Polycarbonate material and preparation method thereof

Abstract

The invention discloses a polycarbonate material and a preparation method thereof. The polycarbonate material is prepared from the following components in parts by mass: 100 parts of polycarbonate, 30 to 50 parts of silicon copolymerized polycarbonate, 3 to 10 parts of brominated polycarbonate, 30 to 50 parts of polysulfone, 2 to 10 parts of polyvinylidene chloride, 10 to 20 parts of polyarylate fiber, 1 to 5 parts of wollastonite, 1 to 5 parts of zinc stannate compound, 0.3 to 1 part of ferrocene and 0.3 to 1 part of phosphorus flame retardant. By adding the polyarylester fiber to form a reinforcing system, on one hand, the characteristics of low smoke density and low heat release of polyarylester are utilized, and on the other hand, the polyarylester is added in a fiber form, so that the problems of large processing temperature difference and poor compatibility of the two materials are solved, and meanwhile, the heat resistance and multi-axis impact resistance of the material are more excellent; the obtained polycarbonate is low in smoke density and low in heat release in the combustion process, and is particularly suitable for being applied to the fields of aviation and railways.

Description

Technical Field

[0001] This application relates to the field of polymer materials, and more particularly to a polycarbonate material and its preparation method. Background Technology

[0002] Polycarbonate (PC), as a thermoplastic engineering plastic, has excellent heat resistance and impact resistance, as well as a very good appearance. It is currently widely used in consumer electronics, automobiles, home appliances, energy storage and other fields.

[0003] PC material has a low limiting oxygen index, reaching V2 level under the UL94 test standard. However, it releases a lot of heat and produces a large amount of smoke when burning, which greatly limits its application in confined spaces such as aircraft cabins and railway cabins. For aerospace, the US Federal Aviation Administration has set standard FAR25.853, and for rail transportation, the European Union has introduced the unified fire protection standard EN45545. With the development of China's large aircraft, the Civil Aviation Administration of China has also set standard CCAR25. These standards all put forward clear requirements for the smoke density and heat release of materials during combustion. These requirements play a crucial role in reducing combustion in aircraft and railway cabins and increasing safety. Therefore, developing a PC material that can meet the requirements of low smoke density and low heat release is of great significance.

[0004] Existing technologies disclose several patents concerning low smoke density and low heat release polycarbonate materials. CN112409770A discloses a low smoke density, low heat release, halogen-free flame-retardant PC material and its preparation method and application, which includes the following components: 10-80wt% polycarbonate, 10-60wt% polycarbonate siloxane copolymer, 4-20wt% organosilicon / phenoxy polyphosphazene copolymer, 5-30wt% mineral powder, and 0.1-5wt% processing aids. The organosilicon / phenoxy polyphosphazene copolymer used in this patent needs to be repolymerized, the raw materials are not readily available, the production cycle is long, and the heat resistance and impact performance of the material will suffer some loss.

[0005] CN109777073A discloses a polycarbonate composition that can effectively reduce smoke density and lower heat release rate, as well as its preparation method. The components are composed of the following parts by weight: 100 parts polycarbonate; 1-30 parts boehmite; 0.1-1.5 parts sulfonate; and 1-12 parts phosphorus-containing compound. The addition of organic phosphorus-containing chemicals in this patent leads to a decrease in the material's heat resistance and impact resistance. Furthermore, the addition of boehmite also significantly reduces the material's physical properties, severely limiting its application scenarios.

[0006] Based on the aforementioned existing technology, it is of great significance to provide a polycarbonate material with excellent comprehensive performance, low smoke density, and low heat release. Summary of the Invention

[0007] In view of this, this application provides a polycarbonate material with low smoke density, low heat release, and that meets the requirements of CCAR25 standard, while also having good overall performance.

[0008] This application provides a polycarbonate material comprising, by weight parts, 100 parts polycarbonate, 30 to 50 parts silicon copolymer polycarbonate, 3 to 10 parts brominated polycarbonate, 30 to 50 parts polysulfone, 2 to 10 parts polyvinylidene chloride, 10 to 20 parts polyarylate fiber, 1 to 5 parts wollastonite, 1 to 5 parts zinc stannate compound, 0.3 to 1 part ferrocene, and 0.3 to 1 part phosphorus-based flame retardant.

[0009] In some specific implementations, the polycarbonate is bisphenol A type polycarbonate with a melt index of 2 g / 10 min to 5 g / 10 min at 300 °C and 1.2 kg.

[0010] In some specific implementations, the melt index of the silicon copolymer polycarbonate at 300°C and 1.2 kg is 8 g / 10 min to 15 g / 10 min, the mass percentage of siloxane in the silicon copolymer polycarbonate is 4% to 6%, and the number of repeating segments of the siloxane chain is greater than 85.

[0011] In some specific implementations, the bromine content in the brominated polycarbonate is 10% to 30%, and the melt index at 300°C and 1.2 kg is 10 g / 10 min to 35 g / 10 min.

[0012] In some specific implementations, the polysulfone is bisphenol A type polysulfone with a melt index of 80g / 10min to 100g / 10min at 360℃ and 10kg.

[0013] In some specific implementations, the polyvinylidene chloride is a vinylidene chloride-methyl acrylate copolymer with a weight-average molecular weight of 80,000 to 100,000.

[0014] In some specific implementations, the polyaryl ester fiber is a liquid crystal polyaryl ester fiber, the tensile strength of the polyaryl ester fiber is 15 cN / dtex to 25 cN / dtex, and the density of the polyaryl ester fiber is 1.42. Up to 1.46 .

[0015] In some specific implementations, the wollastonite particle size is 1-5 μm.

[0016] In some specific implementations, the zinc stannate compound is zinc hydroxystannate.

[0017] In some specific implementations, the ferrocene is crystalline ferrocene with a melting point of 170°C to 174°C.

[0018] In some specific implementations, the phosphorus-based flame retardant includes aluminum tripolyphosphate and / or stannous pyrophosphate.

[0019] This application also provides a method for preparing a polycarbonate material, comprising:

[0020] Polycarbonate, silicone copolymer polycarbonate, brominated polycarbonate, polysulfone and polyvinylidene chloride are mixed to obtain a first mixture;

[0021] A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene and phosphorus-based flame retardant.

[0022] The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

[0023] In some specific implementations, the temperatures of the first to fifth stages of the extrusion are each independently 310°C to 315°C, the temperatures of the fifth stage to the die head are each independently 260°C to 270°C, and the rotation speed is 500 r / min to 600 r / min.

[0024] This application incorporates polyaryl ester fibers to form a reinforcing system. On one hand, polyaryl esters have lower smoke density and lower heat release than polycarbonate. On the other hand, the addition of fibers significantly improves the overall rigidity of the material, resolving the issue of significant temperature differences between the two materials and addressing incompatibility. Furthermore, the material exhibits superior heat resistance and multiaxial impact resistance. By adding a compound of brominated polycarbonate, polysulfone, and polyvinylidene chloride, the low heat release characteristics enhance the overall char formation and flame retardant efficiency of the material. While brominated polycarbonate and polyvinylidene chloride contain halogen elements, which are beneficial for heat release due to their gas-phase flame retardant principle, they can easily generate excessive halogenated hydrocarbon gases, leading to increased smoke density. Therefore, controlling the content of brominated polycarbonate and polyvinylidene chloride within a reasonable range ensures effective heat release without increasing smoke density. Detailed Implementation

[0025] It should be understood that the expression “one or more of…” individually includes each of the objects described after the expression, as well as various different combinations of two or more of the described objects, unless otherwise understood from the context and usage. The expression “and / or” combined with three or more described objects should be understood to have the same meaning, unless otherwise understood from the context.

[0026] The terms “including,” “having,” or “containing,” including the use of their grammatical synonyms, should generally be understood as open-ended and non-restrictive, for example, not excluding other unstated elements or steps, unless otherwise specifically stated or understood from the context.

[0027] It should be understood that the order of steps or the sequence of actions is not important as long as this application remains operational. Furthermore, two or more steps or actions can be performed simultaneously.

[0028] The use of any and all instances or exemplary language such as “e.g.” or “include” in this document is intended merely to better illustrate the application and does not constitute a limitation on the scope of the application. No language in this specification should be construed as indicating that any unclaimed element is essential to the practice of this application.

[0029] Furthermore, the numerical ranges and parameters used to define this application are approximate values, and the relevant values ​​in the specific embodiments have been presented as precisely as possible. However, any numerical value inevitably contains standard deviations due to individual test methods. Therefore, unless otherwise explicitly stated, it should be understood that all ranges, quantities, values, and percentages used in this disclosure are modified with the word "approximately." Here, "approximately" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specific value or range.

[0030] This application provides a polycarbonate material comprising, by weight parts, 100 parts polycarbonate, 30 to 50 parts silicon copolymer polycarbonate, 3 to 10 parts brominated polycarbonate, 30 to 50 parts polysulfone, 2 to 10 parts polyvinylidene chloride, 10 to 20 parts polyarylate fiber, 1 to 5 parts wollastonite, 1 to 5 parts zinc stannate compound, 0.3 to 1 part ferrocene, and 0.3 to 1 part phosphorus-based flame retardant.

[0031] The polycarbonate material described in this application includes polycarbonate. In some specific implementations, the polycarbonate is bisphenol A type polycarbonate (PC) with a melt index of 2 g / 10 min to 5 g / 10 min at 300°C and 1.2 kg, and the test conditions are as follows. For example, the Mitsubishi 7030PJ from Japan. The polycarbonate is in parts by weight of 100.

[0032] The polycarbonate material described in this application includes silicon-copolymer polycarbonate (Si-PC). In some specific implementations, the silicon-copolymer polycarbonate consists of more than 85 repeating siloxane segments, and has a melt index of 8 g / 10 min to 15 g / 10 min at 300°C and 1.2 kg, under the following test conditions. For example, Cangzhou Dahua CH9115LT. The silicon-copolymer polycarbonate contains 4% to 6% siloxane by mass, and the siloxane chain segments have 90 repeating segments. The silicon-copolymer polycarbonate is in the range of 30 to 50 parts by mass, and can be 30, 32, 35, 40, 42, 45, 48, or 50 parts.

[0033] The polycarbonate material described in this application includes brominated polycarbonate. In some specific implementations, the brominated polycarbonate contains 10% to 30% bromine, and has a melt index of 10 g / 10 min to 35 g / 10 min at 300°C and 1.2 kg, under the specified test conditions. For example, Cangzhou Dahua CH6305BR. The brominated polycarbonate is in the range of 3 to 10 parts by mass, and can be 3, 4, 5, 6, 7, 8, 9, or 10 parts.

[0034] The polycarbonate material described in this application includes polysulfone. In some specific implementations, the polysulfone is bisphenol A type polysulfone, with a melt index of 80 g / 10 min to 100 g / 10 min at 360°C and 10 kg, under the following test conditions. Such as BASF Ultrason® S 2010. The polysulfone is in parts by weight of 30 to 50, and can be 30, 32, 35, 38, 40, 42, 45, 48, or 50. To achieve lower smoke density and lower heat release, bisphenol A polysulfone (PSU) was selected, as its structure is closer to that of bisphenol A polycarbonate, resulting in better compatibility. High-flow polysulfone material was also chosen for its superior processability. Furthermore, a silicon-copolymer polycarbonate with more than 85 repeating siloxane segments was incorporated. This avoids the uneven carbon formation during combustion caused by excessive concentration of siloxane segments due to high silicon content, ensuring uniform carbon formation. Simultaneously, the presence of more than 85 repeating siloxane segments in localized areas ensures overall carbon formation capability. The introduction of optimized polysulfone and Si-PC materials significantly enhances the carbon formation capability, resulting in lower smoke density, lower heat release, and superior overall material performance.

[0035] The polycarbonate material described in this application includes polyvinylidene chloride (PVDC). In some specific implementations, the PVDC is a vinylidene chloride-methyl acrylate copolymer with a weight-average molecular weight of 80,000-100,000, such as Dow SARAN® MA 119. The PVDC is present in parts by weight from 2 to 10 parts, specifically 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts. To achieve low heat release and low smoke density during the combustion of PC materials, a compound of brominated polycarbonate, polysulfone, and polyvinylidene chloride is added. This utilizes their low heat release characteristics to improve the overall char formation and flame retardant efficiency of the material. While brominated polycarbonate and polyvinylidene chloride contain halogen elements, which are based on the principle of gas-phase flame retardancy and are beneficial for heat release, they can easily generate excessive halogenated hydrocarbon gases, leading to increased smoke density. Therefore, controlling the content of brominated polycarbonate and polyvinylidene chloride within a reasonable range ensures both effective heat release and prevents an increase in smoke density.

[0036] The polycarbonate material described in this application includes polyarylate fibers. In some specific implementations, the polyarylate fibers are liquid crystal polyarylate fibers, with a tensile strength of 15 cN / dtex to 25 cN / dtex and a density of 1.42. Up to 1.46 Examples include Kuraray VECTRAN™UM from Japan. The polyaryl ester fiber is present in parts by weight of 10 to 20, specifically 10, 12, 14, 15, 16, 18, or 20 parts. To achieve low smoke density, low heat release, good impact resistance, and excellent overall compatibility in PC materials, polyaryl ester fibers are added to form a reinforcing system. This utilizes the lower smoke density and lower heat release of polyaryl ester compared to polycarbonate, and the addition of fibers significantly improves the overall rigidity of the material, resolving the issue of significant temperature differences between the two materials and addressing incompatibility. Furthermore, the material exhibits superior heat resistance and multiaxial impact resistance. In some specific implementations, the polyaryl ester fiber is a liquid crystal polyaryl ester fiber with a tensile strength of 15 cN / dtex to 25 cN / dtex and a density of 1.42. Up to 1.46 .

[0037] To achieve better overall performance in the product, the polyarylate must be incorporated into the product in the form of fibers. The processing temperature of the material should be controlled at 290℃-300℃ to ensure that the material is in a molten state and can be processed, while also ensuring that the form of the polyarylate fibers is not destroyed.

[0038] The polycarbonate material described in this application includes wollastonite. In some specific implementations, the wollastonite particle size is 1-5 μm (D50), such as Dalian Global Minerals Co., Ltd. HK-5000F. The mass fraction of the wollastonite is 1 to 5 parts, and can be 1 part, 2 parts, 3 parts, 4 parts, or 5 parts.

[0039] The polycarbonate material described in this application includes a zinc stannate compound. In some specific implementations, the zinc stannate compound is zinc hydroxystannate, such as the zinc hydroxystannate from Jiangxi Huachun Chemical New Materials Co., Ltd. The zinc stannate compound is present in parts by weight from 1 to 5 parts, and can be 1 part, 2 parts, 3 parts, 4 parts, or 5 parts.

[0040] The polycarbonate material described in this application includes ferrocene. In some specific implementations, the ferrocene is crystalline ferrocene with a melting point of 170℃~174℃, such as the crystalline ferrocene from Tianyuan Aerospace Materials. The mass fraction of the ferrocene is 0.3 parts to 1 part, and can be 0.3 parts, 0.5 parts, 0.8 parts, or 1 part.

[0041] The polycarbonate material described in this application includes a phosphorus-based flame retardant. In some specific implementations, the phosphorus-based flame retardant is aluminum tripolyphosphate and / or stannous pyrophosphate. More preferably, aluminum tripolyphosphate and stannous pyrophosphate are compounded in a 1:1 mass ratio. The mass fraction of the phosphorus-based flame retardant is 0.3 to 1 part, and can be 0.3 parts, 0.5 parts, 0.8 parts, or 1 part.

[0042] To achieve low heat release during the combustion of PC materials and improve their flame-retardant efficiency, a small amount of ferrocene is added. Utilizing ferrocene's combustion-aiding effect, this small addition allows all the beneficial flame-retardant components in the material system to exert their effects almost simultaneously, significantly improving the synergistic effect of various flame-retardant components without causing excessive combustion. Simultaneously, the condensed-phase flame-retardant mechanism of aluminum tripolyphosphate and / or stannous pyrophosphate enables rapid charring on the polycarbonate surface, preventing heat release due to prolonged combustion. Furthermore, the heat absorption of wollastonite and zinc hydroxystannate, combined with the combustion-aiding effect of ferrocene, greatly enhances the flame-retardant efficiency of the halogen flame-retardant system in brominated polycarbonate and polyvinylidene chloride, reducing the maximum heat release and total heat release energy within a certain timeframe during combustion.

[0043] The polycarbonate material provided in this application, through the synergistic effect of the above components, results in a polycarbonate with low smoke density and low heat release during combustion, which can meet the requirements of CCAR25 standard. At the same time, it has excellent heat resistance, multiaxial impact resistance and processing performance, making it particularly suitable for applications in the aerospace and railway fields.

[0044] This application also provides a method for preparing a polycarbonate material, comprising:

[0045] Polycarbonate, silicone copolymer polycarbonate, brominated polycarbonate, polysulfone and polyvinylidene chloride are mixed to obtain a first mixture;

[0046] A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene and phosphorus-based flame retardant.

[0047] The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

[0048] In some specific implementations, the temperatures of the first to fifth stages of the extrusion are each independently 310°C to 315°C, the temperatures of the fifth stage to the die head are each independently 260°C to 270°C, and the rotation speed is 500 r / min to 600 r / min.

[0049] In some specific implementations, the processing temperature for preparing the polycarbonate material into parts is 290℃-300℃.

[0050] The present application is further illustrated below with reference to embodiments. The scope of protection of the present application is not limited to the following embodiments.

[0051] In the following embodiments:

[0052] PC is a bisphenol A type polycarbonate polymerized by phosgene method, with a melt index of 3 g / 10 min. Test conditions... ;

[0053] The Si-PC contains 4% siloxane by mass, and the siloxane chain consists of 90 repeating segments. The melt index is 10 g / 10 min. (Test conditions) ;

[0054] Br-PC is a polycarbonate with a bromine content of 20% and a melt index of 30 g / 10 min. Test conditions... ;

[0055] PSU is bisphenol A type polysulfone, with a melt index of 95 g / 10 min. Test conditions: ;

[0056] PVDC is a copolymer of vinylidene chloride and methyl acrylate, with a weight-average molecular weight of 90,000.

[0057] The polyaryl ester fiber is a liquid crystal polyaryl ester fiber with a tensile strength of 20 cN / dtex and a density of 1.44 g / cm³. 3 ;

[0058] The particle size of wollastonite is 1-5 μm (D50).

[0059] The zinc stannate compound is zinc hydroxystannate;

[0060] Ferrocene is a crystalline form of ferrocene with a melting point of 170℃~174℃.

[0061] The phosphorus-based flame retardant is a mixture of aluminum tripolyphosphate and stannous pyrophosphate in a 1:1 ratio.

[0062] Example 1

[0063] This embodiment provides a polycarbonate material, the components of which are shown in Table 1. The preparation method of the polycarbonate material includes:

[0064] PC, Si-PC, Br-PC, PSU, and PVDC are mixed to obtain the first mixture;

[0065] A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene, aluminum tripolyphosphate, and stannous pyrophosphate.

[0066] The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

[0067] The extrusion temperature for the first to fifth sections is 313℃, the temperature from the fifth section to the die head is 268℃, the rotation speed is 550r / min, and the processing temperature of the sample used for testing is 293℃.

[0068] Example 2

[0069] This embodiment provides a polycarbonate material, the components of which are shown in Table 1. The preparation method of the polycarbonate material includes:

[0070] PC, Si-PC, Br-PC, PSU, and PVDC are mixed to obtain the first mixture;

[0071] A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene, aluminum tripolyphosphate, and stannous pyrophosphate.

[0072] The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

[0073] The extrusion temperature for the first to fifth sections is 311℃, the temperature from the fifth section to the die head is 262℃, the rotation speed is 520r / min, and the processing temperature of the sample used for testing is 292℃.

[0074] Example 3

[0075] This embodiment provides a polycarbonate material, the components of which are shown in Table 1. The preparation method of the polycarbonate material includes:

[0076] PC, Si-PC, Br-PC, PSU, and PVDC are mixed to obtain the first mixture;

[0077] A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene, aluminum tripolyphosphate, and stannous pyrophosphate.

[0078] The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

[0079] The extrusion temperature for the first to fifth sections is 314℃, the temperature from the fifth section to the die head is 269℃, the rotation speed is 580r / min, and the processing temperature of the sample used for testing is 295℃.

[0080] Example 4

[0081] This embodiment provides a polycarbonate material, the components of which are shown in Table 1. The preparation method of the polycarbonate material includes:

[0082] PC, Si-PC, Br-PC, PSU, and PVDC are mixed to obtain the first mixture;

[0083] A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene, aluminum tripolyphosphate, and stannous pyrophosphate.

[0084] The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

[0085] The extrusion temperature for the first to fifth sections is 313℃, the temperature from the fifth section to the die head is 265℃, the rotation speed is 570r / min, and the processing temperature of the sample used for testing is 299℃.

[0086] Comparative Example 1

[0087] This comparative example provides a polycarbonate material, which differs from Example 1 only in that ferrocene is not added.

[0088] Comparative Example 2

[0089] This comparative example provides a polycarbonate material, which differs from Example 1 only in that the mass fraction of ferrocene is 0.2 parts.

[0090] Comparative Example 3

[0091] This comparative example provides a polycarbonate material, which differs from Example 1 only in that the mass fraction of ferrocene is 1.1 parts.

[0092] Comparative Example 4

[0093] This comparative example provides a polycarbonate material that differs from Example 1 only in that PVDC is not added.

[0094] Comparative Example 5

[0095] This comparative example provides a polycarbonate material that differs from Example 1 only in that it does not use Si-PC with a siloxane content of 4-6% composed of siloxane segments with more than 85 repeating segments, but instead uses Si-PC with a siloxane content of 4-6% composed of siloxane segments with 45 repeating segments.

[0096] Comparative Example 6

[0097] This comparative example provides a polycarbonate material, which differs from Example 1 only in that the mass fraction of Br-PC is 11 parts.

[0098] Comparative Example 7

[0099] This comparative example provides a polycarbonate material, which differs from Example 1 only in that the mass fraction of Br-PC is 2 parts.

[0100] Comparative Example 8

[0101] This comparative example provides a polycarbonate material, which differs from Example 2 only in that the polyarylate is not in fibrous form, but is added directly in the form of resin chips.

[0102] Comparative Example 9

[0103] This comparative example provides a polycarbonate material, which differs from Example 2 only in that the mass fraction of PVDC is 11 parts.

[0104] Comparative Example 10

[0105] This comparative example provides a polycarbonate material, which differs from Example 2 only in that the mass fraction of PVDC is 1 part.

[0106] Comparative Example 11

[0107] This comparative example provides a polycarbonate material that differs from Example 3 only in that it does not contain the zinc stantanate compound.

[0108] Comparative Example 12

[0109] This comparative example provides a polycarbonate material that differs from Example 3 only in that wollastonite is not added.

[0110] Comparative Example 13

[0111] This comparative example provides a polycarbonate material that differs from Example 4 only in that PSU is not added.

[0112] Comparative Example 14

[0113] This comparative example provides a polycarbonate material, which differs from Example 4 only in that the processing temperature of the test sample is 310°C.

[0114] Comparative Example 15

[0115] This comparative example provides a polycarbonate material, which differs from Example 4 only in that the phosphorus-based flame retardant in the raw material components is replaced by the same mass of bisphenol A-bis(diphenyl phosphate) flame retardant.

[0116] Table 1

[0117]

[0118] Test methods for the polycarbonate materials provided in Examples 1-4 and Comparative Examples 1-15:

[0119] Smoke density: In accordance with the requirements of Part V of Appendix F of CCAR-25, the maximum smoke density value of 4Dm was tested within 4 minutes;

[0120] Heat release: Test the maximum heat release rate in accordance with the requirements of Part IV of Appendix F of CCAR-25. Total heat release within 2 minutes ;

[0121] Vicat softening point: Refer to ISO 306, B50;

[0122] Multiaxial impact: Refer to ASTM 3763, room temperature, test speed 200 m / min, total energy tested.

[0123] The test results are shown in Table 2-3.

[0124] Table 2

[0125]

[0126] Table 3

[0127]

[0128] As shown in Table 2-3, in Comparative Example 1, since ferrocene was not added to the raw material components, the combustion-supporting effect of ferrocene was missing, which could not improve the flame retardant efficiency of the material and could not achieve a rapid reaction in the short term when the flame retardant was burning. Therefore, the smoke density and heat release energy increased significantly.

[0129] In Comparative Example 2, the ferrocene content was 0.2 parts, which was insufficient to improve the flame retardant efficiency of the material and achieve a rapid response in the short term during the combustion of the flame retardant. As a result, the smoke density and heat release energy increased.

[0130] In Comparative Example 3, the ferrocene content was 1.1 parts, which resulted in excessive combustion-supporting effect. Although it achieved a rapid response in the short term when the flame retardant was burning, the material itself was over-burned, resulting in a significant increase in smoke density and heat release energy.

[0131] In Comparative Example 4, no PVDC was added to the raw material components, resulting in insufficient suppression of smoke density and heat release within the material system, thus leading to an increase in smoke density and heat release energy.

[0132] In Comparative Example 5, the raw material composition did not include Si-PC with a siloxane content of 4-6% consisting of more than 85 repeating siloxane segments. Instead, Si-PC with a siloxane content of 4-6% consisting of 45 repeating siloxane segments was used. During combustion, the material had insufficient local carbonization ability, resulting in increased smoke density and heat release energy, while its multiaxial impact performance was significantly reduced.

[0133] In Comparative Example 6, the amount of Br-PC added to the raw material components was 11 parts. Since Br-PC is a gas-phase flame retardant, a higher content is more likely to produce more smoke, thereby increasing smoke density and heat release.

[0134] In Comparative Example 7, the amount of Br-PC added to the raw material components was 2 parts. Due to the low content of Br-PC, the flame retardant efficiency was insufficient, resulting in an increase in smoke density and heat release energy.

[0135] In Comparative Example 8, the polyarylate in the raw material components was not in fiber form but was added directly in the form of resin chips. This resulted in insufficient compatibility with the resin matrix and no better reinforcing effect, leading to increased smoke density and heat release, while the multiaxial impact performance showed a significant decrease.

[0136] In Comparative Example 9, the amount of PVDC added to the raw material components was 11 parts. Since PVDC is a gas phase flame retardant, a higher content is more likely to produce more smoke, thereby increasing smoke density and heat release.

[0137] In Comparative Example 10, the amount of PVDC added to the raw material components was 1 part. Due to the low PVDC content, the flame retardant efficiency was insufficient, resulting in an increase in smoke density and heat release energy.

[0138] Comparative Example 11 did not contain zinc stannate compounds in its raw material components, resulting in insufficient heat absorption capacity in the flame retardant system, thus increasing the smoke density and heat release energy.

[0139] Comparative Example 12 did not contain wollastonite in its raw material composition, resulting in insufficient heat absorption capacity in the flame retardant system, thus increasing the smoke density and heat release energy.

[0140] Comparative Example 13 did not contain PSU in its raw material composition. As a result, the material's ability to form carbon during combustion decreased, and its rigidity was insufficient. In addition, the number of benzene rings decreased, leading to a significant decrease in multiaxial impact resistance and heat resistance.

[0141] The sample used in Comparative Example 14 was processed at 310℃, which destroyed the structure of the polyarylate fiber in the product. As a result, the smoke density and heat release energy increased, while the multiaxial impact performance and heat resistance decreased.

[0142] In Comparative Example 15, the phosphorus-based flame retardant used was the same mass of bisphenol A-bis(diphenyl phosphate) flame retardant, which resulted in a significant decrease in the heat resistance of the material, a decrease in multiaxial impact performance, and a decrease in flame retardant efficiency, leading to an increase in smoke density and heat release energy.

[0143] The above description is merely a preferred embodiment of this application, but the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in this application, based on the technical solution and application concept of this application, should be included within the scope of protection of this application.

Claims

1. A polycarbonate material, characterized in that, It comprises, by weight parts, 100 parts polycarbonate, 30 to 50 parts silicon copolymer polycarbonate, 3 to 10 parts brominated polycarbonate, 30 to 50 parts polysulfone, 2 to 10 parts polyvinylidene chloride, 10 to 20 parts polyarylate fiber, 1 to 5 parts wollastonite, 1 to 5 parts zinc stannate compound, 0.3 to 1 part ferrocene and 0.3 to 1 part phosphorus flame retardant.

2. The polycarbonate material according to claim 1, characterized in that, The polycarbonate is bisphenol A type polycarbonate with a melt index of 2 g / 10 min to 5 g / 10 min at 300°C and 1.2 kg.

3. The polycarbonate material according to claim 1, characterized in that, The melt index of the silicon copolymer polycarbonate at 300°C and 1.2 kg is 8 g / 10 min to 15 g / 10 min, the mass percentage of siloxane in the silicon copolymer polycarbonate is 4% to 6%, and the number of repeating segments of the siloxane chain is greater than 85.

4. The polycarbonate material according to claim 1, characterized in that, The brominated polycarbonate contains 10% to 30% bromine and has a melt index of 10 g / 10 min to 35 g / 10 min at 300°C and 1.2 kg.

5. The polycarbonate material according to claim 1, characterized in that, The polysulfone is bisphenol A type polysulfone, with a melt index of 80g / 10min to 100g / 10min at 360℃ and 10kg.

6. The polycarbonate material according to claim 1, characterized in that, The polyvinylidene chloride is a copolymer of vinylidene chloride and methyl acrylate, with a weight-average molecular weight of 80,000 to 100,000.

7. The polycarbonate material according to claim 1, characterized in that, The polyaryl ester fiber is a liquid crystal polyaryl ester fiber; the tensile strength of the polyaryl ester fiber is 15 cN / dtex to 25 cN / dtex, and the density of the polyaryl ester fiber is 1.

42. Up to 1.46 ; The wollastonite has a particle size of 1-5 μm.

8. The polycarbonate material according to claim 1, characterized in that, The zinc stannate compound is zinc hydroxystannate; The ferrocene is crystalline ferrocene with a melting point of 170°C to 174°C. The phosphorus-based flame retardant includes aluminum tripolyphosphate and / or stannous pyrophosphate.

9. A method for preparing a polycarbonate material, characterized in that, include: Polycarbonate, silicone copolymer polycarbonate, brominated polycarbonate, polysulfone and polyvinylidene chloride are mixed to obtain a first mixture; A second mixture is obtained by mixing wollastonite, zinc stannate compound, ferrocene and phosphorus-based flame retardant. The first mixture is added from the main feed port of the twin-screw extruder, the polyarylate fiber is added from the fifth feed port of the extruder, and the second mixture is added from the sixth side feed port of the extruder. After extrusion, the mixture is granulated to obtain polycarbonate material.

10. The preparation method according to claim 9, characterized in that, The temperatures of the first to fifth stages of the extrusion process are each independently 310°C to 315°C, and the temperatures of the fifth stage to the die head are each independently 260°C to 270°C, with a rotation speed of 500 r / min to 600 r / min.

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