Hexamethylenediaminetetramethylene phenyl phosphonic acid ammonium salt, process for its preparation and use

Abstract

The application discloses ammonium hexamethylene diamine tetramethylene diphenyl phosphonate, a preparation method and application thereof, and relates to a new IFR, i.e., HDBG, which is synthesized by electrostatic self-assembly with HDTMPA and BG as raw materials, and then is applied in a high polymer material to prepare a high polymer composite material of ammonium hexamethylene diamine tetramethylene diphenyl phosphonate (HDBG) by melt blending. The HDBG has good compatibility with TPU, improves the flame-retardant property of TPU, and takes into account the mechanical property, which is beneficial to further expanding the application range of TPU.

Description

Technical Field

[0001] The invention belongs to the technical field of flame retardant materials, and particularly relates to hexamethylenediaminetetramethylenephenylphosphonic acid ammonium and a preparation method and application thereof. Background Art

[0002] Flame retardants are used to improve the flame resistance of molecular materials by increasing their ignition point or reducing their combustion rate, thereby increasing rescue time, saving lives, and minimizing damage. Halogen-containing flame retardants are relatively inexpensive, stable, require minimal dosage, have high flame retardant efficiency, and are widely adaptable. They also maintain the inherent physical and chemical properties of flame retardant products. However, once a fire breaks out, thermal decomposition and combustion produce large amounts of smoke, hindering firefighting and evacuation. Halogen-free flame retardants are less corrosive and toxic when burned, producing less smoke, minimizing damage to personnel, equipment, and equipment, and facilitating timely evacuation and rescue efforts in the event of a fire. However, halogen-free flame retardants face a common challenge: achieving a satisfactory flame retardant effect and impacting the mechanical and processing properties of the material. Therefore, the development of a new and highly effective halogen-free flame retardant is of great significance. Summary of the Invention

[0003] The present invention aims to overcome the defects of the prior art and provide hexamethylenediaminetetramethylenephenylphosphonic acid ammonium.

[0004] Another object of the present invention is to provide a method for preparing hexamethylenediaminetetramethylenephenylphosphonic acid ammonium.

[0005] Another object of the present invention is to provide the use of hexamethylenediaminetetramethylenephenylphosphonic acid ammonium.

[0006] The technical solutions of the present invention are as follows:

[0007] Hexamethylenediaminetetramethylenephenylphosphonic acid ammonium, its structural formula is

[0008]

[0009] The preparation method of the above-mentioned hexamethylenediaminetetramethylenephenylphosphonic acid ammonium comprises the following steps:

[0010] (1) Mix benzoguanamine (BG), ethanol, and deionized water, and stir at 45-95° C. until completely dissolved to obtain solution A;

[0011] (2) Hexamethylenediaminetetramethylenephosphonic acid (HDTMPA) and deionized water were mixed and stirred at 45-95° C. until completely dissolved to obtain solution B;

[0012] (3) Solution B was slowly added dropwise to solution A, and pre-reacted at 45°C to 95°C for 1 to 2 hours. A nonionic surfactant was added and the reaction was continued at 45°C to 95°C for 1 to 2 hours. The mixture was then cooled to room temperature, ultrasonically dispersed, and allowed to stand to obtain a white precipitate product C.

[0013] (4) The white precipitate product C is separated by filtration and washed with deionized water, and then dried at 60-105°C for 6-24 hours to obtain the product.

[0014] In a preferred embodiment of the present invention, the molar ratio of phenylguanamine to hexamethylenediaminetetramethylenephosphonic acid is 2-10:1-5.

[0015] Further preferably, in the step (1), the ratio of benzoguanamine, ethanol and deionized water is 0.02-0.1 mol: 200-500 mL: 80-150 mL.

[0016] Further preferably, in the step (2), the ratio of hexamethylenediaminetetramethylenephosphonic acid to deionized water is 0.01-0.05 mol:350-600 mL.

[0017] Further preferably, in the step (3), the amount of the nonionic surfactant added is 0.2 to 0.5 wt % of the total amount of phenylguanamine and hexamethylenediaminetetramethylenephosphonic acid.

[0018] More preferably, the nonionic surfactant is at least one of alkyl glucoside (APG), fatty acid glyceride, fatty acid sorbitan (Span) and polysorbate (Tween).

[0019] The above-mentioned hexamethylenediaminetetramethylenephenylphosphonic acid ammonium is used as a TPU flame retardant.

[0020] The use of the above-mentioned hexamethylenediaminetetramethylenephenylphosphonic acid ammonium in the preparation of flame-retardant TPU materials.

[0021] A flame-retardant TPU material, the raw materials of which include TPU and the above-mentioned hexamethylenediaminetetramethylenephenylphosphonic acid ammonium.

[0022] The present invention utilizes HDTMPA and BG as raw materials to synthesize a novel IFR, HDBG, through electrostatic self-assembly. This IFR is then applied to polymer materials to produce a flame-retardant polymer composite material, prepared by melt blending, using hexamethylenediaminetetramethylenephenylphosphonate (HDBG). This HDBG exhibits excellent compatibility with TPU, increasing the elongation at break of the TPU / 5D2 composite by 5.6% and achieving a tensile strength retention of 94.6%. This demonstrates that HDBG improves the flame retardancy of TPU while also maintaining mechanical properties, potentially expanding the application of TPU. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Shown in Example 2 of the present invention: (a, b) microscopic morphology of HDBG (D2), (c) FTIR spectrum analysis and (d) XRD spectrum analysis.

[0024] Figure 2 Shows the XPS full spectrum, O1s, N1s and C1s spectra and peak separation results of HDBG (D2) and HDTMPA in Example 2 of the present invention.

[0025] Figure 3 The cone calorimetry test results of Example 6 of the present invention and Comparative Examples 1 and 3 are shown. DETAILED DESCRIPTION

[0026] The technical solution of the present invention is further illustrated and described below through specific implementation methods in conjunction with the accompanying drawings.

[0027] Example 1

[0028] BG (0.02 mol, 3.7 g), ethanol (200 mL, 157.8 g), and deionized water (150 mL, 150 g) were added to a three-necked flask and heated with stirring at 45°C until completely dissolved, yielding Solution A1. HDTMPA (0.01 mol, 4.9 g) and deionized water (350 mL, 350 g) were then added to a beaker and heated with stirring at 45°C until completely dissolved, yielding Solution B1. Solution B1 was then slowly added dropwise to Solution A1, and the reaction temperature was controlled at 45°C for a pre-reaction of 2 h. A surfactant, fatty acid glyceride (0.0172 g, representing 0.2% of the total weight of BG + HDTMPA), was then added. The reaction was continued at 45°C for 1 h, then cooled to room temperature and ultrasonically dispersed for 15 min. After standing for 2 h, a white precipitate, Product C1, was obtained. Product C1 was separated by filtration and washed five times with deionized water. Finally, the product was dried at 60 °C for 24 h to obtain the target product D1, namely HDBG.

[0029] Example 2

[0030] Solution BG (0.04 mol, i.e. 7.4 g), ethanol (400 mL, i.e. 315.6 g) and deionized water (80 mL, i.e. 80 g) were added to a three-necked flask, heated and stirred at 80°C until completely dissolved to obtain solution A2; then, HDTMPA (0.03 mol, i.e. 14.7 g) and deionized water (500 mL, i.e. 500 g) were added to a beaker, heated and stirred at 80°C until completely dissolved to obtain solution B2. Then, solution B2 was slowly dripped into solution A2, the reaction temperature was controlled at 80°C for pre-reaction for 2 hours, and then the surfactant fatty acid sorbitan (accounting for 0.4% of the total mass of BG+HDTMPA, i.e. 0.0884 g) was added, and the reaction was continued at 80°C for 2 hours, then cooled to room temperature, ultrasonically dispersed for 30 minutes, and allowed to stand for 4 hours to obtain a white precipitate product C2. C2 was separated by suction and washed 3 times with deionized water. Finally, dried at 80°C for 12 hours) to obtain the following: Figure 1 and Figure 2 And the target product D2 shown in Table 1 is HDBG.

[0031] Table 1 Elemental composition analysis of HDBG (D2)

[0032]

[0033]

[0034] Example 3

[0035] Solution BG (0.1 mol, 18.5 g), ethanol (500 mL, 394.5 g), and deionized water (150 mL, 150 g) were added to a three-necked flask and heated at 95°C with stirring until completely dissolved, yielding Solution A3. HDTMPA (0.03 mol, 14.7 g) and deionized water (600 mL, 600 g) were then added to a beaker and heated at 95°C with stirring until completely dissolved, yielding Solution B3. Solution B3 was then slowly added dropwise to Solution A3, and the reaction temperature was controlled at 95°C for a pre-reaction of 2 h. Surfactant APG (0.166 g, representing 0.5% of the total weight of BG + HDTMPA) was then added. The reaction was continued at 95°C for another 2 h, then cooled to room temperature and ultrasonically dispersed for 60 min. After standing for 6 h, a white precipitate, C3, was obtained. C3 was separated by filtration and washed five times with deionized water. Finally, the product was dried at 105 °C for 24 h to obtain the target product D3, namely HDBG.

[0036] Example 4

[0037] Solution BG (0.06 mol, 11.1 g), ethanol (500 mL, 394.5 g), and deionized water (100 mL, 100 g) were added to a three-necked flask and heated with stirring at 70°C until completely dissolved, yielding Solution A4. HDTMPA (0.04 mol, 19.6 g) and deionized water (350 mL, 350 g) were then added to a beaker and heated with stirring at 90°C until completely dissolved, yielding Solution B4. Solution B4 was then slowly added dropwise to Solution A4, and the reaction temperature was controlled at 80°C for a pre-reaction of 1.5 h. The surfactant polysorbate (0.0921 g, representing 0.3% of the total weight of BG + HDTMPA) was then added. The reaction was continued at 80°C for 1 h, then cooled to room temperature and ultrasonically dispersed for 45 min. After standing for 4 h, a white precipitate, C4, was obtained. C4 was separated by filtration and washed three times with deionized water. Finally, the product was dried at 90 °C for 24 h to obtain the target product D4, namely HDBG.

[0038] The following examples and comparative examples are used to further illustrate the flame retardant effect of the HDBG flame retardant synthesized by the present invention. In terms of application, the HDBG synthesized in Example 2, namely D2, is used as a flame retardant and flame retardant application in TPU is used as an example to illustrate the flame retardant effect of the synthesized HDBG.

[0039] Example 5

[0040] First, TPU and flame retardant D2 were vacuum dried at 80°C for 24 hours; then, TPU (92 parts) and flame retardant D2 (8 parts) were fully blended to obtain E5; then E5 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled at 130°C, 170°C, and 175°C, respectively, and extruded at a speed of 30 r / min to obtain a mixture F5; finally, F5 was added to an injection molding machine and injection molded at 175°C to obtain a flame retardant standard specimen G5 for testing.

[0041] Example 6

[0042] First, TPU and flame retardant D2 were vacuum dried at 110°C for 4 h; then, TPU (95 parts) and flame retardant D2 (5 parts) were fully blended to obtain E6; then E6 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled at 155°C, 180°C, and 185°C, respectively, and extruded at a speed of 50 r / min to obtain a mixture F6; finally, F6 was added to an injection molding machine and injection molded at 180°C to obtain a flame retardant standard specimen G6 for testing.

[0043] Example 7

[0044] First, TPU and flame retardant D2 were vacuum dried at 100°C for 12 hours; then, TPU (94 parts) and flame retardant D2 (6 parts) were fully blended to obtain E7; then E7 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled to 200°C, 200°C, and 200°C, respectively, and extruded at a speed of 40 r / min to obtain a mixture F7; finally, F7 was added to an injection molding machine and injection molded at 190°C to obtain a flame retardant standard specimen G7 for testing.

[0045] Example 8

[0046] First, TPU and flame retardant D2 were vacuum dried at 100°C for 12 hours; then, TPU (93 parts) and flame retardant D2 (7 parts) were fully blended to obtain E8; then E8 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled to 160°C, 175°C, and 175°C, respectively, and extruded at a speed of 40 r / min to obtain a mixture F8; finally, F8 was added to an injection molding machine and injection molded at 180°C to obtain a flame retardant standard specimen G8 for testing.

[0047] Comparative Example 1

[0048] First, TPU was vacuum dried at 110°C for 4 hours; then, TPU (100 parts) was mixed to obtain E9; then E9 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled at 155°C, 180°C, and 185°C, respectively, and extruded at a speed of 50 r / min to obtain a mixture F9; finally, F9 was added to an injection molding machine and injection molded at 180°C to obtain a flame-retardant standard specimen G9 for testing.

[0049] Comparative Example 2

[0050] First, TPU and flame retardant BG were vacuum dried at 110°C for 4 hours; then, TPU (95 parts) and flame retardant BG (5 parts) were fully blended to obtain E10; then E10 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled at 155°C, 180°C, and 185°C, respectively, and extruded at a speed of 50 r / min to obtain a mixture F10; finally, F10 was added to an injection molding machine and injection molded at 180°C to obtain a flame retardant standard specimen G10 for testing.

[0051] Comparative Example 3

[0052] First, TPU and flame retardant HDTMPA were vacuum dried at 110°C for 4 h; then, TPU (95 parts) and flame retardant HDTMPA (5 parts) were fully blended to obtain E11; then E11 was added to a twin-screw extruder, and the temperatures of zones 1 to 3 of the twin-screw extruder were controlled at 155°C, 180°C, and 185°C, respectively, and extruded at a speed of 50 r / min to obtain mixture F11; finally, F11 was added to an injection molding machine and injection molded at 180°C to obtain flame-retardant standard specimen G11 for testing.

[0053] The UL-94 and limiting oxygen index (LOI) of Examples 5 to 8 and Comparative Examples 1 to 3 are shown in Table 2 below:

[0054] Table 2

[0055]

[0056] The results of the vertical burning test show that when only 5% HDBG (D2) is added, the TPU / D2 composite material reaches the UL-94V-0 grade, showing excellent flame retardant properties.

[0057] The test results of tensile strength and elongation at break of Examples 5 to 8 and Comparative Examples 1 to 3 are shown in Table 3 below:

[0058] Table 3

[0059]

[0060]

[0061] The results of tensile strength and elongation at break tests show that HDBG (D2) has good compatibility with TPU. The elongation at break of the TPU / 5D2 composite material increased by 5.6%, and the tensile strength retention rate reached 94.6%, indicating that HDBG (D2) improves the flame retardant properties of TPU while taking into account the mechanical properties.

[0062] The cone calorimetry test results of Example 6, Comparative Example 1 and Comparative Example 3 are as follows: Figure 3 As shown, it can be seen that G6 prepared in Example 6 exhibits obvious flame retardant properties.

[0063] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made within the scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. Hexamethylenediaminetetramethylenephenylphosphonic acid ammonium, characterized in that: Its structural formula is 2. The method for preparing hexamethylenediaminetetramethylenephenylphosphonic acid ammonium according to claim 1, wherein: The steps include: (1) Mix benzoguanamine, ethanol, and deionized water, and stir at 45-95° C. until completely dissolved to obtain solution A; (2) Hexamethylenediaminetetramethylenephosphonic acid and deionized water are mixed and stirred at 45-95° C. until completely dissolved to obtain solution B; (3) Solution B was slowly added dropwise to solution A, and pre-reacted at 45°C to 95°C for 1 to 2 hours. A nonionic surfactant was added and the reaction was continued at 45°C to 95°C for 1 to 2 hours. The mixture was then cooled to room temperature, ultrasonically dispersed, and allowed to stand to obtain a white precipitate product C. (4) The white precipitate product C is separated by filtration and washed with deionized water, and then dried at 60-105°C for 6-24 hours to obtain the product.

3. The preparation method according to claim 2, wherein: The molar ratio of the phenylguanamine to hexamethylenediaminetetramethylenephosphonic acid is 2-10:1-5.

4. The preparation method according to claim 3, wherein: In the step (1), the ratio of benzoguanamine, ethanol and deionized water is 0.02-0.1 mol: 200-500 mL: 80-150 mL.

5. The preparation method according to claim 3, wherein: In the step (2), the ratio of hexamethylenediaminetetramethylenephosphonic acid to deionized water is 0.01-0.05 mol:350-600 mL.

6. The preparation method according to claim 3, wherein: In the step (3), the amount of the nonionic surfactant added is 0.2 to 0.5 wt % of the total amount of phenylguanamine and hexamethylenediaminetetramethylenephosphonic acid.

7. The preparation method according to claim 6, wherein: The nonionic surfactant is at least one of alkyl glucoside, fatty acid glyceride, fatty acid sorbitan and polysorbate.

8. Use of the hexamethylenediaminetetramethylenephenylphosphonic acid ammonium according to claim 1 as a TPU flame retardant.

9. Use of the hexamethylenediaminetetramethylenephenylphosphonic acid ammonium according to claim 1 in the preparation of flame-retardant TPU materials.

10. A flame retardant TPU material, characterized by: The raw materials include TPU and the hexamethylenediaminetetramethylenephenylphosphonic acid ammonium as claimed in claim 1.

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