Phosphorus-nitrogen-zinc Two-dimensional Supramolecular Coated Molybdenum Disulfide Hybrid Flame Retardant and Application Thereof

Abstract

The disclosure discloses a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid flame retardant and application thereof, and belongs to the technical field of halogen-free flame retardant. Components of the phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material in the disclosure include, by weight, 1-2 parts of molybdenum disulfide, 1-1.5 parts of zinc salt, 5-8 parts of a nitrogen-containing compound and 5-10 parts of a phosphorus-containing compound. As a flame retardant, the hybrid material of the disclosure effectively exerts an organic-inorganic synergistic flame retardant effect; the flame retardant efficiency of molybdenum disulfide is improved; the addition amount of the flame retardant in a matrix is reduced; the mechanical properties of the matrix can be improved at the same time; and the material has a very good application prospect.

Claims

1. A phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material, comprising the following components by weight: 1-2 parts of molybdenum disulfide, 1-1.5 parts of zinc salt, 5-8 parts of a nitrogen-containing compound and 5-10 parts of a phosphorus-containing compound.

2. The hybrid material according to claim 1, wherein the phosphorus-containing compound comprises one or more of phytic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, amino trimethylene phosphonic acid and ethylenediamine tetramethylene phosphonic acid.

3. The hybrid material according to claim 1, wherein the zinc salt comprises one or more of zinc acetate, zinc chloride and zinc nitrate.

4. The hybrid material according to claim 1, wherein the nitrogen-containing compound comprises one or more of polyethyleneimine, melamine, p-phenylenediamine, ethylenediamine and thiourea.

5. The hybrid material according to claim 1, wherein a preparation method of the hybrid material comprises: preparing the components according to parts by weight and mixing molybdenum disulfide nanosheets, the zinc salt, the nitrogen-containing compound and the phosphorus-containing compound in an aqueous solution for a complete reaction to obtain the hybrid material.

6. The hybrid material according to claim 5, wherein a reaction temperature is 10-60° C.

7. The hybrid material according to claim 1, wherein the phosphorus-containing compound is one or more of phytic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, amino trimethylene phosphonic acid and ethylenediamine tetramethylene phosphonic acid; the zinc salt is one or more of zinc acetate, zinc chloride and zinc nitrate; and the nitrogen-containing compound is one or more of polyethyleneimine, melamine, p-phenylenediamine, ethylenediamine and thiourea.

8. A flame retardant polyacrylonitrile fiber with components containing the hybrid material according to claim 1.

9. The flame retardant polyacrylonitrile fiber according to claim 8, wherein a preparation method of the flame retardant polyacrylonitrile fiber comprises adding the hybrid material according to claim 1 into a polyacrylonitrile spinning solution and then carrying out wet spinning.

10. The flame retardant polyacrylonitrile fiber according to claim 9, wherein a content of the hybrid material is 1%-3% of mass of the flame retardant polyacrylonitrile fiber.

Description

BRIEF DESCRIPTION OF FIGURES

[0019] FIG. 1 is an SEM diagram of a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material obtained in Example 1;

[0020] FIG. 2 is a TEM diagram of the phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material obtained in Example 1;

[0021] FIG. 3 is a thermogravimetric (TG) diagram of a polyacrylonitrile fiber and flame retardant polyacrylonitrile fiber obtained in Example 1;

[0022] FIG. 4 is a diagram showing the heat release rate of the polyacrylonitrile fiber and flame retardant polyacrylonitrile fiber obtained in Example 1;

[0023] FIG. 5 is a diagram showing the total heat release amount of the polyacrylonitrile fiber and flame retardant polyacrylonitrile fiber obtained in Example 1; and

[0024] FIG. 6 is a diagram showing the limit oxygen index of the polyacrylonitrile fiber and flame retardant polyacrylonitrile fiber obtained in Example 1.

DETAILED DESCRIPTION

[0025] A test method: in the disclosure, a miniature calorimeter is used to measure the heat release rate and the total heat release amount; a thermogravimetric analyzer is used to measure the thermogravimetric (TG) diagram; a limit oxygen index instrument is used to measure the limit oxygen index of a fabric made of the flame retardant fiber (GB 5454-1997, LOI<22, inflammable; 22≤LOI≤27, flammable; LOI>27, nonflammable); an XQ-2 single fiber strength tester is used to test the strength of the flame retardant polyacrylonitrile fiber.

EXAMPLE 1

[0026] Preparation of a flame retardant: 0.5 g of melamine and 0.1 g of zinc acetate are dissolved in 200 mL of deionized water, and then 0.1 g of molybdenum disulfide nanosheets are added into the aqueous solution and ultrasonically dispersed uniformly for 2 hours to obtain a dispersion; 0.5 g of phytic acid is slowly added dropwise into the dispersion and stirred at 30° C. for 4 hours. Finally, the mixture is subjected to centrifugal cleaning with deionized water and vacuum drying at 60° C. to obtain a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material.

[0027] After SEM and TEM tests, corresponding topography diagrams are obtained and shown in FIG. 1 and FIG. 2 respectively. According to FIGS. 1 to 2, it can be seen that the surface of the obtained hybrid material is rough, the surfaces of the molybdenum disulfide nanosheets have block-like loads, presenting an obvious sandwich structure, and the molybdenum disulfide nanosheets are successfully coated with the surface flake two-dimensional supramolecules.

[0028] Preparation of a flame retardant polyacrylonitrile fiber: 0.06 g of the phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material is weighed and ultrasonically dispersed in 15 g of N,N-dimethylformamide, 3 g of polyacrylonitrile powder is added and dissolved at 80° C. for 8 hours, and then the mixture is placed in a vacuum oven at 60° C. for 2 hours for defoaming to obtain a spinning solution. The obtained spinning solution is subjected to spinning with a TYD01 spinning syringe pump. The spinning parameters are: speed 10 μL min.sup.−1, needle inner diameter 0.3 mm, and coagulation bath DMF aqueous solution (DMF content 60%); an obtained polyacrylonitrile fiber is dried at 60° C. for 24 hours to obtain the flame retardant polyacrylonitrile fiber.

[0029] The obtained flame retardant polyacrylonitrile fiber is subjected to thermogravimetric analysis, heat release rate test, total heat release amount test and limit oxygen index test, and results are shown in FIG. 3 to FIG. 6 respectively. The specific performance results are shown in Table 1.

EXAMPLE 2

[0030] Preparation of a flame retardant: 0.8 g of melamine and 0.15 g of zinc acetate are dissolved in 200 mL of deionized water, and then 0.2 g of molybdenum disulfide nanosheets are added into the solution and ultrasonically dispersed uniformly for 2 hours to obtain a dispersion; 1 g of phytic acid is slowly added dropwise into the dispersion and stirred at 30° C. for 4 hours. Finally, the mixture is subjected to centrifugal cleaning with deionized water and vacuum drying at 60° C. to obtain a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material.

[0031] Preparation of a flame retardant polyacrylonitrile fiber: With reference to Example 1, a flame retardant polyacrylonitrile fiber is prepared. The specific performance parameters are shown in Table 1.

EXAMPLE 3

[0032] Preparation of a flame retardant: 0.5 g of melamine and 0.1 g of zinc acetate are dissolved in 200 mL of deionized water, and then 0.1 g of molybdenum disulfide nanosheets are added into the solution and ultrasonically dispersed uniformly for 2 hours to obtain a dispersion; 0.5 g of phytic acid is slowly added dropwise into the dispersion and stirred at 60° C. for 4 hours. Finally, the mixture is subjected to centrifugal cleaning with deionized water and vacuum drying at 60° C. to obtain a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material.

[0033] Preparation of a flame retardant polyacrylonitrile fiber: With reference to Example 1, a flame retardant polyacrylonitrile fiber is prepared. The specific performance parameters are shown in Table 1.

EXAMPLE 4

[0034] Preparation of a flame retardant: 0.5 g of polyethyleneimine and 0.1 g of zinc acetate are dissolved in 200 mL of deionized water, and then 0.1 g of molybdenum disulfide nanosheets are added into the solution and ultrasonically dispersed uniformly for 2 hours to obtain a dispersion; 0.8 g of phytic acid is slowly added dropwise into the dispersion and stirred at 10° C. for 8 hours. Finally, the mixture is subjected to centrifugal cleaning with deionized water and vacuum drying at 60° C. to obtain a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material.

[0035] Preparation of a flame retardant polyacrylonitrile fiber: With reference to Example 1, a flame retardant polyacrylonitrile fiber is prepared. The specific performance parameters are shown in Table 1.

EXAMPLE 5

[0036] Preparation of a flame retardant: 0.5 g of polyethyleneimine and 0.1 g of zinc acetate are dissolved in 200 mL of deionized water, and then 0.2 g of molybdenum disulfide nanosheets are added into the solution and ultrasonically dispersed uniformly for 2 hours to obtain a dispersion; 1 g of amino trimethylene phosphonic acid is slowly added dropwise into the dispersion and stirred at 30° C. for 4 hours. Finally, the mixture is subjected to centrifugal cleaning with deionized water and vacuum drying at 60° C. to obtain a phosphorus-nitrogen-zinc two-dimensional supramolecular coated molybdenum disulfide hybrid material.

[0037] Preparation of a flame retardant polyacrylonitrile fiber: With reference to Example 1, a flame retardant polyacrylonitrile fiber is prepared. The specific performance parameters are shown in Table 1.

EXAMPLE 6

[0038] A flame retardant material is prepared with reference to Example 1, and then with reference to the preparation method of the flame retardant polyacrylonitrile fiber in Example 1, a flame retardant PAN fiber is prepared by only changing the amount of the flame retardant into 0.3 g and keeping other conditions unchanged. The specific performance parameters are shown in Table 1.

TABLE-US-00001 TABLE 1 Flame retardant performance data of flame retardant PAN fibers in different examples Maximum Total Residual heat heat Limit Elong- carbon release release oxygen Breaking ation amount rate amount index strength at break Sample (%) (W/g) (kJ/g) (%) (cN) (%) Pure PAN 48.5 182.4 26.6 17.8 56.3 7.2 fiber Example 1 60.2 84.6 19.9 27.9 84.6 9.2 Example 2 58.8 91.3 20.2 27.2 76.8 8.3 Example 3 59.1 88.7 20.7 27.5 81.2 8.6 Example 4 58.3 92.1 18.5 27.2 77.5 7.9 Example 5 58.4 90.2 20.8 27.4 79.8 8.7 Example 6 64.3 78.6 17.8 28.8 53.2 6.8

EXAMPLE 7

Optimization of Preparation Conditions of a Flame Retardant

[0039] With reference to Example 1, the addition amount mass ratio of molybdenum disulfide to zinc acetate to melamine to phytic acid is replaced with the amount ratio shown in Table 2 to prepare a flame retardant PAN fiber. The specific performance parameters of an obtained flame retardant PAN fiber are shown in Table 2.

TABLE-US-00002 TABLE 2 Flame retardant performance of flame retardants prepared according to different mass ratios of molybdenum disulfide to zinc acetate to melamine to phytic acid Mass part ratio of Residual Maximum Total Limit molybdenum disulfide to carbon heat heat release oxygen zinc acetate to melamine amount release rate amount index to phytic acid (%) (W/g) (kJ/g) (%) 0.5:1:5:5 54.2 125.2 24.4 25.4 1:0.5:5:5 56.4 136.2 22.5 26.7 1:1:15:10 56.8 129.9 21.2 26.4

COMPARATIVE EXAMPLE 1

[0040] With reference to the preparation method of the flame retardant polyacrylonitrile fiber in Example 1, flame retardant compounds are respectively replaced with a melamine-cyanuric acid supramolecular/molybdenum disulfide (MCA/MoS2) hybrid material and a molybdenum disulfide nanosheet/silicon dioxide hybrid material to obtain flame retardant polyacrylonitrile fibers. The obtained performance results are shown in Table 3.

TABLE-US-00003 TABLE 3 Performance results of flame retardant polyacrylonitrile fibers prepared by different flame retardants Residual Total heat carbon Maximum heat release Limit amount release rate amount oxygen Flame retardant (%) (W/g) (kJ/g) index (%) MCA/MoS.sub.2 hybrid 55.8 112.3 23.7 25.9 material Molybdenum disulfide nanosheet/silicon 55.5 116.6 25.9 25.5 dioxide hybrid material