High-temperature-resistant flame-retardant polyester composite material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and provides a high-temperature-resistant flame-retardant polyester composite material and a preparation method thereof. The high-temperature-resistant flame-retardant polyester composite material comprises the following components in parts by mass: 50-60 parts of polyester resin, 1-5 parts of a flexibilizer and 15-20 parts of a flame retardant, and the flame retardant is prepared from the following raw materials: a phosphorus-containing flame retardant, metal hydroxide and fluorosilane. According to the technical scheme, the problem of poor flame retardance of the polyester composite 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 high temperature resistant flame retardant polyester composite material and a preparation method thereof. Background Art

[0002] Polyester material is a polymer compound made from polyacids and polyols through a condensation reaction. It has the advantages of high mechanical strength, excellent wear resistance, good dimensional stability and easy processing. It is widely used in packaging, textiles, electronics and other industries, and occupies a very important position in people's daily lives.

[0003] Polyester materials include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polytrimethylene terephthalate (PTT), etc. Although they have many excellent properties, they are flammable and will burn under the action of external heat and fire sources, which can easily cause fires, thus greatly limiting their application.

[0004] At present, the flame retardancy of polyester materials is generally improved by adding flame retardants to prepare polyester composite materials. However, as people pay more and more attention to their own safety and property safety, higher requirements are placed on the flame retardancy of polyester composite materials. Summary of the invention

[0005] The invention provides a high temperature resistant flame retardant polyester composite material and a preparation method thereof, which solves the problem of poor flame retardancy of the polyester composite material in the related art.

[0006] The technical solution of the present invention is as follows: A high-temperature resistant flame-retardant polyester composite material comprises the following components in parts by weight: 50-60 parts of polyester resin, 1-5 parts of toughening agent, and 15-20 parts of flame retardant, wherein the raw materials of the flame retardant include phosphorus-containing flame retardant, metal hydroxide and fluorosilane.

[0007] In the present invention, a toughening agent is added to improve the brittleness of the material, increase the toughness of the material, and improve the flexural strength and impact strength. The toughening agent can be toughening agent AX8900, ethylene-acrylate-glycidyl methacrylate terpolymer, etc., preferably toughening agent AX8900.

[0008] In the present invention, metal hydroxide is added to improve the flame retardancy of the material and has smoke suppression properties. The metal hydroxide can be any one or more metal hydroxides with flame retardant effects, such as magnesium hydroxide, aluminum hydroxide, etc., preferably aluminum hydroxide.

[0009] As a further technical solution, the mass ratio of the phosphorus-containing flame retardant and fluorosilane to the metal hydroxide is 3:17 to 5:15.

[0010] The inventors have found that when the mass ratio of the phosphorus-containing flame retardant and fluorosilane to the metal hydroxide is 3:17-5:15, the high temperature resistance of the polyester composite material is further improved.

[0011] As a further technical solution, the polyester resin includes one or more of PET resin, PEN resin, PBT resin, PBS resin, and PTT resin.

[0012] As a further technical solution, the mass ratio of the phosphorus-containing flame retardant to fluorosilane is 1.5:3.5~2:3.

[0013] The present invention limits the mass ratio of the phosphorus-containing flame retardant to the fluorosilane to 1.5:3.5-2:3, thereby further improving the high temperature resistance of the polyester composite material.

[0014] In the present invention, phosphorus-containing flame retardant is added. Since phosphorus element will be oxidized to generate free radical scavengers such as PO·, PO2· and HPO· during the combustion process, it can combine with highly active hydrogen radicals and hydroxyl radicals to inhibit the combustion chain reaction, and at the same time promote the dehydration of the polymer burning on the surface to form a protective carbon layer, which has the effect of improving the flame retardancy. The phosphorus-containing flame retardant can be any one or more substances containing phosphorus element, for example, it can be phosphate, halogenated phosphate, phosphite, red phosphorus, phosphate, polyphosphate, cyclophosphamide, etc., preferably ammonium polyphosphate, triammonium phosphate, tris (2-chloroethyl) phosphate, cyclophosphamide, more preferably cyclophosphamide.

[0015] The inventors have found that when the phosphorus-containing flame retardant is cyclophosphamide, the high temperature resistance of the polyester composite material is further improved.

[0016] Fluorosilane is added in the present invention to improve the flame retardancy of the polyester composite material by introducing fluorine atoms. Fluorosilane can be any one or more silanes containing fluorine elements, such as triphenylfluorosilane, 1,2,2-trifluorovinyltriphenylsilane, etc., preferably 1,2,2-trifluorovinyltriphenylsilane.

[0017] As a further technical solution, the flame retardant includes a phosphorus-containing flame retardant-coated metal hydroxide and also includes fluorosilane.

[0018] In the present invention, the phosphorus-containing flame retardant is used to coat the metal hydroxide, thereby improving the affinity between the metal hydroxide and the polyester resin and further improving the high temperature resistance of the polyester composite material.

[0019] As a further technical solution, the preparation method of the phosphorus-containing flame retardant coated metal hydroxide comprises the following steps: dissolving the phosphorus-containing flame retardant, adding the metal hydroxide and mixing evenly, and drying to obtain the phosphorus-containing flame retardant coated metal hydroxide.

[0020] As a further technical solution, it also includes at least one of the following features: antioxidant, lubricant, antistatic agent, nucleating agent, colorant.

[0021] When the high temperature resistant flame retardant polyester composite material in the present invention also includes an antioxidant, the antioxidant capacity of the material is improved by adding the antioxidant, and the antioxidant can be antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 264, antioxidant 3114, antioxidant 300, etc.

[0022] When the high temperature resistant flame retardant polyester composite material in the present invention also includes a lubricant, the lubricant is added to reduce the friction and adhesion between the melt and the processing machinery (such as a barrel, a screw) or a molding mold and inside the melt, thereby improving processing fluidity, production efficiency and material appearance quality. The lubricant can be stearic acid amide, oleic acid amide, sodium stearate, zinc stearate, silicone oil, paraffin oil, etc.

[0023] When the high temperature resistant flame retardant polyester composite material in the present invention further includes an antistatic agent, a channel for leakage of charges is formed by adding the antistatic agent to avoid accumulation of static charges. The antistatic agent may be antistatic agent SN, antistatic agent TM, antistatic agent ECH, and the like.

[0024] When the high temperature resistant flame retardant polyester composite material in the present invention further includes a nucleating agent, the molding cycle is shortened by adding the nucleating agent, and the rigidity, heat deformation temperature and creep resistance of the material are improved. The nucleating agent can be an inorganic nucleating agent and / or an organic nucleating agent, for example, talcum powder, silicon dioxide, calcium carbonate, sodium bis(4-tert-butylphenyl) phosphate, sodium 2,2'-methylenebis(4,6-tert-butylphenyl) phosphate, etc.

[0025] When the high temperature resistant flame retardant polyester composite material in the present invention also includes a color former, a certain color is given to the material by adding the color former, which not only makes the material more beautiful, but also improves the optical properties of the material. The colorant can be an organic pigment and / or an inorganic pigment, for example, it can be carbon black, titanium dioxide, chrome yellow, iron red, phthalocyanine blue, phthalocyanine green G, permanent yellow HR, permanent yellow GR, permanent orange G, vat brilliant orange GR, etc.

[0026] The present invention also proposes a method for preparing a high temperature resistant flame retardant polyester composite material, comprising the following steps: uniformly mixing the components in mass parts, melting, extruding, and granulating to obtain the high temperature resistant flame retardant polyester composite material.

[0027] The working principle and beneficial effects of the present invention are: The present invention provides a polyester composite material, comprising a polyester resin, a toughening agent and a flame retardant. The flame retardancy of the polyester composite material is improved by compounding a phosphorus-containing flame retardant, a metal hydroxide and a fluorosilane as raw materials of the flame retardant, thereby solving the problem of poor flame retardancy of the polyester composite material. In addition, the compounding of the phosphorus-containing flame retardant, the metal hydroxide and the fluorosilane also improves the high temperature resistance of the polyester composite material. DETAILED DESCRIPTION

[0028] 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.

[0029] The parameters of the raw materials in the following examples and comparative examples are as follows: PET resin is PET American DuPont 415HP; The PBT resin is PBT 4012G RESIN; The particle size of aluminum hydroxide is 800 mesh; The particle size of calcium carbonate is 1250 mesh; The particle size of magnesium hydroxide is 800 mesh; The particle size of talc is 1250 mesh.

[0030] Example 1 60 parts of PET resin, 5 parts of toughening agent AX8900, 4.8 parts of ammonium polyphosphate, 3.2 parts of 1,2,2-trifluorovinyl triphenylsilane and 12 parts of aluminum hydroxide were uniformly mixed, melted, extruded and granulated to obtain a polyester composite material.

[0031] Example 2 55 parts of PBT resin, 3 parts of toughening agent AX8900, 3.6 parts of triammonium phosphate, 2.4 parts of 1,2,2-trifluorovinyl triphenylsilane, 9 parts of magnesium hydroxide, 0.5 parts of oleic acid amide, 0.5 parts of antioxidant 264 and 3.5 parts of calcium carbonate were uniformly mixed, melted, extruded and granulated to obtain a polyester composite material.

[0032] Example 3 50 parts of PET resin, 1 part of toughening agent AX8900, 4.8 parts of tris(2-chloroethyl)phosphate, 3.2 parts of 1,2,2-trifluorovinyltriphenylsilane, 12 parts of aluminum hydroxide and 5 parts of talc were uniformly mixed, melted, extruded and granulated to obtain a polyester composite material.

[0033] Example 4 The only difference from Example 1 is: 3 parts of ammonium polyphosphate, 2 parts of 1,2,2-trifluorovinyltriphenylsilane, and 15 parts of aluminum hydroxide.

[0034] Example 5 The only difference from Example 1 is: 1.8 parts of ammonium polyphosphate, 1.2 parts of 1,2,2-trifluorovinyltriphenylsilane, and 17 parts of aluminum hydroxide.

[0035] Example 6 The only difference from Example 1 is: 0.6 parts of ammonium polyphosphate, 0.4 parts of 1,2,2-trifluorovinyltriphenylsilane, and 19 parts of aluminum hydroxide.

[0036] Example 7 The only difference from Example 4 is: 2 parts of ammonium polyphosphate and 3 parts of 1,2,2-trifluorovinyltriphenylsilane.

[0037] Example 8 The only difference from Example 4 is: 1.5 parts of ammonium polyphosphate and 3.5 parts of 1,2,2-trifluorovinyltriphenylsilane.

[0038] Example 9 The only difference from Example 4 is: 1 part of ammonium polyphosphate and 4 parts of 1,2,2-trifluorovinyltriphenylsilane.

[0039] Example 10 The only difference from Example 7 is that ammonium polyphosphate is replaced by an equal amount of cyclophosphamide.

[0040] Embodiment 11 60 parts of PET resin, 5 parts of toughening agent AX8900, 17 parts of phosphorus-containing flame retardant coated metal hydroxide, and 3 parts of 1,2,2-trifluorovinyl triphenylsilane were mixed evenly, melted, extruded, and granulated to obtain a polyester composite material; The preparation method of phosphorus-containing flame retardant coated metal hydroxide comprises the following steps: dissolving 2 parts of cyclophosphamide in 25 parts of ethanol, adding 15 parts of aluminum hydroxide, mixing evenly, and drying to obtain phosphorus-containing flame retardant coated metal hydroxide.

[0041] Comparative Example 1 60 parts of PET resin, 5 parts of toughening agent AX8900, 8 parts of ammonium polyphosphate and 12 parts of aluminum hydroxide were uniformly mixed, melted, extruded and granulated to obtain a polyester composite material.

[0042] Comparative Example 2 60 parts of PET resin, 5 parts of toughening agent AX8900, 8 parts of 1,2,2-trifluorovinyl triphenylsilane and 12 parts of aluminum hydroxide were uniformly mixed, melted, extruded and granulated to obtain a polyester composite material.

[0043] Comparative Example 3 60 parts of PET resin, 5 parts of toughening agent AX8900, 4.8 parts of ammonium polyphosphate, 3.2 parts of triphenylchlorosilane and 12 parts of aluminum hydroxide were uniformly mixed, melted, extruded and granulated to obtain a polyester composite material.

[0044] Performance Testing: (1) Tensile property: After making a 1A dumbbell-shaped specimen according to the method in GB / T 1040.2-2022, perform heat aging treatment at 150°C for 48 h according to the method in GB / T7141-2008, where the heat aging test chamber is method A; perform initial tensile strength and tensile strength after heat aging tests according to the method in GB / T1040.1-2018, with a test speed of 50 mm / min. The average of 5 test results is taken as the final result, and the rate of change is calculated according to the following formula: Change rate = (initial tensile strength - tensile strength after heat aging) ÷ initial tensile strength × 100%; (2) Flame retardancy: Vertical combustion test was conducted according to the method in UL-94, and the sample thickness was 1.6 mm; The test results are recorded in Table 1.

[0045] Table 1 Test results of polyester composite materials performance

[0046] It can be seen from Table 1 that the polyester composite material provided by the present invention has good high temperature resistance and flame retardancy.

[0047] Compared with Comparative Examples 1 to 3, the thermal aging change rate of the polyester composite material obtained by compounding the phosphorus-containing flame retardant, metal hydroxide and fluorosilane in Example 1 is lower than that of Comparative Examples 1 to 3, and the vertical combustion grade is V-0, indicating that the compound use of the phosphorus-containing flame retardant, metal hydroxide and fluorosilane can improve the high temperature resistance and flame retardancy of the polyester composite material.

[0048] The thermal aging change rate of the polyester composite material obtained in Examples 4 to 5 is lower than that in Examples 1 and 6, indicating that when the mass ratio of the phosphorus-containing flame retardant and the fluorosilane to the metal hydroxide is 3:17 to 5:15, the high temperature resistance of the polyester composite material can be further improved.

[0049] The thermal aging change rate of the polyester composite material obtained in Examples 7 to 8 is lower than that in Examples 4 and 9, indicating that the mass ratio of the phosphorus-containing flame retardant to the fluorosilane is 1.5:3.5 to 2:3, which can further improve the high temperature resistance of the polyester composite material.

[0050] The thermal aging change rate of the polyester composite material obtained in Example 10 is lower than that in Example 7, indicating that when the phosphorus-containing flame retardant is cyclophosphamide, the high temperature resistance of the polyester composite material can be further improved.

[0051] The thermal aging change rate of the polyester composite material obtained in Example 11 is lower than that in Example 10, indicating that the use of phosphorus-containing flame retardants to coat metal hydroxides can further improve the high temperature resistance of the polyester composite material.

[0052] 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 high temperature resistant flame retardant polyester composite material, characterized in that: The invention comprises the following components in parts by weight: 50-60 parts of polyester resin, 1-5 parts of toughening agent and 15-20 parts of flame retardant. The raw materials of the flame retardant comprise phosphorus-containing flame retardant, metal hydroxide and fluorosilane.

2. The high temperature resistant flame retardant polyester composite material according to claim 1, characterized in that: The mass ratio of the phosphorus-containing flame retardant and the fluorosilane to the metal hydroxide is 3:17 to 5:

15.

3. The high temperature resistant flame retardant polyester composite material according to claim 1, characterized in that: The polyester resin includes one or more of PET resin, PEN resin, PBT resin, PBS resin and PTT resin.

4. The high temperature resistant flame retardant polyester composite material according to claim 1, characterized in that: The mass ratio of the phosphorus-containing flame retardant to fluorosilane is 1.5:3.5-2:

3.

5. The high temperature resistant flame retardant polyester composite material according to claim 4, characterized in that: The phosphorus-containing flame retardant is cyclophosphamide.

6. The high temperature resistant flame retardant polyester composite material according to claim 4, characterized in that: The fluorosilane is 1,2,2-trifluorovinyltriphenylsilane.

7. The high temperature resistant flame retardant polyester composite material according to claim 1, characterized in that: The flame retardant comprises a phosphorus-containing flame retardant-coated metal hydroxide and further comprises fluorosilane.

8. The high temperature resistant flame retardant polyester composite material according to claim 7, characterized in that: The preparation method of the phosphorus-containing flame retardant coated metal hydroxide comprises the following steps: dissolving the phosphorus-containing flame retardant, adding the metal hydroxide, mixing evenly, and drying to obtain the phosphorus-containing flame retardant coated metal hydroxide.

9. The high temperature resistant flame retardant polyester composite material according to claim 1, characterized in that: It also includes at least one of the following features: antioxidant, lubricant, antistatic agent, nucleating agent, colorant.

10. The method for preparing a high temperature resistant flame retardant polyester composite material according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: uniformly mixing the components in parts by mass, melting, extruding and granulating to obtain a high temperature resistant and flame retardant polyester composite material.

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