained is designated A), and 0.01mol of aluminum sulfate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Al, wherein the yield is 84%.

Example 12

0.03mol of D-AT is dissolved in 60ml of N' -N-dimethylformamide (the solution obtained is designated A), and 0.01mol of aluminum sulfate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 15ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-AT-Al, wherein the yield is 80%.

Example 13

0.03mol of D-MBZ is dissolved in 60ml of deionized water (the resulting solution is designated A), and 0.01mol of aluminum sulfate is dissolved in 20ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-MBZ-Al, wherein the yield is 85%.

Example 14

0.03mol of D-MBZ was dissolved in 60ml of deionized water (the resulting solution is designated A), and 0.01mol of aluminum nitrate nonahydrate was dissolved in 20ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-MBZ-Al, wherein the yield is 86%.

Example 15

0.03mol of B-ATA is dissolved in 60ml of absolute ethanol (the solution obtained is denoted A), and 0.01mol of aluminum sulfate is dissolved in 20ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 30ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product B-ATA-Al with the yield of 80%.

Example 16

0.03mol of B-ATA is dissolved in 60ml of absolute ethanol (the solution obtained is denoted A), and 0.01mol of aluminum sulfate is dissolved in 20ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 30ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product B-ATA-Al with the yield of 80%.

Example 17

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is denoted A), and 0.02mol of zinc nitrate hexahydrate is dissolved in 40ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Zn, wherein the yield is 82%.

Example 18

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is denoted A), and 0.01mol of zinc nitrate hexahydrate is dissolved in 40ml of absolute ethanol (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Zn with the yield of 88%.

Example 19

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is marked as A), and 0.01mol of zinc sulfate nonahydrate is dissolved in 40ml of absolute ethanol (the solution obtained is marked as B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Zn, wherein the yield is 84%.

Example 20

0.04mol of D-5-AT is dissolved in 80ml of N' N-dimethylformamide (the solution obtained is designated A), and 0.02mol of zinc acetate is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 30ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Zn with the yield of 86%.

Example 21

0.03mol of D-ATA is dissolved in 60ml of methanol (the resulting solution is designated A), and 0.01mol of ferric chloride is dissolved in 20ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 15ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Fe, wherein the yield is 85%.

Example 22

0.03mol of D-ATA is dissolved in 60ml of absolute ethanol (the solution obtained is designated A), and 0.01mol of ferric nitrate nonahydrate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 15ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Fe, wherein the yield is 87%.

Example 23

0.03mol of D-ATA is dissolved in 60ml of absolute ethanol (the solution obtained is designated A), and 0.01mol of iron sulfate is dissolved in 20ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 15ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Fe, wherein the yield is 85%.

Example 24

0.03mol of D-ABZ was dissolved in 60ml of absolute ethanol (the resulting solution is designated A), and 0.01mol of iron nitrate nonahydrate was dissolved in 20ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ABZ-Fe, wherein the yield is 85%.

Example 25

0.03mol of D-ABZ was dissolved in 60ml of absolute ethanol (the resulting solution is designated A), and 0.01mol of ferric chloride was dissolved in 20ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 2 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ABZ-Fe, wherein the yield is 88%.

Example 26

0.06mol of D-5-AT is dissolved in 80ml of N' N-dimethylformamide (the resulting solution is designated A), and 0.01mol of cobalt nitrate hexahydrate is dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Co, wherein the yield is 86%.

Example 27

0.06mol of D-5-AT is dissolved in 80ml of N' -dimethylformamide (the solution obtained is denoted by A) and 0.01mol of cobalt dichloride is dissolved in 40ml of deionized water (the solution obtained is denoted by B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Co, wherein the yield is 86%.

Example 28

0.06mol of D-5-AT is dissolved in 80ml of N' N-dimethylformamide (the solution obtained is designated A), and 0.01mol of cobalt sulfate is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Co, wherein the yield is 88%.

Example 29

0.04mol of D-ATA is dissolved in 80ml of absolute ethyl alcohol (the solution obtained is marked as A), and 0.01mol of cobalt carbonate is dissolved in 40ml of deionized water (the solution obtained is marked as B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product with deionized water for 3 times, and washing with absolute ethyl alcohol for 1 time to obtain a product D-ATA-Co, wherein the yield is 85%.

Example 30

0.06mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is designated A), and 0.01mol of cobalt acetate is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 30ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and then washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-ATA-Co, wherein the yield is 84%.

Example 31

0.06mol of D-MBZ was dissolved in 80ml of absolute ethanol (the resulting solution is designated A) and 0.01mol of cobalt acetate was dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 30ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-MBZ-Co, wherein the yield is 88%.

Example 32

0.04mol of D-MBZ is dissolved in 80ml of absolute ethanol (the solution obtained is designated A) and 0.01mol of cobalt dichloride is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and then washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-MBZ-Co, wherein the yield is 86%.

Example 33

0.04mol of D-2-ABZ was dissolved in 80ml of methanol (the resulting solution is designated A), and 0.01mol of cobalt acetate was dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using methanol to obtain a product D-2-ABZ-Co, wherein the yield is 85%.

Example 34

0.04mol of D-2-ABZ was dissolved in 80ml of absolute ethanol (the resulting solution is designated A), and 0.01mol of cobalt nitrate hexahydrate was dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and then washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-2-ABZ-Co, wherein the yield is 88%.

Example 35

0.06mol of D-ABZ was dissolved in 100ml of absolute ethanol (the resulting solution is designated A), and 0.01mol of nickel nitrate hexahydrate was dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and then washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-ABZ-Ni, wherein the yield is 83%.

Example 36

0.06mol of D-ABZ was dissolved in 100ml of absolute ethanol (the resulting solution is designated A) and 0.01mol of nickel sulfate was dissolved in 40ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and then washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-ABZ-Ni, wherein the yield is 86%.

Example 37

0.04mol of D-5-AT is dissolved in 80ml of N' N-dimethylformamide (the solution obtained is designated A), and 0.02mol of nickel sulfate is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 30ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Ni, wherein the yield is 83%.

Example 38

0.06mol of D-5-AT is dissolved in 100ml of N' N-dimethylformamide (the solution obtained is designated A), and 0.01mol of nickel chloride hexahydrate is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, and washing the crude product for 3 times by using deionized water to obtain a product D-5-AT-Ni, wherein the yield is 85%.

Example 39

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is denoted A), and 0.02mol of nickel nitrate hexahydrate is dissolved in 40ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and obtaining a product P-ATA-Ni after 1 time by using absolute ethyl alcohol, wherein the yield is 85%.

Example 40

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is denoted A), and 0.04mol of silver nitrate is dissolved in 40ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-ATA-Ag, wherein the yield is 80%.

EXAMPLE 41

0.04mol of D-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is designated A), and 0.04mol of silver nitrite is dissolved in 40ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L sodium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-ATA-Ag, wherein the yield is 87%.

Example 42

0.02mol of B-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is denoted A), and 0.04mol of silver nitrite is dissolved in 80ml of deionized water (the solution obtained is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 12 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product B-ATA-Ag, wherein the yield is 80%.

Example 43

0.02mol of B-ATA is dissolved in 40ml of N' N-dimethylformamide (the resulting solution is denoted A), and 0.04mol of silver nitrate is dissolved in 80ml of deionized water (the resulting solution is denoted B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 15 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product B-ATA-Ag, wherein the yield is 85%.

Example 44

0.01mol of D-3-ATA is dissolved in 80ml of absolute ethanol (the solution obtained is designated A), and 0.02mol of zinc nitrate hexahydrate is dissolved in 80ml of deionized water (the solution obtained is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 35 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 8 hours. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-3-ATA-Zn, wherein the yield is 80%.

Example 45

0.01mol of D-3-ATA is dissolved in 40ml of N' N-dimethylformamide (the resulting solution is designated A), and 0.01mol of silver nitrate is dissolved in 80ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 6 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-3-ATA-Ag, wherein the yield is 85%.

Example 46

0.02mol of P-3-ATA is dissolved in 80ml of methanol (the resulting solution is designated A), and 0.04mol of ferric nitrate nonahydrate is dissolved in 100ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 45 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 5 hours of reaction. And (3) removing the solvent by vacuum filtration to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product P-3-ATA-Fe, wherein the yield is 75%.

Example 47

0.02mol of D-3-AT was dissolved in 80ml of N' N-dimethylformamide (the resulting solution is designated A), and 0.015mol of cobalt nitrate hexahydrate was dissolved in 100ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 40ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 60 ℃ until the pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 10 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-3-AT-Co, wherein the yield is 75%.

Example 48

0.01mol of D-3-AT is dissolved in 80ml of methanol (the resulting solution is designated A), and 0.01mol of silver nitrate is dissolved in 80ml of deionized water (the resulting solution is designated B). The resulting solution A was charged into a three-necked flask equipped with a thermometer and a mechanical stirrer, and 20ml of a 1mol/L potassium hydroxide solution was dropwise added to the three-necked flask through a constant pressure dropping funnel, followed by reaction at 25 ℃ until pH was 7. Then, the solution B was added dropwise to the above solution, and the reaction was stopped after 2 hours of reaction. And (3) carrying out suction filtration under reduced pressure to remove the solvent to obtain a crude product, washing the crude product for 3 times by using deionized water, and washing the crude product for 1 time by using absolute ethyl alcohol to obtain a product D-3-AT-Ag, wherein the yield is 70%.

The infrared spectrogram and XRD spectrogram of the phosphorus-containing triazole metal complex flame retardant (synthesized in the examples 18 and 22) are respectively shown in figures 1 and 2, and the data in the figures shows that the phosphorus-containing triazole metal complex is successfully synthesized.