High-efficiency flame retardant suitable for flame-retardant PET (polyethylene terephthalate) as well as preparation method and application of high-efficiency flame retardant

Abstract

The invention discloses a high-efficiency flame retardant applicable to flame-retardant PET (polyethylene terephthalate) as well as a preparation method and application of the high-efficiency flame retardant, and belongs to the technical field of flame-retardant PET. The nano co-doped flame retardant is prepared from the following raw materials in parts by weight: 12 to 16 parts of nano magnesium hydroxide, 20 to 24 parts of calcined desert sand, 7 to 13 parts of nano lignin, 4 to 6 parts of melamine, 1 to 3 parts of tetrasodium glutamate diacetate and 4 to 6 parts of HK550 coupling agent; the preparation method of the calcined desert sand comprises the following steps: mixing desert sand with the particle size of 200-300 meshes and desert sand with the particle size of 800-1000 meshes, calcining the mixture in a muffle furnace at 1000-1100 DEG C for 30-40 minutes, taking out the calcined desert sand, and grinding Then a NaOH solution with the concentration of 0.5-0.8% is added at the temperature of 75-78 DEG C, surface alkali treatment is conducted on the desert sand, and the NaOH solution is completely adsorbed by the desert sand. According to the mode, the molecular structure and the adding mode of the nanometer co-doped flame retardant are optimized, so that the bonding strength of the nanometer co-doped flame retardant and PET is better, the nanometer co-doped flame retardant is stable under the high-temperature condition and good in flame retardant efficiency, and the adding amount is remarkably reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of flame - retardant PET, and specifically relates to a high - efficiency flame retardant suitable for flame - retardant PET, its preparation method and application. Background Art

[0002] Nano - flame retardants are widely used. For example, nano - Mg(OH)2 has advantages such as non - toxicity, rich content, and low price. It has the volume effect and surface effect of nanomaterials, so it is a better flame retardant applied in polymer materials (such as PET). However, due to problems such as inter - particle aggregation and strong hydrophilicity of nano - magnesium hydroxide, its compatibility with polymer materials is poor, so it needs to be modified.

[0003] For example, Chinese invention patent CN 114773669 A discloses a modified nano - magnesium hydroxide flame retardant and its preparation method, which uses a micro - channel reaction method to react an aqueous sodium hydroxide solution with an aqueous magnesium chloride solution to produce a modified nano - magnesium hydroxide flame retardant. However, after the reaction, it is washed with deionized water many times, generating a large amount of wastewater. At the same time, when it is used, the flame retardant is directly added to the polymer material for melt blending. To ensure the flame - retardant effect, the addition amount of the flame retardant in the polymer material is generally large.

[0004] Based on this, the present invention designs a high - efficiency flame retardant suitable for flame - retardant PET, its preparation method and application to solve the above problems. Summary of the Invention

[0005] In view of the above - mentioned drawbacks of the prior art, the present invention provides a high - efficiency flame retardant suitable for flame - retardant PET, its preparation method and application.

[0006] To achieve the above - mentioned purposes, the present invention is realized through the following technical solutions:

[0007] A high - efficiency flame retardant suitable for flame - retardant PET uses a nano - co - doped flame retardant, and the nano - co - doped flame retardant includes the following raw materials in parts by weight: 12 - 16 parts of nano - magnesium hydroxide, 20 - 24 parts of calcined desert sand, 7 - 13 parts of nano - lignin, 4 - 6 parts of melamine, 1 - 3 parts of glutamate diacetate tetrasodium, and 4 - 6 parts of HK550 coupling agent;

[0008] Preparation method of calcined desert sand: Mix desert sand with particle sizes of 200 - 300 mesh and 800 - 1000 mesh, place it in a muffle furnace and calcine at 1000 - 1100 °C for 30 - 40 min, take it out and grind it to the nanoscale; then at 75 - 78 °C, add a NaOH solution with a concentration of 0.5 - 0.8% to perform surface alkali treatment on the desert sand, and the NaOH solution is completely adsorbed by the desert sand.

[0009] Furthermore, desert sand with a particle size of 200 - 300 mesh and 800 - 1000 mesh is mixed at a mass ratio of 1:5 - 8.

[0010] Furthermore, the NaOH solution is 4 - 8% of the mass of the desert sand.

[0011] Furthermore, the desert sand is subjected to surface alkali treatment for 20 - 30 min.

[0012] To better achieve the object of the present invention, the present invention also provides a preparation method of the above-mentioned high - efficiency flame retardant applicable to flame - retardant PET, comprising the following steps:

[0013] (1) Weigh 12 - 16 parts of nano - magnesium hydroxide, 8 - 11 parts of calcined desert sand, 7 - 13 parts of nano - lignin, 4 - 6 parts of melamine, 1 - 3 parts of glutamate diacetic acid tetrasodium, and 4 - 6 parts of HK550 coupling agent;

[0014] (2) After mixing nano - magnesium hydroxide and glutamate diacetic acid tetrasodium, dissolve them in water, heat to 85 - 90 °C, then add melamine, stir and mix for 1 h; cool down to 45 - 70 °C, dropwise add HK550 coupling agent at a dropping rate of 20 - 40 drops / min and a stirring speed of 1500 - 2000 r / min; then continue to dropwise add nano - lignin at a dropping rate of 50 - 70 drops / min and a stirring speed of 1000 - 2000 r / min;

[0015] (3) Add calcined desert sand, and the mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand to obtain a nano - co - doped flame retardant;

[0016] (4) Place the nano - co - doped flame retardant in a plasma treatment device for plasma treatment;

[0017] (5) Use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano - co - doped flame retardant.

[0018] Furthermore, after mixing nano - magnesium hydroxide and glutamate diacetic acid tetrasodium, dissolve them in 1.3 - 2 times the volume of water.

[0019] Furthermore, the plasma treatment power is 68 W / L.

[0020] Furthermore, the picosecond laser irradiation parameters are: the central wavelength of the laser is 1026 nm, the repetition frequency is 50 kHz, and the pulse width is 6 ps.

[0021] To better achieve the object of the present invention, the present invention also provides an application of the above - mentioned high - efficiency flame retardant in the preparation of flame - retardant PET.

[0022] Further, it includes the following steps: placing the nano co-doped flame retardant in a plasma treatment device for plasma treatment; then using a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant, and then co-mixing and extruding the high-efficiency flame retardant with the PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.2-1.6 wt%.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention adsorbs the mixed liquid in the micropores of the calcined desert sand, with high bonding strength, and at the same time is beneficial to improving the compatibility with polymer materials to obtain a nano co-doped flame retardant; then, through plasma treatment and picosecond laser irradiation treatment, the surface morphology of the nano co-doped flame retardant is reconstructed, optimizing the molecular structure and addition method of the flame retardant, making the bonding strength between the nano co-doped flame retardant and PET better, stable under high-temperature conditions, with good flame retardant efficiency, and the addition amount is significantly reduced. The present invention does not produce waste water and is more environmentally friendly. Specific embodiments

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0025] Example 1: In some embodiments, a preparation method of a high-efficiency flame retardant applicable to flame-retardant PET includes the following steps:

[0026] (1) Preparation of calcined desert sand: Mix desert sand with particle sizes of 200 mesh and 1000 mesh in a mass ratio of 1:5, place it in a muffle furnace and calcine it at 1100 °C for 30 min, take it out and grind it to the nanoscale; then at 78 °C, add a NaOH solution with a concentration of 0.5%, and the NaOH solution is 8% of the mass of the desert sand, and perform surface alkali treatment on the desert sand for 20 min. The NaOH solution is completely adsorbed by the desert sand and no filtration treatment is required.

[0027] (2) Weigh 12 parts of nano magnesium hydroxide, 11 parts of calcined desert sand, 7 parts of nano lignin, 6 parts of melamine, 1 part of glutamate diacetic acid tetrasodium, and 6 parts of HK550 coupling agent;

[0028] (3) Mix nanometer magnesium hydroxide and tetrasodium glutamate diacetate, dissolve them in water with a volume 1.3 times that of the mixture, heat to 90 °C, add melamine, and stir and mix for 1 h; then cool to 45 °C, dropwise add the HK550 coupling agent at a dropping rate of 40 drops / min and a stirring speed of 1500 r / min; then continue to dropwise add nanometer lignin at a dropping rate of 70 drops / min and a stirring speed of 1000 r / min;

[0029] (4) Add calcined desert sand. The mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand, with high bonding strength and being conducive to improving the compatibility with polymer materials, thus obtaining a nano co-doped flame retardant;

[0030] After that, the high-efficiency flame retardant is used to prepare flame-retardant PET, including the following steps:

[0031] (5) Place the nano co-doped flame retardant in a plasma treatment device with a plasma treatment power of 68 W / L;

[0032] (6) Use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant.

[0033] The picosecond laser irradiation parameters are: the central wavelength of the laser is 1026 nm, the repetition frequency is 50 kHz, and the pulse width is 6 ps;

[0034] (7) Co-extrude the high-efficiency flame retardant and PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.2 wt%.

[0035] The present invention realizes the reconstruction of the surface morphology of the nano co-doped flame retardant through plasma treatment and picosecond laser irradiation treatment, optimizes the molecular structure and addition method of the flame retardant, makes the bonding strength between the nano co-doped flame retardant and PET better, stable under high-temperature conditions, with good flame-retardant efficiency, and significantly reduces the addition amount.

[0036] Example 2: In some embodiments, a preparation method of a high-efficiency flame retardant applicable to flame-retardant PET includes the following steps:

[0037] (1) Preparation of calcined desert sand: Mix desert sand with particle sizes of 300 mesh and 800 mesh according to a mass ratio of 1:8, place it in a muffle furnace and calcine at 1000 °C for 40 min, take it out and grind it to the nanoscale; then at 75 °C, add a NaOH solution with a concentration of 0.8%, and the NaOH solution is 4% of the mass of the desert sand, perform surface alkali treatment on the desert sand for 30 min, and the NaOH solution is completely adsorbed by the desert sand without filtration treatment.

[0038] (2) Weigh 16 parts of nano magnesium hydroxide, 8 parts of calcined desert sand, 13 parts of nano lignin, 4 parts of melamine, 3 parts of glutamate diacetate tetrasodium, and 4 parts of HK550 coupling agent;

[0039] (3) After mixing nano magnesium hydroxide and glutamate diacetate tetrasodium, dissolve them in water with a volume 2 times that of the mixture, heat to 85 °C, add melamine, and stir and mix for 1 h; then cool to 70 °C, dropwise add HK550 coupling agent at a dropping rate of 20 drops / min and a stirring speed of 2000 r / min; then continue to dropwise add nano lignin at a dropping rate of 50 drops / min and a stirring speed of 2000 r / min;

[0040] (4) Add calcined desert sand, and the mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand to obtain a nano co-doped flame retardant;

[0041] After that, the high-efficiency flame retardant is used to prepare flame-retardant PET, including the following steps:

[0042] (5) Place the nano co-doped flame retardant in a plasma treatment device, and the plasma treatment power is 68 W / L;

[0043] (6) Use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant.

[0044] The picosecond laser irradiation parameters are: the central wavelength of the laser is 1026 nm, the repetition frequency is 50 kHz, and the pulse width is 6 ps.

[0045] (7) Co-mix and extrude the high-efficiency flame retardant with PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.6 wt%.

[0046] Through plasma treatment and picosecond laser irradiation treatment, the surface morphology of the nano co-doped flame retardant is reconstructed, the molecular structure and addition method of the flame retardant are optimized, so that the bonding strength between the nano co-doped flame retardant and PET is better, stable under high-temperature conditions, with good flame retardancy efficiency, and the addition amount is significantly reduced.

[0047] Example 3: In some embodiments, a preparation method of a high-efficiency flame retardant applicable to flame-retardant PET includes the following steps:

[0048] (1) Preparation of calcined desert sand: Mix desert sand with particle sizes of 250 mesh and 900 mesh according to a mass ratio of 1:6, place it in a muffle furnace and calcine at 1050 °C for 35 min, take it out and grind it to the nanoscale; then at 76 °C, add a NaOH solution with a concentration of 0.7%, and the NaOH solution is 6% of the mass of the desert sand, and perform surface alkali treatment on the desert sand for 22 min. The NaOH solution is completely adsorbed by the desert sand and no filtration treatment is required.

[0049] (2) Weigh 14 parts of nano magnesium hydroxide, 9 parts of calcined desert sand, 10 parts of nano lignin, 5 parts of melamine, 2 parts of glutamate diacetic acid tetrasodium, and 5 parts of HK550 coupling agent;

[0050] (3) After mixing nano magnesium hydroxide and glutamate diacetic acid tetrasodium, dissolve them in 1.5 times the volume of water. After heating to 88 °C, add melamine and stir for 1 h; then cool down to 60 °C, and dropwise add HK550 coupling agent at a dropping rate of 30 drops / min and a stirring speed of 1800 r / min; then continue to dropwise add nano lignin at a dropping rate of 60 drops / min and a stirring speed of 1600 r / min;

[0051] (4) Add calcined desert sand, and the mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand to obtain a nano co-doped flame retardant;

[0052] After that, the high-efficiency flame retardant is used to prepare flame-retardant PET, including the following steps:

[0053] (5) Place the nano co-doped flame retardant in a plasma treatment device, and the plasma treatment power is 68 W / L;

[0054] (6) Use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant.

[0055] The picosecond laser irradiation parameters are: the central wavelength of the laser is 1026 nm, the repetition frequency is 50 kHz, and the pulse width is 6 ps.

[0056] (7) Mix and extrude the high-efficiency flame retardant with PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.4 wt%.

[0057] By means of plasma treatment and picosecond laser irradiation treatment, the surface morphology of the nano co-doped flame retardant is reconstructed, the molecular structure and addition method of the flame retardant are optimized, so that the bonding strength between the nano co-doped flame retardant and PET is better, stable under high-temperature conditions, with good flame retardancy efficiency, and the addition amount is significantly reduced.

[0058] Comparative Example 1

[0059] A preparation method of a high-efficiency flame retardant applicable to flame-retardant PET, including the following steps:

[0060] (1) Preparation of calcined desert sand: Mix desert sand with particle sizes of 250 mesh and 900 mesh in a mass ratio of 1:6, place it in a muffle furnace and calcine at 1050 °C for 35 min, then take it out and grind it to the nanoscale; then at 76 °C, add a NaOH solution with a concentration of 0.7%, and the NaOH solution is 6% of the mass of the desert sand, and perform surface alkali treatment on the desert sand for 22 min. The NaOH solution is completely adsorbed by the desert sand and no filtration treatment is required.

[0061] (2) Weigh 14 parts of nano magnesium hydroxide, 9 parts of calcined desert sand, 10 parts of nano lignin, 5 parts of melamine, 2 parts of glutamate diacetic acid tetrasodium, and 5 parts of HK550 coupling agent;

[0062] (3) After mixing nano magnesium hydroxide and glutamate diacetic acid tetrasodium, dissolve them in 1.5 times the volume of water, heat to 88 °C, then add melamine, stir and mix for 1 h; cool to 60 °C, dropwise add HK550 coupling agent at a dropping rate of 30 drops / min and a stirring speed of 1800 r / min; then continue to dropwise add nano lignin at a dropping rate of 60 drops / min and a stirring speed of 1600 r / min;

[0063] (4) Add calcined desert sand, and the mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand to obtain a nano co-doped flame retardant;

[0064] Then, the high-efficiency flame retardant is used to prepare flame-retardant PET, including the following steps:

[0065] (5) Directly blend and extrude the high-efficiency flame retardant with PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.4 wt%.

[0066] Comparative Example 2

[0067] A preparation method of a high-efficiency flame retardant applicable to flame-retardant PET, including the following steps:

[0068] (1) Preparation of calcined desert sand: Place desert sand with a particle size of 250 mesh in a muffle furnace and calcine at 1050 °C for 35 min, then take it out and grind it to the nanoscale; then at 76 °C, add a NaOH solution with a concentration of 0.7%, and the NaOH solution is 6% of the mass of the desert sand, and perform surface alkali treatment on the desert sand for 22 min. The NaOH solution is completely adsorbed by the desert sand and no filtration treatment is required.

[0069] (2) Weigh 14 parts of nano magnesium hydroxide, 9 parts of calcined desert sand, 10 parts of nano lignin, 5 parts of melamine, 2 parts of glutamate diacetic acid tetrasodium, and 5 parts of HK550 coupling agent;

[0070] (3) Mix nano magnesium hydroxide and tetrasodium glutamate diacetate, dissolve them in 1.5 times the volume of water, heat to 88 °C, add melamine, stir and mix for 1 h; then cool to 60 °C, dropwise add HK550 coupling agent at a dropping rate of 30 drops / min and a stirring speed of 1800 r / min; then continue to dropwise add nano lignin at a dropping rate of 60 drops / min and a stirring speed of 1600 r / min;

[0071] (4) Add calcined desert sand, and the mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand to obtain a nano co-doped flame retardant;

[0072] After that, the high-efficiency flame retardant is used to prepare flame-retardant PET, including the following steps:

[0073] (5) Place the nano co-doped flame retardant in a plasma treatment device, and the plasma treatment power is 68 W / L;

[0074] (6) Use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant.

[0075] The picosecond laser irradiation parameters are: the central wavelength of the laser is 1026 nm, the repetition frequency is 50 kHz, and the pulse width is 6 ps.

[0076] (7) Co-mix and extrude the high-efficiency flame retardant with the PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.4 wt%.

[0077] Test example: Perform the following performance tests on the flame-retardant PET obtained in Examples 1-3 and Comparative Examples 1-2:

[0078] Tensile strength (ASTM D63803);

[0079] Oxygen index LOI (GB / T 2406.22009);

[0080] Vertical and horizontal burning grades (GB / T 2408-2021); the specimen size is 130×13 mm, ignition for 10 min; at the same time, observe whether there are flaming drips. The test results are shown in Table 1.

[0081] Table 1 Performance test results of the flame-retardant PET in Examples 1-3 and Comparative Examples 1-2

[0082] Group Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tensile Strength / MPa 60.3 58.3 59.1 49.6 51.3 LOI / % 34.2 38.7 36.5 30.2 28.9 Vertical / Level V-0 V-0 V-0 V-1 V-0 Horizontal / Level HB1 HB1 HB1 HB2 HB2 Flammable Dripping None None None None Yes

[0083] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. An efficient flame retardant applicable to flame-retardant PET, characterized in that, Using a nano co-doped flame retardant, the nano co-doped flame retardant comprises the following raw materials in parts by weight: 12-16 parts of nano magnesium hydroxide, 20-24 parts of calcined desert sand, 7-13 parts of nano lignin, 4-6 parts of melamine, 1-3 parts of glutamate diacetic acid tetrasodium, and 4-6 parts of HK550 coupling agent; Preparation method of calcined desert sand: Mix desert sand with particle sizes of 200-300 mesh and 800-1000 mesh, place it in a muffle furnace and calcine at 1000-1100 °C for 30-40 min, take it out and grind it to the nano level; then at 75-78 °C, add a NaOH solution with a concentration of 0.5-0.8%, and perform surface alkali treatment on the desert sand. The NaOH solution is completely adsorbed by the desert sand.

2. The high-efficiency flame retardant applicable to flame-retardant PET according to claim 1, wherein Mix desert sand with particle sizes of 200-300 mesh and 800-1000 mesh according to a mass ratio of 1:5-8.

3. The high-efficiency flame retardant applicable to flame-retardant PET according to claim 2, characterized in that, The NaOH solution is 4-8% of the mass of the desert sand.

4. The high-efficiency flame retardant applicable to flame-retardant PET according to claim 3, characterized in that, Perform surface alkali treatment on the desert sand for 20-30 min.

5. A preparation method of an efficient flame retardant applicable to flame-retardant PET according to claim 4, characterized in that, It includes the following steps: (1) Weigh 12-16 parts of nano magnesium hydroxide, 8-11 parts of calcined desert sand, 7-13 parts of nano lignin, 4-6 parts of melamine, 1-3 parts of glutamate diacetic acid tetrasodium, and 4-6 parts of HK550 coupling agent; (2) After mixing nano magnesium hydroxide and glutamate diacetic acid tetrasodium, dissolve them in water, heat to 85-90 °C, then add melamine, stir and mix for 1 h; cool down to 45-70 °C, dropwise add HK550 coupling agent, the dropping speed is 20-40 drops / min, and the stirring speed is 1500-2000 r / min; Then continue to dropwise add nano lignin, the dropping speed is 50-70 drops / min, and the stirring speed is 1000-2000 r / min; (3) Add calcined desert sand, and the mixed solution obtained in the previous step is adsorbed in the micropores of the calcined desert sand to obtain the nano co-doped flame retardant; (4) Place the nano co-doped flame retardant in a plasma treatment device for plasma treatment; (5) Use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant.

6. The preparation method of the high-efficiency flame retardant applicable to flame-retardant PET according to claim 5, characterized in that After mixing nano magnesium hydroxide and glutamate diacetic acid tetrasodium, dissolve them in 1.3-2 times the volume of water.

7. The preparation method of the high-efficiency flame retardant applicable to flame-retardant PET according to claim 6, characterized in that, The plasma treatment power is 68 W / L.

8. The preparation method of the high-efficiency flame retardant applicable to flame-retardant PET according to claim 7, characterized in that, The picosecond laser irradiation parameters are: the central wavelength of the laser is 1026 nm, the repetition frequency is 50 kHz, and the pulse width is 6 ps.

9. Application of the high-efficiency flame retardant according to claim 4 in the preparation of flame-retardant PET.

10. Use of the high-efficiency flame retardant according to claim 9 in the preparation of flame-retardant PET, characterized in that, It includes the following steps: Place the nano co-doped flame retardant in a plasma treatment device for plasma treatment; then use a picosecond laser irradiator to perform picosecond laser irradiation treatment on the surface of the nano co-doped flame retardant, and then co-mix and extrude the high-efficiency flame retardant with the PET masterbatch to obtain flame-retardant PET; the content of the high-efficiency flame retardant in the flame-retardant PET is 1.2-1.6 wt%.