Flame-retardant material containing diisobutyl aluminum hypophosphite and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and provides a flame-retardant material containing diisobutyl aluminum hypophosphite and a preparation method thereof. The flame-retardant material containing the diisobutyl aluminum hypophosphite is prepared from the following raw material components in parts by mass: 40 to 85 parts of polyester resin, 3 to 15 parts of the diisobutyl aluminum hypophosphite, 3 to 10 parts of diethyl aluminum hypophosphite, 3 to 10 parts of brominated epoxy resin, 3 to 10 parts of aluminum hypophosphite and 0 to 35 parts of glass fiber. According to the technical scheme, the problem that the flame retardance of a material is low when an organic flame retardant is added into a high polymer material in the prior art is solved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a flame retardant material containing diisobutyl aluminum hypophosphite and a preparation method thereof. Background Art

[0002] Polymer materials are widely used in people's daily lives. Due to their flammable properties, when they come into contact with high-temperature heat sources, they will generate a large amount of combustible gas, non-combustible gas and carbonized residue. The combustible gas mixes with oxygen and will burn when the temperature reaches the ignition point or encounters other fire sources, endangering personal and property safety.

[0003] Flame retardants are protective agents that can prevent combustibles and flammable materials from igniting or slow down the spread of flames. They are divided into organic flame retardants and inorganic flame retardants, and can be used to improve the flame resistance of materials. Adding flame retardants to polymer materials can help reduce the flammability of materials, prevent the spread of flames, and reduce smoke generation.

[0004] Compared with organic flame retardants, inorganic flame retardants have low toxicity, are non-volatile, non-precipitating, low price, and low smoke emission, but they will reduce the processability, formability, mechanical properties, electrical properties, etc. of polymer materials. Therefore, in order to ensure the molding processability and physical properties of polymer materials, organic flame retardants are generally added to improve the flame retardancy of the materials. However, the flame retardant effect of currently available organic flame retardants is not ideal. Even if they are added to polymer materials, the flame retardancy of the resulting materials is still relatively low. Summary of the invention

[0005] The invention provides a flame retardant material containing diisobutyl aluminum hypophosphite and a preparation method thereof, which solves the problem in the related art that the flame retardancy of the material is low when an organic flame retardant is added to a polymer material.

[0006] The technical solution of the present invention is as follows: The flame retardant material containing diisobutyl aluminum hypophosphite comprises the following components in parts by mass: 40-85 parts of polyester resin, 3-15 parts of diisobutyl aluminum hypophosphite, 3-10 parts of diethyl aluminum hypophosphite, 3-10 parts of brominated epoxy resin, 3-10 parts of aluminum hypophosphite and 0-35 parts of glass fiber.

[0007] As a further technical solution, the raw materials also include 1 to 15 parts of cyclotriphosphazene-PMMH-6 polymer.

[0008] The present invention adds cyclotriphosphazene-PMMH-6 polymer, CAS No. 77958-57-7, and uses the cyclotriphosphazene-PMMH-6 polymer in combination with diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin, and aluminum hypophosphite to further improve the flame retardancy and mechanical strength of the material, especially the tensile strength. The improvement of tensile strength has greatly broadened the application of flame retardant materials, and can be applied to the insulation layer and sheath layer of wires and cables to withstand the stretching of the cables during installation and use to avoid damage; it can also be applied to conveyor belts to ensure that the conveyor belts are not easy to break during operation, ensuring the safety and efficiency of material transportation; it can also be used for decorative materials to ensure the stability and durability of the materials during use, and avoid safety hazards caused by material damage.

[0009] As a further technical solution, the mass ratio of the diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin, and aluminum hypophosphite to the mass ratio of the cyclotriphosphazene-PMMH-6 polymer is 3:2-4:1.

[0010] In the present invention, the mass ratio of diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin, aluminum hypophosphite and cyclotriphosphazene-PMMH-6 polymer is optimized to 3:2-4:1, thereby further improving the mechanical strength of the material.

[0011] As a further technical solution, the glass fiber is a nitrogen-bicyclic phosphate composite glass fiber, and the mass ratio of the nitrogen-bicyclic phosphate composite glass fiber to the polyester resin is 3-7:12.

[0012] The invention adds azabicyclic phosphate composite glass fiber to further improve the mechanical strength of the material. The hydroxyl group on the surface of the glass fiber can form a hydrogen bond with the carbonyl group, nitro group, etc. in the azabicyclic phosphate, so that the azabicyclic phosphate is coated on the surface of the glass fiber to improve the dispersion effect of the glass fiber and the fusion with the matrix material, and to exert the reinforcing effect of the glass fiber to a greater extent, thereby improving the mechanical strength of the material.

[0013] As a further technical solution, the raw materials of the azabicyclic phosphate composite glass fiber include azabicyclic phosphate and glass fiber in a mass ratio of 1 to 5:50.

[0014] As a further technical solution, the raw materials of the azabicyclic phosphate composite glass fiber include azabicyclic phosphate and glass fiber in a mass ratio of 3:50.

[0015] The inventors have found through experiments that when the mass ratio of azabicyclic phosphate to glass fiber is 3:50, the azabicyclic phosphate has the best coating effect on the glass fiber, further improving the mechanical strength of the material.

[0016] As a further technical solution, the preparation method of the azabicyclic phosphate composite glass fiber comprises the following steps: dissolving the azabicyclic phosphate in a solvent, adding glass fiber to mix, and drying to obtain the azabicyclic phosphate composite glass fiber.

[0017] The solvent in the present invention can be selected from any one or more solvents that can dissolve azabicyclic phosphate, preferably acetonitrile.

[0018] As a further technical solution, the mixing time is 30 to 60 minutes.

[0019] As a further technical solution, the polyester resin includes one or more of PBT resin, PET resin, and PC resin.

[0020] In the present invention, PBT resin is polybutylene terephthalate resin, PET resin is polyethylene terephthalate resin, and PC resin is polycarbonate resin.

[0021] As a further technical solution, the raw materials also include 0.2 to 0.5 parts of antioxidant.

[0022] The raw materials of the flame retardant material of the present invention also include an antioxidant. The antioxidant is added to inhibit or delay the degradation of the material due to the action of oxygen or ozone in the atmosphere.

[0023] As a further technical solution, the antioxidant includes one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 264, antioxidant 3114, and antioxidant 300.

[0024] The invention also proposes a method for preparing the flame retardant material containing diisobutyl aluminum hypophosphite, comprising the following steps: mixing the raw materials uniformly, melting, extruding, and granulating to obtain the flame retardant material containing diisobutyl aluminum hypophosphite.

[0025] The working principle and beneficial effects of the present invention are: 1. The polyester resin used as the matrix material in the present invention provides good heat resistance, moisture resistance, oil resistance, acid resistance, chemical resistance, air tightness, transparency and high mechanical strength. The halogen-free phosphorus flame retardant diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite and aluminum hypophosphite are used in combination with the bromine flame retardant brominated epoxy resin to significantly improve the flame retardancy of the material and make the material more difficult to burn.

[0026] 2. The diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite and aluminum hypophosphite in the present invention have good compatibility with the polyester resin and are not easy to precipitate, which ensures the stable performance of the material during long-term use and helps to maintain the flame retardancy and mechanical properties of the material. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] The parameters of the raw materials in the following examples and comparative examples are as follows: The PBT resin is PBT 1100A; PC resin is Chimei PC-115 from Taiwan, China; PET resin is PET YS-Y01; The glass fiber had a diameter of 10 μm and a length of 3 mm.

[0029] Example 1 60 parts of PBT resin, 10 parts of diisobutyl aluminum hypophosphite, 5 parts of diethyl aluminum hypophosphite, 5 parts of brominated epoxy resin, 5 parts of aluminum hypophosphite and 15 parts of glass fiber are uniformly mixed, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum hypophosphite.

[0030] Example 2 28 parts of PC resin, 12 parts of PBT resin, 3 parts of diisobutyl aluminum hypophosphite, 3 parts of diethyl aluminum hypophosphite, 3 parts of brominated epoxy resin, 10 parts of aluminum hypophosphite and 0.2 parts of antioxidant 1010 were mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum hypophosphite.

[0031] Example 3 85 parts of PET resin, 15 parts of diisobutyl aluminum hypophosphite, 10 parts of diethyl aluminum hypophosphite, 10 parts of brominated epoxy resin, 3 parts of aluminum hypophosphite, 35 parts of glass fiber and 0.5 parts of antioxidant 1076 were mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum hypophosphite.

[0032] Example 4 60 parts of PBT resin, 9.6 parts of diisobutyl aluminum phosphite, 4.8 parts of diethyl aluminum phosphite, 4.8 parts of brominated epoxy resin, 4.8 parts of aluminum phosphite, 1 part of cyclotriphosphazene-PMMH-6 polymer and 15 parts of glass fiber were mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum phosphite.

[0033] Example 5 60 parts of PBT resin, 8 parts of diisobutyl aluminum phosphite, 4 parts of diethyl aluminum phosphite, 4 parts of brominated epoxy resin, 4 parts of aluminum phosphite, 5 parts of cyclotriphosphazene-PMMH-6 polymer and 15 parts of glass fiber are mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum phosphite.

[0034] Example 6 60 parts of PBT resin, 6 parts of diisobutyl aluminum phosphite, 3 parts of diethyl aluminum phosphite, 3 parts of brominated epoxy resin, 3 parts of aluminum phosphite, 10 parts of cyclotriphosphazene-PMMH-6 polymer and 15 parts of glass fiber are mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum phosphite.

[0035] Example 7 60 parts of PBT resin, 4 parts of diisobutyl aluminum phosphite, 2 parts of diethyl aluminum phosphite, 2 parts of brominated epoxy resin, 2 parts of aluminum phosphite, 15 parts of cyclotriphosphazene-PMMH-6 polymer and 15 parts of glass fiber are mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum phosphite.

[0036] Example 8 The only difference from Example 6 is that the glass fiber is azabicyclic phosphate composite glass fiber, and the preparation method is as follows: After dissolving 1 part of azabicyclic phosphate in 70 parts of acetonitrile, 50 parts of glass fiber was added, stirred for 30 minutes, and dried to obtain azabicyclic phosphate composite glass fiber.

[0037] Example 9 The only difference from Example 8 is that: 25 parts of azabicyclic phosphate composite glass fiber, the preparation method is as follows: After dissolving 1 part of azabicyclic phosphate in 70 parts of acetonitrile, 50 parts of glass fiber was added, stirred for 45 minutes, and dried to obtain azabicyclic phosphate composite glass fiber.

[0038] Example 10 The only difference from Example 8 is that: 35 parts of azabicyclic phosphate composite glass fiber, the preparation method is as follows: After dissolving 1 part of azabicyclic phosphate in 70 parts of acetonitrile, 50 parts of glass fiber was added, stirred for 60 minutes, and dried to obtain azabicyclic phosphate composite glass fiber.

[0039] Embodiment 11 The only difference from Example 9 is that the azabicyclic phosphate composite glass fiber is prepared as follows: After 3 parts of azabicyclic phosphate were dissolved in 70 parts of acetonitrile, 50 parts of glass fiber were added, stirred for 45 minutes, and dried to obtain azabicyclic phosphate composite glass fiber.

[0040] Example 12 The only difference from Example 9 is that the azabicyclic phosphate composite glass fiber is prepared as follows: After dissolving 5 parts of azabicyclic phosphate in 70 parts of acetonitrile, 50 parts of glass fiber were added, stirred for 45 minutes, and dried to obtain azabicyclic phosphate composite glass fiber.

[0041] Embodiment 13 60 parts of PBT resin, 6 parts of diisobutyl aluminum phosphite, 3 parts of diethyl aluminum phosphite, 3 parts of brominated epoxy resin, 3 parts of aluminum phosphite, 10 parts of cyclotriphosphazene-PMMH-6 polymer, 15 parts of glass fiber and 0.3 parts of azabicyclic phosphate are mixed evenly, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum phosphite.

[0042] Comparative Example 1 60 parts of PBT resin, 12.5 parts of diisobutyl aluminum hypophosphite, 6.25 parts of diethyl aluminum hypophosphite, 6.25 parts of aluminum hypophosphite and 15 parts of glass fiber were uniformly mixed, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum hypophosphite.

[0043] Comparative Example 2 60 parts of PBT resin, 12.5 parts of diisobutyl aluminum phosphite, 6.25 parts of diethyl aluminum phosphite, 6.25 parts of brominated epoxy resin and 15 parts of glass fiber were uniformly mixed, melted, extruded and granulated to obtain a flame retardant material containing diisobutyl aluminum phosphite.

[0044] The flame retardant grades of the flame retardant materials obtained in Examples 1 to 13 and Comparative Examples 1 to 2 were tested with reference to the method in UL94, with the sample thicknesses of 1.6 mm and 0.8 mm, respectively; the tensile strength was tested with reference to the method in GB / T 1040.2-2022, with the sample thickness of 4 mm and the test speed of 5 mm / min; the results are recorded in Table 1.

[0045] Table 1 Flame retardancy and mechanical strength of flame retardant materials

[0046] As can be seen from Table 1, the flame retardant material provided by the present invention has good flame retardancy and high mechanical strength. In Example 1, diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin and aluminum hypophosphite are used in combination, and the flame retardant grade (UL94, 1.6mm) and flame retardant grade (UL94, 0.8mm) of the flame retardant material prepared are higher than those of Comparative Examples 1 to 2, indicating that the use of diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin and aluminum hypophosphite can improve the flame retardancy of the flame retardant material. In addition, the flame retardant grade (UL94, 0.8mm) and tensile strength of the flame retardant material prepared in Examples 4 to 7 are higher than those in Example 1, indicating that the use of cyclotriphosphazene-PMMH-6 polymer with diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin and aluminum hypophosphite can further improve the flame retardancy of the material, while also improving the mechanical strength of the material.

[0047] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A flame retardant material containing diisobutyl aluminum hypophosphite, characterized in that: The raw materials include the following components in parts by weight: 40-85 parts of polyester resin, 3-15 parts of diisobutyl aluminum hypophosphite, 3-10 parts of diethyl aluminum hypophosphite, 3-10 parts of brominated epoxy resin, 3-10 parts of aluminum hypophosphite, and 0-35 parts of glass fiber.

2. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 1, characterized in that: The raw materials also include 1 to 15 parts of cyclotriphosphazene-PMMH-6 polymer.

3. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 2, characterized in that: The mass ratio of the diisobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, brominated epoxy resin, and aluminum hypophosphite to the mass ratio of the cyclotriphosphazene-PMMH-6 polymer is 3:2-4:

1.

4. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 2, characterized in that: The glass fiber is a nitrogen-containing bicyclic phosphate composite glass fiber, and the mass ratio of the nitrogen-containing bicyclic phosphate composite glass fiber to the polyester resin is 3-7:

12.

5. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 4, characterized in that: The raw materials of the azabicyclic phosphate composite glass fiber include azabicyclic phosphate and glass fiber in a mass ratio of 1 to 5:

50.

6. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 5, characterized in that: The preparation method of the azabicyclic phosphate composite glass fiber comprises the following steps: dissolving the azabicyclic phosphate in a solvent, adding glass fiber to mix, and drying to obtain the azabicyclic phosphate composite glass fiber.

7. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 6, characterized in that: The mixing time is 30 to 60 minutes.

8. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 1, characterized in that: The polyester resin includes one or more of PBT resin, PET resin and PC resin.

9. The flame retardant material containing diisobutyl aluminum hypophosphite according to claim 1, characterized in that: The raw materials also include 0.2-0.5 parts of antioxidant.

10. The method for preparing a flame retardant material containing diisobutyl aluminum hypophosphite according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing the raw materials uniformly, melting, extruding and granulating to obtain a flame retardant material containing diisobutyl aluminum hypophosphite.

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