Polycarbonate composite material as well as preparation method and application thereof

Abstract

The invention provides a polycarbonate composite material as well as a preparation method and application thereof, and the polycarbonate composite material is prepared from the following raw materials in percentage by weight: 68-93% of polycarbonate; 2%-7% of silicone rubber; 5%-10% of a silicon flame retardant; 10%-15% of heat-resistant filler; and 0.65%-2.5% of an auxiliary agent. According to the polycarbonate composite material provided by the invention, the silicone rubber, the silicon flame retardant and the heat-resistant filler are introduced and compounded for use, so that the polycarbonate composite material has excellent CTI (comparative tracking index) performance, good flame retardant property and excellent thermal stability at the same time.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and relates to a polycarbonate composite material, a preparation method and an application thereof, and specifically relates to a halogen-free flame-retardant, high-heat-resistant polycarbonate composite material with a high tracking index resistance, a preparation method and an application thereof. Background Art

[0002] Polycarbonate (PC) is a high-performance engineering plastic with excellent mechanical properties, transparency and chemical resistance. As one of the fastest-growing engineering plastics, PC has a wide range of applications. However, when the aromatic polymer of PC degrades, it first forms phenyl radicals, which then recombine to form a graphite-like structure. These structures with carbon-carbon double bonds as the skeleton have good conductivity and are prone to electrical tracking, which limits its application range. In addition, the flame retardant properties and thermal stability of PC have always been a problem that has plagued its application.

[0003] Therefore, in the art, it is desired to develop a polycarbonate composite material which simultaneously has a high tracking index, good flame retardant properties and thermal stability. Summary of the invention

[0004] In view of the deficiencies in the prior art, the object of the present invention is to provide a polycarbonate composite material and a preparation method and application thereof, and specifically to provide a halogen-free flame retardant, high-heat-resistant polycarbonate composite material with a high tracking index resistance and a preparation method and application thereof.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a polycarbonate composite material, wherein the raw materials for preparing the polycarbonate composite material include the following components by weight percentage:

[0007]

[0008]

[0009] The polycarbonate composite material provided by the present invention introduces silicone rubber, a silicone flame retardant and a heat-resistant filler, and the three are used in combination, so that the polycarbonate composite material has excellent CTI (comparative tracking index) performance, good flame retardant performance and excellent thermal stability.

[0010] The present invention utilizes silicone rubber to fill and modify polycarbonate, utilizes the poor electrical conductivity of heteroatoms, and hinders the development of electrical traces, thereby improving the CTI performance of the polycarbonate composite material; the use of a silicon-based flame retardant can catalyze the carbonization of polycarbonate during combustion, thereby achieving the purpose of flame retardancy, and, compared with inorganic flame retardants, the present invention uses a silicon-based flame retardant with better flame retardant performance when the amount added is small.

[0011] In the present invention, in terms of weight percentage of the raw materials for preparing the polycarbonate composite material, the amount of polycarbonate can be 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0012] In the present invention, in terms of weight percentage of the raw materials for preparing the polycarbonate composite material, the amount of silicone rubber can be 2%, 3%, 4%, 5%, 6%, 7%, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0013] In the present invention, in terms of weight percentage of the raw materials for preparing the polycarbonate composite material, the amount of silicone-based flame retardant can be 5%, 6%, 7%, 8%, 9%, 10%, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0014] In the present invention, in terms of weight percentage of the raw materials for preparing the polycarbonate composite material, the amount of heat-resistant filler can be 10%, 11%, 12%, 13%, 14%, 15%, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0015] In the present invention, in terms of weight percentage of the raw materials for preparing the polycarbonate composite material, the amount of additives can be 0.65%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0016] Preferably, the polycarbonate is a thermoplastic polycarbonate, including thermoplastic aromatic polyester carbonate.

[0017] Preferably, the polycarbonate has a molecular weight of 10,000 - 40,000 g / mol, such as 10,000 g / mol, 12,000 g / mol, 14,000 g / mol, 16,000 g / mol, 18,000 g / mol, 20,000 g / mol, 22,000 g / mol, 24,000 g / mol, 26,000 g / mol, 28,000 g / mol, 30,000 g / mol, 32,000 g / mol, 34,000 g / mol, 36,000 g / mol, 38,000 g / mol, 40,000 g / mol, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range. Preferably, it is 12,000 - 34,000 g / mol, more preferably 15,000 - 35,000 g / mol.

[0018] Preferably, the silicone rubber has a molecular weight of 20,000 - 40,000 g / mol, such as 20,000 g / mol, 22,000 g / mol, 24,000 g / mol, 26,000 g / mol, 28,000 g / mol, 30,000 g / mol, 32,000 g / mol, 34,000 g / mol, 36,000 g / mol, 38,000 g / mol, 40,000 g / mol, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0019] Preferably, the silicon-based flame retardant includes any one or a combination of at least two of silsesquioxane flame retardants, silicone-based flame retardants, and polysiloxane flame retardants.

[0020] Preferably, the heat-resistant filler includes a POM-modified talc-filled masterbatch. As a preferred technical solution of the present invention, using a POM-modified talc-filled masterbatch as the heat-resistant filler can, on the one hand, improve the heat resistance of the polycarbonate composite material, and on the other hand, it has good compatibility with the matrix material polycarbonate.

[0021] Preferably, in the POM-modified talc-filled masterbatch, based on the mass of talc being 100%, the dosage of POM is 60% - 95%, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, etc., as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0022] Preferably, the additives include any one or a combination of at least two of antioxidants, anti-dripping agents, and other additives.

[0023] Preferably, the antioxidant includes, but is not limited to, organic phosphites such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite (e.g., "IRGAFOS 168" or "I-168"), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, etc., alkylated monophenols or polyphenols: alkylation reaction products of polyphenols and dienes, such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, etc.; butylated reaction products of p-cresol or dicyclopentadiene; hydroxylated thiodiphenyl ethers, alkylidene bisphenols, benzyl compounds, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, esters of β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid with mono- or polyhydric alcohols, esters of thioalkyl or thioaryl compounds, such as distearyl thiodipropionate, dilauryl thiodipropionate, bis(tridecyl) thiodipropionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], etc., amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, etc., or combinations comprising at least one of the aforementioned antioxidants.

[0024] Preferably, based on 100% of the total weight of the raw materials for preparing the polycarbonate composite material, the addition amount of the antioxidant is 0.3% - 1.5%, such as 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc., and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0025] The present invention does not limit the specific type of the anti-dripping agent. Preferably, the anti-dripping agent includes K-PT202 KSAN-Sabic IP.

[0026] Preferably, based on 100% of the total weight of the raw materials for preparing the polycarbonate composite material, the addition amount of the anti-dripping agent is 0.05% - 0.5%, such as 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, etc., and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0027] Preferably, the other additives include heat stabilizers.

[0028] Preferably, the heat stabilizer includes organic phosphites.

[0029] Preferably, the organic phosphite includes triphenyl phosphite and / or tris(2,6-dimethylphenyl) phosphite. The amount of the heat stabilizer is generally 0.0001% to 2% by weight of the total polycarbonate composition.

[0030] Preferably, based on the total weight of the raw materials for preparing the polycarbonate composite being 100%, the addition amount of the other additives is 0.3% - 0.5%, such as 0.3%, 0.32%, 0.34%, 0.36%, 0.38%, 0.4%, 0.42%, 0.44%, 0.46%, 0.48%, 0.5%, etc., as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0031] As a preferred technical solution of the present invention, the raw materials for preparing the polycarbonate composite, by weight percentage, include the following components:

[0032]

[0033]

[0034] In a second aspect, the present invention provides a method for preparing the polycarbonate composite as described in the first aspect. The preparation method includes the following steps:

[0035] Mix the formulated amounts of polycarbonate, silicone rubber, silicone-based flame retardant, heat-resistant filler, and additives, and then perform melt co-extrusion and pelletization to obtain the polycarbonate composite.

[0036] Preferably, the mixing is carried out in a high-speed mixer.

[0037] Preferably, the mixing time is 3 - 10 min, such as 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, etc., as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0038] Preferably, the melt co-extrusion is carried out in a twin-screw extruder.

[0039] Preferably, the extrusion temperature of the twin-screw extruder is as follows: the temperature of the first zone is 80-120 °C (such as 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, etc.), the temperature of the second zone is 260-270 °C (such as 260 °C, 265 °C, 270 °C, etc.), the temperature of the third zone is 275-285 °C (such as 275 °C, 280 °C, 285 °C, etc.), the temperature of the fourth zone is 280-290 °C (such as 280 °C, 285 °C, 290 °C, etc.), the temperature of the fifth zone is 270-280 °C (such as 270 °C, 275 °C, 280 °C, etc.), the temperature of the sixth zone is 270-280 °C (such as 270 °C, 275 °C, 280 °C, etc.), the temperature of the seventh zone is 270-280 °C (such as 270 °C, 275 °C, 280 °C, etc.), the temperature of the eighth zone is 265-275 °C (such as 265 °C, 270 °C, 275 °C, etc.), the temperature of the ninth zone is 265-275 °C (such as 265 °C, 270 °C, 275 °C, etc.), the temperature of the tenth zone is 275-285 °C (such as 275 °C, 280 °C, 285 °C, etc.), the temperature of the eleventh zone is 275-285 °C (such as 275 °C, 280 °C, 285 °C, etc.).

[0040] Preferably, the rotational speed of the twin-screw extruder is 550-650 revolutions per minute, such as 550 revolutions per minute, 560 revolutions per minute, 570 revolutions per minute, 580 revolutions per minute, 590 revolutions per minute, 600 revolutions per minute, 610 revolutions per minute, 620 revolutions per minute, 630 revolutions per minute, 640 revolutions per minute, 650 revolutions per minute, etc., and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. The residence time is 2-5 min, such as 2 min, 3 min, 4 min, 5 min, etc., and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0041] In the third aspect, the present invention provides an application of the polycarbonate composite material as described in the first aspect in communication equipment and electronic appliances.

[0042] Compared with the prior art, the present invention has at least the following beneficial effects:

[0043] The polycarbonate composite material provided by the present invention, by introducing silicone rubber, silicone-based flame retardant, and heat-resistant filler and using them in combination, enables the polycarbonate composite material to simultaneously have excellent CTI (comparative tracking index) performance, good flame retardant performance, and excellent thermal stability. Detailed implementation manners

[0044] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0045] Unless otherwise specified, the raw material information used in the following examples and comparative examples of the present invention is shown in Table 1 below.

[0046] Table 1

[0047]

[0048] Example 1

[0049] In this example, a polycarbonate composite material is provided. The preparation raw materials of the polycarbonate composite material, calculated by weight percentage, include the following components:

[0050]

[0051] The specific information of each component is shown in Table 1.

[0052] The preparation method includes the following steps:

[0053] Mix the above components evenly in a high-speed mixer for 5 minutes, and then add the mixed raw materials to a twin-screw extruder for melt co-extrusion. The temperature of the extruder: the temperature of the first zone is 100°C, the temperature of the second zone is 270°C, the temperature of the third zone is 280°C, the temperature of the fourth zone is 285°C, the temperature of the fifth zone is 275°C, the temperature of the sixth zone is 275°C, the temperature of the seventh zone is 275°C, the temperature of the eighth zone is 270°C, the temperature of the ninth zone is 270°C, the temperature of the tenth zone is 280°C, and the temperature of the eleventh zone is 280°C; the screw speed of the extruder is 600 revolutions per minute, and the residence time is 3 minutes; after extrusion by the screw, it is cooled, dried, and pelletized to obtain the polycarbonate composite material.

[0054] Examples 2-6

[0055] In Examples 2-6, a polycarbonate composite material is respectively provided. The difference from Example 1 is only that the dosages (weight percentages) of each component are different, as shown in Table 2 specifically.

[0056] Table 2

[0057]

[0058]

[0059] Comparative Example 1

[0060] The difference between this comparative example and Example 1 is only that the preparation raw materials do not include silicone rubber, and the weight percentage of polycarbonate is 82%.

[0061] Comparative Example 2

[0062] The difference between this comparative example and Example 1 is only that the preparation raw materials do not include a silicon-based flame retardant, and the weight percentage of polycarbonate is 82%.

[0063] Comparative Example 3

[0064] The difference between this comparative example and Example 1 is only that the preparation raw materials do not include a POM modified talc powder filled masterbatch, and the weight percentage of polycarbonate is 89%.

[0065] Comparative Example 4

[0066] The difference between this comparative example and Example 1 is only that the silicon-based flame retardant is replaced with an equal weight of the inorganic flame retardant magnesium hydroxide.

[0067] Perform performance tests on the polycarbonate composites provided in the examples and comparative examples. The test methods are as follows:

[0068] (1) Tensile strength: Tested with reference to ISO 527-2 1A at a rate of 50 mm / min;

[0069] (2) Flexural modulus: Tested with reference to ISO 178;

[0070] (3) ISO normal temperature notched impact strength: Tested with reference to ISO 179-1eA;

[0071] (4) Vicat softening point temperature: Tested with reference to ISO306 / B50;

[0072] (5) Melt index: Tested with reference to ISO 1133;

[0073] (6) Flame retardant grade: Tested with reference to UL94 1.6 mm flame retardant splines;

[0074] (7) CTI: Tested with reference to IEC60112.

[0075] The performance test results are shown in Table 3.

[0076] Table 3

[0077]

[0078] As can be seen from Table 3, the polycarbonate composites provided in the examples of the present invention all have excellent CTI performance (CTI: 400 - 600), good flame retardant performance (all V-0), and excellent thermal stability (Vicat softening point temperature: 132 - 141 °C).

[0079] Compared with Example 1, the CTI value of the polycarbonate composite material provided by Comparative Example 1 is lower; the flame retardancy of the polycarbonate composite material provided by Comparative Example 2 is HB; the heat distortion temperature of the polycarbonate composite material provided by Comparative Example 3 is lower; the flame retardancy of the polycarbonate composite material provided by Comparative Example 4 deteriorates and the CTI value decreases.

[0080] The applicant declares that the present invention illustrates the polycarbonate composite material and its preparation method and application through the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is, it does not mean that the present invention must rely on the above-mentioned examples to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A polycarbonate composite material, characterized in that: The raw materials for preparing the polycarbonate composite material include the following components by weight percentage:

2. The polycarbonate composite material according to claim 1, characterized in that: The polycarbonate is a thermoplastic polycarbonate, including a thermoplastic aromatic polyester carbonate; Preferably, the molecular weight of the polycarbonate is 10000-40000 g / mol, preferably 12000-34000 g / mol, more preferably 15000-35000 g / mol; Preferably, the molecular weight of the silicone rubber is 20000-40000 g / mol; Preferably, the silicon-based flame retardant includes any one of silsesquioxane flame retardants, silicone flame retardants, and polysiloxane flame retardants, or a combination of at least two of them.

3. The polycarbonate composite material according to claim 1 or 2, characterized in that: The heat-resistant filler includes a POM modified talc powder filling masterbatch; Preferably, in the POM-modified talc powder filling masterbatch, based on 100% by mass of talc powder, the amount of POM is 60%-95%.

4. The polycarbonate composite material according to any one of claims 1 to 3, characterized in that: The auxiliary agent includes any one of an antioxidant, an anti-dripping agent, and other auxiliary agents, or a combination of at least two of them.

5. The polycarbonate composite material according to claim 4, characterized in that: Based on the total weight of the raw materials for preparing the polycarbonate composite material being 100%, the added amount of the antioxidant is 0.3%-1.5%; Preferably, based on 100% of the total weight of the raw materials for preparing the polycarbonate composite material, the added amount of the anti-dripping agent is 0.05%-0.5%.

6. The polycarbonate composite material according to claim 4 or 5, characterized in that: The other additives include heat stabilizers; Preferably, the thermal stabilizer comprises an organic phosphite; Preferably, the organic phosphite comprises triphenyl phosphite and / or tris(2,6-dimethylphenyl)phosphite; Preferably, based on 100% of the total weight of the raw materials for preparing the polycarbonate composite material, the added amount of the other additives is 0.3%-0.5%.

7. The polycarbonate composite material according to any one of claims 1 to 6, characterized in that: The raw materials for preparing the polycarbonate composite material include the following components by weight percentage:

8. A method for preparing a polycarbonate composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The polycarbonate composite material is obtained by mixing the polycarbonate, silicone rubber, silicone flame retardant, heat-resistant filler and auxiliary agent in a prescribed amount, and then melt-coextruding and pelletizing.

9. The preparation method according to claim 8, characterized in that: The mixing is carried out in a high-speed mixer; Preferably, the mixing time is 3-10 min; Preferably, the melt coextrusion is carried out in a twin-screw extruder; Preferably, the extrusion temperature of the twin-screw extruder is: the temperature of zone 1 is 80-120°C, the temperature of zone 2 is 260-270°C, the temperature of zone 3 is 275-285°C, the temperature of zone 4 is 280-290°C, the temperature of zone 5 is 270-280°C, the temperature of zone 6 is 270-280°C, the temperature of zone 7 is 270-280°C, the temperature of zone 8 is 265-275°C, the temperature of zone 9 is 265-275°C, the temperature of zone 10 is 275-285°C, and the temperature of zone 11 is 275-285°C; Preferably, the rotation speed of the twin-screw extruder is 550-650 rpm, and the residence time is 2-5 min.

10. Use of the polycarbonate composite material according to any one of claims 1 to 7 in communication equipment and electronic appliances.

Images