A ablative-resistant polycarbonate composition and a preparation method and application thereof

Abstract

The present application relates to a kind of ablative-resistant polycarbonate compositions and its preparation method and application, and ablative-resistant polycarbonate compositions include the following weight parts components: PC resin 40~70 parts;Reinforcing fiber 10~30 parts;Ablative-resistant agent 5~20 parts;Flame retardant 15~25 parts;Other auxiliary agent 0.1~2 parts;The ablative-resistant agent includes pyrolite.Compared with prior art, the present application has the advantages of improving the ablative-resistant performance of material, etc..

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to an ablation-resistant polycarbonate composition, its preparation method, and its application. Background Technology

[0002] Polycarbonate (PC) is widely used in the automotive, aerospace, and electronics industries due to its high transparency and balanced mechanical properties. However, conventional PC's ablation resistance is unsatisfactory, making it difficult to meet the safety requirements of new energy batteries and other applications. Ablation-resistant functionalized flame-retardant PC can not only increase product design freedom and meet the multi-scenario, multi-functional needs of energy storage and power batteries, but also significantly reduce weight compared to sheet metal parts, potentially reducing carbon dioxide and solid waste emissions by tens of thousands of tons annually. Therefore, developing ablation-resistant functionalized flame-retardant PC materials is an urgent priority and can provide ablation-resistant solutions for the battery industry, facilitating high-quality iteration of related components for new energy vehicles.

[0003] When subjected to flame impact, the carbonization of the resin and the erosion of the carbonized layer are crucial. The key features of ablation-resistant functional materials should include: 1. Maintaining the structural integrity as much as possible during flame erosion; 2. Blocking heat to the greatest extent possible, keeping the back surface temperature as low as possible, and avoiding damage to the substrate by thermal or chemical reactions; 3. Having a carbon layer of a certain thickness and the carbon layer porosity should be as low as possible.

[0004] Patent CN105385136A discloses a basalt fiber-reinforced halogen-free flame-retardant polycarbonate composite material and its preparation method, comprising the following raw materials in parts by weight: 30-50 parts polycarbonate; 10-30 parts basalt fiber; 20-25 parts halogen-free flame retardant; 2-5 parts synergistic flame retardant; 1-5 parts toughening agent; 2-5 parts compatibilizer; 1-3 parts coupling agent; 0.6-5 parts heat stabilizer; 0.2-0.8 parts antioxidant; and 0.9-1.4 parts processing aid. This composite material incorporates basalt fiber as a reinforcing medium and halogen-free compounds as flame retardants, improving mechanical properties and reducing smoke density. However, its effect on improving the material's ablation resistance is limited. Summary of the Invention

[0005] The purpose of this invention is to provide an ablation-resistant polycarbonate composition, its preparation method, and its application, thereby improving the ablation resistance of the material.

[0006] The objective of this invention can be achieved through the following technical solution: an ablation-resistant polycarbonate composition comprising the following components in parts by weight:

[0007]

[0008] The heat-resistant agent includes igneous rocks.

[0009] Preferably, the fire-resistant agent is acidic igneous rock.

[0010] More preferably, the acidic igneous rock has a silica content of 68% to 90% and a mesh size of 500 to 1200 mesh.

[0011] Preferably, the flame retardant is a sulfonate flame retardant.

[0012] More preferably, the flame retardant is one or more of aromatic sulfonate flame retardants and phenoxy polyphosphazene flame retardants.

[0013] More preferably, the flame retardant is one or more of potassium 3-benzenesulfonylbenzenesulfonate and phenoxy polyphosphazene.

[0014] Preferably, the PC resin is bisphenol A type polycarbonate with a melt index (300℃*1.2kg) of 9 to 23 g / min.

[0015] Preferably, the reinforcing fiber is basalt fiber (chopped), with a length of 5-50 mm and a diameter of 7-25 μm.

[0016] Preferably, the other additives include antioxidants, lubricants, and / or colorants.

[0017] More preferably, the antioxidant is one or more of antioxidant 1076, antioxidant 1010, antioxidant 168 or antioxidant 618.

[0018] More preferably, the lubricant is one or more of silicone powder, paraffin wax, stearic acid, butyl stearate, or ethylene bis-stearamide.

[0019] More preferably, the pigment is inorganic carbon black.

[0020] More preferably, the other additives include antioxidants, lubricants, and colorants;

[0021] More preferably, the weight ratio of the antioxidant, lubricant and colorant is 1:(2.5-3.5):(4.5-5.5).

[0022] A method for preparing the above-mentioned ablation-resistant polycarbonate composition includes the following steps:

[0023] (1) Prepare the components according to the following weight proportions:

[0024]

[0025] (2) After the PC resin, flame retardant and other additives are mixed evenly in a high-speed mixer, they are added to the screw extruder through the main feed port. The reinforcing fiber and the ablation resistant agent are added to the screw extruder through the side feed port. The extrusion is carried out under the conditions of an extrusion temperature of 240-280℃ and a screw speed of 300-500 rpm. The mixture is then cooled and granulated to obtain the ablation resistant polycarbonate composition.

[0026] An application of the above-mentioned ablation-resistant polycarbonate composition is to use the polycarbonate composition in the field of new energy batteries.

[0027] Preferably, the polycarbonate composition is used to prepare the top cover of the new energy battery box and the top cover of the battery pack.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. In this invention, igneous rocks melt at high temperatures to form a glassy protective layer, which isolates oxygen and absorbs the heat generated by combustion, promoting the densification of the carbon layer and reducing porosity.

[0030] 2. The basalt fiber of the present invention forms a three-dimensional reinforcing network at high temperature, which effectively inhibits the delamination and melting of the material during flame erosion. The silicate components on the fiber surface chemically bond with the matrix resin to form a stable interpenetrating network at high temperature, which delays the decomposition of the matrix. The fiber network maintains the overall structure of the material and prevents ablation and perforation.

[0031] 3. The sulfonates of this invention can catalyze the formation of carbon. The sulfonates work synergistically with the acidic components of igneous rocks to accelerate the densification process of the carbon layer.

[0032] 4. The endothermic melting of igneous rock and the endothermic decomposition of sulfonates in this invention reduce the surface temperature of the material and delay thermal decomposition. Thermodynamically, this reduces the total thermal conductivity. The carbon layer and the molten layer inhibit secondary oxidation and thermal decomposition of the substrate and improve chemical stability. The rigid network of basalt fibers inhibits thermal expansion. The multi-component synergistic "melting-carbonization-reinforcement" composite mechanism improves the ablation resistance of the material.

[0033] 5. This invention significantly improves the thermal insulation performance of polycarbonate under flame burning conditions, while also enhancing the material's ablation resistance. Furthermore, it exhibits excellent processing performance, good formability, and good dimensional stability, thus broadening the application scenarios of traditional materials in the new energy field. Attached Figure Description

[0034] Figure 1 This is a test diagram of the ablation resistance of the ablation-resistant polycarbonate composition of the present invention;

[0035] Figure 2 These are photographs of the ablation-resistant polycarbonate composition of the present invention after ablation.

[0036] Figure 3 This is a photograph of a conventional material after ablation. Detailed Implementation

[0037] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0038] Unless otherwise specified, the reagents, methods, instruments, and equipment used in this invention are conventional in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0039] A method for preparing an ablation-resistant polycarbonate composition, the method comprising the following steps:

[0040] The raw materials are mixed according to the weight proportions in Table 1 and added to a twin-screw extruder. The mixture is then melt-extruded at an extrusion temperature of 240-280℃ and a screw speed of 300-500 rpm. After cooling and granulation, the product is obtained.

[0041] The materials in Table 1 are as follows:

[0042] PC resin: Mitsubishi Chemical's 7025PJ;

[0043] Reinforcing fiber: basalt fiber, Guizhou Shixin short-cut basalt fiber with a length of 5-50mm and a diameter of 7-25μm;

[0044] Burn-resistant agent: acidic igneous rock, igneous rock from Dongfeng Mining, with a silica content of 70% and a mesh size of 600;

[0045] Flame retardant: Potassium 3-benzenesulfonylbenzenesulfonate from Hubei Chenghai; flame retardant HPCTP from Weihai Jinwei, with potassium 3-benzenesulfonylbenzenesulfonate / HPCTP added at a weight ratio of 3:1;

[0046] Talc powder: Xufeng's XFH-8860-Y6;

[0047] The antioxidant is BASF's IRGANOX 1010;

[0048] The lubricant is Chenguang's GM-100 silicone powder;

[0049] Pigment: Carbon black, commercially available;

[0050] The above-described embodiments will be described in more detail below with reference to specific examples.

[0051] Example 1

[0052] A method for preparing an ablation-resistant polycarbonate composition, comprising the following specific steps:

[0053] According to the weight parts in Table 1, weigh 60 parts by weight of PC resin, 25 parts by weight of flame retardant, 0.1 parts by weight of antioxidant, 0.3 parts by weight of lubricant, and 0.5 parts by weight of color powder. Mix the PC resin, flame retardant, antioxidant, lubricant, and color powder evenly in a high-speed mixer and add them to a twin-screw extruder through the main feed port. Weigh 15 parts by weight of reinforcing fiber and 20 parts by weight of pyrolysis resistant agent and add them to the twin-screw extruder through the side feed port for melt blending and extrusion. After cooling, pelletizing, and drying, obtain the pyrolysis resistant polycarbonate composition.

[0054] The extruder's process conditions are as follows: Zone 1 temperature 240℃, Zone 2 temperature 250℃, Zone 3 temperature 260℃, Zone 4 temperature 270℃, Zone 5 temperature 270℃, Zone 6 temperature 270℃, Zone 7 temperature 265℃, Zone 8 temperature 265℃, Zone 9 temperature 270℃, twin screw speed 500rpm, extrusion temperature 270℃, and extrusion pressure 3MPa.

[0055] Table 1. Parts by weight of the formulations in Examples 1-4 and Comparative Examples 1-2

[0056]

[0057] Note: In Table 1, "-" indicates that the component is not present.

[0058] Examples 2-4

[0059] A method for preparing an ablation-resistant polycarbonate composition, comprising the following specific steps:

[0060] According to the weight parts in Table 1, weigh PC resin, flame retardant, antioxidant, lubricant, and color powder, and mix them evenly in a high-speed mixer. Add the mixture to a twin-screw extruder through the main feed port. Weigh reinforcing fiber and scorch resistant agent, and add them to the twin-screw extruder through the side feed port for melt blending and extrusion. After cooling, pelletizing, and drying, obtain an ablation-resistant polycarbonate composition.

[0061] The extruder's process conditions are as follows: Zone 1 temperature 240℃, Zone 2 temperature 250℃, Zone 3 temperature 260℃, Zone 4 temperature 270℃, Zone 5 temperature 270℃, Zone 6 temperature 270℃, Zone 7 temperature 265℃, Zone 8 temperature 265℃, Zone 9 temperature 270℃, twin screw speed 500rpm, extrusion temperature 270℃, and extrusion pressure 3MPa.

[0062] Comparative Examples 1-6

[0063] A method for preparing a polycarbonate composition, comprising the following specific steps:

[0064] Weigh each component according to the weight parts in Table 1, and add each component to the twin-screw extruder according to the feeding method of the embodiment. In Comparative Example 5, the talc powder is added in the same way as the calciner.

[0065] The extruder's process conditions are as follows: Zone 1 temperature 240℃, Zone 2 temperature 250℃, Zone 3 temperature 260℃, Zone 4 temperature 270℃, Zone 5 temperature 270℃, Zone 6 temperature 270℃, Zone 7 temperature 265℃, Zone 8 temperature 265℃, Zone 9 temperature 270℃, twin screw speed 500rpm, extrusion temperature 270℃, and extrusion pressure 3MPa.

[0066] Mechanical properties and ablation resistance tests:

[0067] The polycarbonate composition particles obtained in Examples 1-4 and Comparative Examples 1-6 were injection molded to prepare test strips and test plates. After drying at 100°C for 4 hours, the performance was evaluated, and the results are shown in Table 2.

[0068] Table 2 Performance Comparison of Comparative Examples and Examples

[0069]

[0070] The flow length ratio test conditions were: injection temperature 290℃, pressure 40MPa, speed 40ccm / s, cooling time 15s, and mold temperature 90℃.

[0071] The test method for ablation resistance (level) is as follows: The material is processed into a flat sample with a thickness of 150×150×3mm. The test is conducted with the flame of a high-temperature butane torch 5cm away from the sample. Observe whether the sample exhibits burn-through, dripping, or other phenomena. If the sample structure remains largely intact without burn-through, dripping, or other phenomena, it is considered to have excellent ablation resistance.

[0072] Comparing Examples 1-4 with Comparative Examples 1-4, it is evident that the unmodified polycarbonate composite material exhibits very poor ablation resistance. In Examples 1-4, the addition of reinforcing fibers and ablation resistant agents improved the ablation resistance of the polycarbonate composite material; no burn-through was observed after 10 minutes of ablation at 1300°C. Comparing Examples 1-4 with Comparative Examples 1-4, it is clear that adding reinforcing fibers and ablation resistant agents can significantly improve the ablation resistance of polycarbonate, and the temperature on the back side of the sample decreased significantly, indicating that the addition of reinforcing fibers and ablation resistant agents can mitigate heat conduction. Comparing Examples 1-4 with Comparative Examples 1-4, it is evident that adjusting the appropriate ratio of reinforcing fibers and ablation resistant agents did not reduce the flow length to length ratio, indicating that the examples possess good processability.

[0073] Comparing Example 1 and Comparative Example 5, it can be seen that adding a heat-resistant agent, compared with adding a filler, is more conducive to the vitrification and heat resistance when combined with reinforcing fibers, which is beneficial to improving the ablation resistance of the material.

[0074] Comparing Example 1 and Comparative Example 6, it can be seen that adding too much flame retardant not only fails to achieve the expected ablation resistance effect, but also easily leads to the deterioration of material properties.

[0075] like Figure 1 As shown, a butane flame gun was used to vertically spray flame onto the test sample to test the material's ablation resistance. Figure 2 The image shows the test sample of Example 1 after being ablated at 1300℃ for 10 minutes. It can be seen that the sample is relatively intact and no burn-through phenomenon has occurred. Figure 3 The photo shows a test sample made from a commercially available sabic EXL9330 under the same conditions. It can be seen that the sample was burned through.

[0076] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. An ablation-resistant polycarbonate composition, characterized in that, Includes the following components by weight: 60-70 parts of PC resin; 10-30 parts of reinforcing fiber; 5-20 parts of heat-resistant agent; 15-20 parts flame retardant; Other auxiliary agents: 0.1-2 parts; The refractory agent is an acidic igneous rock with a mesh size of 500-1200 mesh; The flame retardant is an aromatic sulfonate flame retardant and a phenoxy polyphosphazene flame retardant; The reinforcing fiber is a short-cut basalt fiber with a length of 5~50mm and a diameter of 7~25μm.

2. The ablation-resistant polycarbonate composition according to claim 1, characterized in that, The PC resin is bisphenol A type polycarbonate, 300℃ At 1.2 kg, the melt flow index is 9~23 g / min.

3. The ablation-resistant polycarbonate composition according to claim 1, characterized in that, The other additives include antioxidants, lubricants, and / or colorants.

4. The ablation-resistant polycarbonate composition according to claim 3, characterized in that, The antioxidant is one or more of antioxidant 1076, antioxidant 1010, antioxidant 168 or antioxidant 618; The lubricant is one or more of silicone powder, paraffin wax, stearic acid, butyl stearate, or ethylene bis-stearamide; The pigment is inorganic carbon black.

5. The ablation-resistant polycarbonate composition according to claim 3, characterized in that, The other additives include antioxidants, lubricants, and colorants; The weight ratio of the antioxidant, lubricant and colorant is 1: (2.5~3.5): (4.5~5.5).

6. A method for preparing the ablation-resistant polycarbonate composition according to any one of claims 1 to 3, characterized in that, Includes the following steps: PC resin, flame retardant and other additives are mixed evenly in a high-speed mixer and then fed into a screw extruder through the main feed port. Reinforcing fibers and ablation resistant agent are fed into the screw extruder through the side feed port. The mixture is melt-extruded at an extrusion temperature of 240-280℃ and a screw speed of 300-500 rpm, cooled and granulated to obtain the ablation resistant polycarbonate composition.

7. The application of the ablation-resistant polycarbonate composition according to any one of claims 1 to 3, characterized in that, The polycarbonate composition is used in the field of new energy batteries.

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