Flame retardant composition for ceramic polyolefin resin and preparation method thereof

Abstract

The invention provides a flame retardant composition for ceramic polyolefin resin and a preparation method of the flame retardant composition. The composition comprises the following raw materials in parts by weight: 64-90 parts of ceramic powder and 7-15 parts of an intumescent flame retardant. According to the invention, not only can the flame retardant property of the polyolefin resin material be improved, but also the ceramic layer and the polyolefin matrix can be tightly bonded in the ceramization process, so that the density and strength of the ceramic layer are effectively improved.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and particularly relates to a flame retardant composition for ceramic polyolefin resin and a preparation method thereof. Background Art

[0002] Ceramic polyolefin is a new type of refractory material. It is a special composite material made of polyolefin as a matrix and incorporating ceramic fillers, fluxing agents, flame retardants, and other additives. When exposed to fire or high temperatures, the ceramic fillers in ceramic polyolefin are sintered into a ceramic body with a certain mechanical strength, thus providing heat insulation and oxygen isolation. The formation of this ceramic body helps maintain the structural integrity of the material at high temperatures and reduce the spread of fire. Ceramic polyolefin products have a wide range of applications in various fields, including aerospace, automotive, electronics, and medical devices. Due to their high strength, light weight, and high-temperature resistance, they can be used to manufacture lightweight structural parts, components for high-temperature environments, and applications requiring high rigidity and wear resistance. However, most ceramic polyolefins currently suffer from problems such as high ceramic forming temperatures, insufficient ceramic density, and low ceramic strength, which to some extent hinder their application and development. Summary of the Invention

[0003] The purpose of the present invention is to address the above-mentioned problems existing in the prior art and to provide a flame retardant composition for ceramic polyolefin resin and a preparation method thereof, which can make the ceramic forming temperature of ceramic polyolefin resin low, the ceramic forming density and high strength.

[0004] To achieve the above objectives, the technical solutions of the present invention are as follows:

[0005] In a first aspect, the present invention provides a flame retardant composition for ceramicizing polyolefin resin, wherein the raw material composition and weight ratio thereof include: 64-90 parts of ceramic powder and 7-15 parts of intumescent flame retardant.

[0006] The porcelain powder includes porcelain powder A and porcelain powder B, and the weight ratio of porcelain powder A to porcelain powder B is 60-80:4-10;

[0007] The porcelain powder A is at least one of wollastonite, calcium silicate, mica powder, montmorillonite, and halloysite powder;

[0008] The porcelain powder B is at least one of precipitated silica, fumed silica, bentonite, calcium carbonate, and magnesium carbonate.

[0009] The porcelain powder A is calcium silicate, and the porcelain powder B is fumed silica.

[0010] The intumescent flame retardant comprises flame retardant C and flame retardant D, wherein the weight ratio of flame retardant C to flame retardant D is 2-5:5-10;

[0011] The flame retardant C is at least one of piperazine pyrophosphate, ammonium polyphosphate, melamine polyphosphate, triazine carbonizing agent, pentaerythritol, and melamine cyanurate;

[0012] The flame retardant D is at least one of aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

[0013] The flame retardant C is a mixture of ammonium polyphosphate and a triazine carbon-forming agent, and the weight ratio of ammonium polyphosphate to the triazine carbon-forming agent is 1.5-2.5:1;

[0014] The flame retardant D is aluminum hydroxide.

[0015] The raw material composition of the composition further includes a flux and a surface modifier, and the weight ratio of the flux, the surface modifier and the porcelain powder is 9-15:1-5:64-90;

[0016] The flux is at least one of zinc borate, borax, zinc oxide, magnesium oxide, calcium oxide and low-melting-point glass powder;

[0017] The surface modifier is at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.

[0018] The flux is low-melting-point glass powder, and the surface modifier is a silane coupling agent.

[0019] In a second aspect, the present invention provides a method for preparing a flame retardant composition for ceramic polyolefin resin, comprising:

[0020] First, porcelain powder, intumescent flame retardant and flux are uniformly mixed in a required proportion, and then a surface modifier is added to perform surface modification treatment to obtain a flame retardant composition.

[0021] The surface modification temperature is 103-107°C.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The raw material composition and weight ratio of a flame retardant composition for ceramicizing polyolefin resins of the present invention include: 64-90 parts by weight of ceramic powder and 7-15 parts by weight of intumescent flame retardant. By adding a small amount of intumescent flame retardant to the ceramic powder, this design not only improves the flame retardancy of the polyolefin resin material but also ensures a tight bond between the ceramic layer and the polyolefin substrate during the ceramicization process, effectively increasing the density and strength of the ceramic layer.

[0024] 2. The raw material composition of the flame retardant composition for ceramic polyolefin resin of the present invention also includes a surface modifier, which can modify the ceramic powder and the intumescent flame retardant at 103-107°C, thereby improving the interfacial compatibility with the silicone resin and the mechanical properties of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Schematic diagram of the modification reaction in Example 1.

[0026] Figure 2 This is a diagram showing the porcelain effect after firing of Example 1.

[0027] Figure 3 This is a diagram of the porcelain effect after firing of Example 2.

[0028] Figure 4 This is a diagram of the porcelain effect after firing of Example 3.

[0029] Figure 5 This is a diagram showing the porcelain effect after firing of Example 4.

[0030] Figure 6 This is a diagram showing the porcelain effect after firing of Example 5.

[0031] Figure 7 This is a diagram of the porcelain effect after firing of comparative example 1.

[0032] Figure 8 This is a diagram of the porcelain effect after firing of comparative example 2.

[0033] Figure 9 This is a diagram of the porcelain effect after firing of comparative example 3. DETAILED DESCRIPTION

[0034] The present invention will be further described in detail below with reference to specific embodiments and the accompanying drawings.

[0035] The present invention proposes a flame retardant composition for ceramicized polyolefin resin. The composition combines a small amount of intumescent flame retardant with ceramic powder. The intumescent flame retardant expands into char at high temperature. During the formation process, the char layer tightly bonds the ceramic layer to the polymer matrix, thereby improving the density and strength of the ceramic layer.

[0036] Example 1:

[0037] A flame retardant composition for ceramicizing polyolefin resin, comprising the following raw materials in parts by weight: ceramic powder A (calcium silicate, 85%), ceramic powder B (fumed silica, 5%), flame retardant C (a mixture of ammonium polyphosphate and a triazine carbonizing agent, 3%), flame retardant D (aluminum hydroxide, 5%), flux (low-melting-point glass powder, 10%), and silane coupling agent KH-5502.

[0038] The preparation method of the above composition is:

[0039] First, add porcelain powder A, porcelain powder B, flame retardant C, flame retardant D and flux in the required amount into a high-speed mixer, stir while heating to 105 ° C, then add silane coupling agent to the above mixture, stir and react for 30 minutes to complete the surface modification, and obtain a flame retardant composition. The principle diagram of the stirring modification reaction is as follows Figure 1 shown.

[0040] Example 2:

[0041] The difference from Example 1 is that:

[0042] The raw material composition and weight proportions of the flame retardant composition are: porcelain powder A-calcium silicate 75, porcelain powder B-fumed silica 5, flame retardant C-a mixture of piperazine pyrophosphate and melamine polyphosphate in a weight ratio of 1.5:1 10, flame retardant D-aluminum hydroxide 5, flux-low melting point glass powder 13, silane coupling agent KK-5501.

[0043] Example 3:

[0044] The difference from Example 1 is that:

[0045] The raw material composition and weight proportions of the flame retardant composition are: porcelain powder A-calcium silicate 85, porcelain powder B-fumed silica 5, flame retardant C-a mixture of piperazine pyrophosphate and melamine polyphosphate 3, flame retardant D-aluminum hydroxide 5, flux-zinc borate 10, silane coupling agent KK-5505.

[0046] Example 4:

[0047] The difference from Example 1 is that:

[0048] The raw material composition and weight proportions of the flame retardant composition are: porcelain powder A-calcium silicate 60, porcelain powder B-bentonite 5, flame retardant C-a mixture of piperazine pyrophosphate and melamine polyphosphate 7, flame retardant D-aluminum hydroxide 5, flux-low melting point glass powder 12, silane coupling agent KK-5503.

[0049] Example 5:

[0050] The difference from Example 1 is that:

[0051] The raw material composition and weight proportions of the flame retardant composition are: porcelain powder A-wollastonite 85, porcelain powder B-fumed silica 5, flame retardant C-a mixture of ammonium polyphosphate and triazine carbonizing agent 5, flame retardant D-aluminum hydroxide 5, flux-low melting point glass powder 10, silane coupling agent KK-5502.

[0052] Comparative Example 1:

[0053] A composition for ceramicizing polyolefin resin, the raw material composition and weight parts of the composition are: ceramic powder A-calcium silicate 85, ceramic powder B-fumed white carbon black 5, flux-low melting point glass powder 10, silane coupling agent KK-5502.

[0054] The specific preparation method of the above composition is the same as that of Example 1.

[0055] Comparative Example 2:

[0056] A flame retardant composition for ceramicizing polyolefin resins, comprising the following raw materials in parts by weight: 85 parts of ceramic powder A-calcium silicate, 5 parts of ceramic powder B-fumed silica, 8 parts of a non-expanding flame retardant-diethylaluminum hypophosphite, 10 parts of a flux-low-melting-point glass powder, and 2 parts of a silane coupling agent KK-5502.

[0057] The specific preparation method of the above composition is the same as that of Example 1.

[0058] Comparative Example 3:

[0059] A flame retardant composition for ceramicizing polyolefin resin, comprising the following raw materials in parts by weight: 85 parts of ceramic powder A-calcium silicate, 5 parts of ceramic powder B-fumed silica, 8 parts of a non-expanding flame retardant-phosphate flame retardant, 10 parts of a flux-low melting point glass powder, and 2 parts of a silane coupling agent KK-5502.

[0060] The specific preparation method of the above composition is the same as that of Example 1.

[0061] Performance Verification:

[0062] A polypropylene resin composition was prepared according to a formulation comprising 55 parts by mass of polypropylene (melt flow rate = 8 g / 10 min at 230° C., load 2.16 kg, measured in accordance with JIS K7210), 0.1 part by mass of calcium stearate (organic crystal nucleating agent), 0.1 part by mass of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid methyl]methane (phenolic antioxidant), 0.1 part by mass of tris(2,4-di-tert-butylphenyl) phosphite (phosphorus antioxidant), and 0.3 part by mass of glycerol monostearate (lubricant). 45 parts by mass of the compositions obtained in Examples 1-5 and Comparative Examples 1-3 were added to the polypropylene resin composition to obtain flame-retardant resin compositions of each case. Each flame retardant resin composition was then pressed at 220°C and 10 MPa for 15 minutes to obtain a flame retardant test piece with a length of 127 mm, a width of 10.7 mm, and a thickness of 4 mm, and a porcelain-forming performance test plate with a length of 140 mm, a width of 120 mm, and a thickness of 2 mm.

[0063] 1. Flame retardancy evaluation

[0064] Each flame retardant test specimen was held vertically, and a burner was applied to the lower end for 10 seconds. The flame was then removed, and the time it took for the fire on each specimen to extinguish was measured. Then, while the fire was extinguished, the flame was applied a second time for 10 seconds, and the time it took for the fire to extinguish was measured again. The cotton underneath the specimen was also evaluated for ignition due to the falling flame. The flammability rating was determined according to the UL-94V standard based on the first and second burning times and whether the cotton caught fire. The results are shown in Table 1. V0 is the highest flammability rating, and flame retardancy decreases in the order of V1 to V2.

[0065] 2. Porcelain performance test

[0066] Each porcelain performance test plate was held vertically and burned with the flame of a butane torch for 15 minutes. The porcelain forming time, porcelain forming temperature, porcelain forming density and strength of each test plate were then tested. The results are shown in Table 1. Figure 2-9 shown.

[0067] Table 1 Performance test results of each test board

[0068]

[0069] Note: Flexural strength test standard (ASTM C773)

[0070] Compressive strength test standard (ISO 14704)

[0071] From Table 1, Figure 2-9 It can be seen that the polypropylene material samples obtained in Examples 1-5 all passed the UL-94V-0 flame retardant test, and the test plates quickly formed porcelain after being burned with the flame of a butane spray gun. The ceramic layer was tightly connected to the substrate and had high strength, indicating that they had good flame retardant properties and porcelain-forming properties. The flame-retardant polypropylene material samples produced using Comparative Examples 1-3 all failed to pass the UL-94V-0 flame retardant test. In addition, the test plates of Comparative Examples 1-3 formed porcelain slowly after being burned with the flame of a butane spray gun, the ceramic layer was not tightly connected to the substrate, and the strength was also low, indicating that the porcelain-forming properties were poorer than those of the Examples.

[0072] The above results show that the flame retardant composition for ceramic polyolefin prepared by the present invention has better flame retardancy, and the polyolefin resin composition prepared using the same has excellent rapid ceramic-forming performance.

Claims

1. A flame retardant composition for ceramic polyolefin resin, characterized in that: The raw material composition and weight ratio of the composition include: 64-90 parts of porcelain powder and 7-15 parts of intumescent flame retardant.

2. The flame retardant composition for ceramic polyolefin resin according to claim 1, characterized in that: The porcelain powder includes porcelain powder A and porcelain powder B, and the weight ratio of porcelain powder A to porcelain powder B is 60-80:4-10; The porcelain powder A is at least one of wollastonite, calcium silicate, mica powder, montmorillonite, and halloysite powder; The porcelain powder B is at least one of precipitated silica, fumed silica, bentonite, calcium carbonate, and magnesium carbonate.

3. The flame retardant composition for ceramic polyolefin resin according to claim 2, characterized in that: The porcelain powder A is calcium silicate, and the porcelain powder B is fumed silica.

4. A flame retardant composition for ceramic polyolefin resin according to claim 1 or 2, characterized in that: The intumescent flame retardant comprises flame retardant C and flame retardant D, wherein the weight ratio of flame retardant C to flame retardant D is 2-5:5-10; The flame retardant C is at least one of piperazine pyrophosphate, ammonium polyphosphate, melamine polyphosphate, triazine carbonizing agent, pentaerythritol, and melamine cyanurate; The flame retardant D is at least one of aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

5. The flame retardant composition for ceramic polyolefin resin according to claim 4, characterized in that: The flame retardant C is a mixture of ammonium polyphosphate and triazine carbonizing agent; The flame retardant D is aluminum hydroxide.

6. The flame retardant composition for ceramic polyolefin resin according to claim 1, characterized in that: The raw material composition of the composition further includes a flux and a surface modifier, and the weight ratio of the flux, the surface modifier and the porcelain powder is 9-15:1-5:64-90; The flux is at least one of zinc borate, borax, zinc oxide, magnesium oxide, calcium oxide and low-melting-point glass powder; The surface modifier is at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.

7. The flame retardant composition for ceramic polyolefin resin according to claim 6, characterized in that: The flux is low-melting-point glass powder, and the surface modifier is a silane coupling agent.

8. A method for preparing the flame retardant composition for ceramic polyolefin resin according to claim 6, characterized in that: The preparation method comprises: First, porcelain powder, intumescent flame retardant and flux are uniformly mixed in a required proportion, and then a surface modifier is added to perform surface modification treatment to obtain a flame retardant composition.

9. The method for preparing a flame retardant composition for ceramic polyolefin resin according to claim 8, characterized in that: The surface modification temperature is 103-107°C.

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