Flame-retardant polycarbonate composite material as well as preparation method and application thereof

Abstract

The invention discloses a flame-retardant polycarbonate composite material which comprises the following components in parts by weight: 80-90 parts of polycarbonate; 5-12 parts of a brominated flame retardant; 0.2 to 2 parts of an anthraquinone compound; 0.5-3 parts of an IPT functional filler; the IPT functional filler is selected from at least one of kaolin, titanium dioxide and quartz. The flame-retardant polycarbonate composite material has the advantages that the flame-retardant performance is 1.5 mmV-0, 1.0 mm is larger than or equal to V-1, and the IPT is larger than 1.5 KV.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a flame-retardant polycarbonate composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Polycarbonate (PC) is a common engineering plastic with excellent mechanical properties and heat resistance, having advantages such as high strength and elastic modulus, high impact strength, high heat resistance, free dyeability, low molding shrinkage rate, good dimensional stability, and excellent fatigue resistance. Modified PC products are widely used in multiple fields such as automotive parts, industrial machinery parts, optical discs, packaging, office equipment such as computers, medical care, films, leisure, and protective equipment.

[0003] In some fields of electronics and electrical appliances, high tracking resistance performance has become a hot spot and a difficult point in the research and development of flame-retardant PC products. Especially in the rapidly developing photovoltaic and new energy industries, higher requirements are put forward for the tracking resistance performance of materials, among which it is required that IPT (inclined plate method tracking resistance test) is greater than or equal to 1.5 KV, and the flame retardancy meets V-0.

[0004] Patent CN 116333475 A discloses a halogen-free flame-retardant polycarbonate composition, a preparation method thereof, and an application thereof, which uses a combination of a phosphorus-based flame retardant, an ultraviolet absorber, and a silicone-based flame retardant. However, this type of system will limit the tracking resistance performance of the material and also reduce the heat resistance performance.

[0005] Patent CN116041871 B discloses a flame-retardant masterbatch and a high-CTI flame-retardant PC product. Compared with the prior art, the present invention adds substances such as aluminum hydroxide and silicon-based additives to the raw material formula. However, adding the aluminum hydroxide flame-retardant masterbatch will still cause the mechanical properties and flame retardancy of PC to decrease during degradation. Summary of the Invention

[0006] The purpose of the present invention is to overcome the above technical defects and provide a flame-retardant polycarbonate composite material having a 1.5 mm V-0 flame retardancy, 1.0 mm ≥ V-1, and IPT > 1.5 KV.

[0007] The present invention is achieved through the following technical solutions: A flame-retardant polycarbonate composite material, by weight, comprises the following components: 80 - 90 parts of polycarbonate; 5 - 12 parts of brominated flame retardant; 0.2 - 2 parts of anthraquinone compound; 0.5 - 3 parts of IPT functional filler; The IPT functional filler is selected from at least one of kaolin, titanium dioxide, and quartz.

[0008] In the flame-retardant polycarbonate composite material of the present invention, the polycarbonate accounts for not less than 70 wt% of the total weight. The polycarbonate can be 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, etc., the bromine-based flame retardant can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, etc., the anthraquinone compound can be 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2.0 parts, etc., and the IPT functional filler can be 0.5 parts, 0.7 parts, 0.9 parts, 1.1 parts, 1.3 parts, 1.5 parts, 1.7 parts, 1.9 parts, 2.1 parts, 2.3 parts, 2.5 parts, 2.7 parts, 2.9 parts, 3.0 parts, etc.

[0009] The anthraquinone compound is selected from at least one of 1-nitroanthraquinone, 2,6-dibromoanthraquinone, 14H-anthra[2.1.9-MNA]thioxanthen-14-one, 9,10-anthraquinone, 2-hydroxymethylanthraquinone, alizarin, alizarin-2-methyl ether, emodin, physcion, 2,5,7-trihydroxyemodin, 1,4,6,8-tetrahydroxy-3-methylanthraquinone.

[0010] Preferably, the IPT functional filler is selected from quartz.

[0011] Preferably, the kaolin is selected from calcined kaolin.

[0012] The average particle size range of the IPT functional filler is 0.1 - 6 μm. The average particle size is tested by a laser particle size analyzer. The average particle size of the IPT functional filler can be 0.1 μm, 0.5 μm, 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6.0 μm.

[0013] The bromine-based flame retardant is selected from at least one of decabromodiphenylethane, brominated epoxy, brominated polycarbonate, brominated polystyrene, brominated triazine; preferably brominated polystyrene.

[0014] The melt flow rate of the polycarbonate is 10 - 30 g / 10 min, test conditions: 300 °C / 1.2 kg, standard: GB / T 3682.1 - 2018.

[0015] By weight, it further includes 0 - 2 parts of a dripping inhibitor; the dripping inhibitor is selected from polytetrafluoroethylene.

[0016] Whether to add 0 - 3 parts of additives can be selected according to actual needs, and the additives are selected from at least one of antioxidants, lubricants, toughening agents, and mold release agents.

[0017] The preparation method of the flame-retardant polycarbonate composite material of the present invention comprises the following steps: Mix each component evenly according to the ratio, and extrude and pelletize through a twin-screw extruder to obtain the flame-retardant polycarbonate composite material. Among them, the temperature range of the barrel is 250 - 280 °C, and the rotation speed range is 600 - 800 rpm.

[0018] The application of the flame-retardant polycarbonate composite material of the present invention is used for preparing electronic and electrical accessories.

[0019] The present invention has the following beneficial effects: 1. During the IPT test, free radicals are easily generated due to the degradation of the material under a high electric field. Therefore, when a brominated flame retardant is applied in this process, it can also capture the free radicals generated by the material under a high electric field, thereby inhibiting the destruction of the PC molecules by the chain reaction, and thus improving the IPT performance of the material.

[0020] 2. Anthraquinone compounds can capture high-energy electrons and weaken the electron energy. Therefore, when used in polycarbonate, it can play an unexpected role in reducing the impact of electrons on the polymer molecular chain under a strong electric field. At the same time, in a thermal oxygen environment, the active α-H structure with rich electron cloud density cleaved from the anthraquinone structure competes to participate in the electrophilic substitution reaction with the acyl cation generated by the PC Fries rearrangement dissociation, making it difficult for the PC to crosslink into carbon and slowing down the formation of the conductive carbon path, thereby improving the IPT performance of the material.

[0021] 3. The IPT functional filler can not only improve the rigidity of the material, but also fill the defects in the PC, reducing the occurrence of partial discharge. When partial discharge occurs in the insulation, if the discharge channel is difficult to continue to expand after reaching the IPT functional filler, the electrical tree is thus inhibited to a certain extent, thereby improving the IPT performance of the material. Specific embodiments

[0022] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0023] The sources of the raw materials used in the present invention are as follows: PC resin - 1: TRIREX 3020PJ, melt flow rate 23 g / 10 min, Samyang, Korea; PC resin - 2: TRIREX 3030PJ, melt flow rate 3 g / 10 min, Samyang, Korea; Brominated polycarbonate: FG - 8500, Teijin.

[0024] Brominated polystyrene: SAYTEX HP-5010, Albemarle, USA; Decabromodiphenylethane: SAYTEX 8010, Albemarle, USA; Brominated epoxy: CR-2360, Suzhou Borida; Anthraquinone compounds-1: 1-nitroanthraquinone, Shanghai MacLean Biochemical Technology; Anthraquinone compounds-2: 2,6-dibromoanthraquinone, Beijing Bailingwei Technology; Anthraquinone compounds-3: 14H-anthraquinone[2.1.9-MNA]thioxanthen-14-one, Anaiji Chemical; Polytetrafluoroethylene: POLYB FS-200, Hannano Technology; Kaolin: calcined kaolin, average particle size 6 μm, purchased from Yuanlei Powder; Titanium dioxide: average particle size 1.8 μm, purchased from Connors; Quartz: Quartz powder, average particle size is 5 microns, source powder; Antioxidant: Antioxidant 1010, commercially available; Embodiment and comparative example Preparation method of flame retardant polycarbonate composite material: according to the ratio, each component is mixed evenly, and extruded and granulated by a twin-screw extruder to obtain a flame retardant polycarbonate composite material, wherein the temperature range of the screw barrel is 250-280°C.

[0025] Various test methods: (1) Flame retardancy: refer to the vertical burning test standard of UL94; (2) IPT test: refer to ASTM D2303 standard.

[0026] Table 1: Weight content of each component of flame retardant polycarbonate composite material of Examples 1-6 and test results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PC Resin-1 85 90 85 85 85 PC Resin-2 80 Brominated Polystyrene 5 8 12 Brominated Polycarbonate 8 Decabromodiphenylethane 8 Brominated Epoxy 8 Anthraquinone Compound-1 2 1 0.2 1 1 1 Quartz 0.5 1.5 3 1.5 1.5 1.5 Polytetrafluoroethylene 0.5 Antioxidant 0.5 0.5 Flammability (1.5mm) V-0 V-0 V-0 V-0 V-0 V-0 Flammability (1.0mm) V-1 V-0 V-0 V-1 V-1 V-1 IPT, KV 1.8 1.7 1.5 1.6 1.6 1.6 It can be seen from Examples 2 / 4 / 5 / 6 that when the flame retardant is preferably brominated polystyrene, the flame retardancy is better and the IPT is higher.

[0027] Table 2: Weight content of each component of the flame retardant polycarbonate composite material of Examples 7-10 and test results Example 7 Example 8 Example 9 Example 10 PC Resin-1 85 85 85 85 Brominated Polystyrene 8 8 8 8 Anthraquinone Compound-1 1 1 Anthraquinone Compound-2 1 Anthraquinone Compound-3 1 Quartz 1.5 1.5 Kaolin 1.5 Titanium Dioxide 1.5 Flammability (1.5mm) V-0 V-0 V-0 V-0 Flammability (1.0mm) V-0 V-0 V-1 V-1 IPT, KV 1.7 1.7 1.5 1.5 It can be seen from Examples 2 / 9 / 10 that quartz is the preferred IPT functional filler.

[0028] Table 3: Weight content of each component of the flame retardant polycarbonate composite material and test results of the comparative example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PC Resin-1 85 85 85 85 Brominated Polystyrene 8 8 8 8 Anthraquinone Compound-1 3 1 1 Quartz 1.5 1.5 5 Flammability (1.5mm) V-0 V-0 V-0 V-0 Flammability (1.0mm) V-0 V-1 V-0 V-2 IPT, KV 1.0 1.3 1.2 1.0 It can be seen from Comparative Example 1 that the IPT is low when no anthraquinone compound is contained.

[0029] As can be seen from Comparative Example 2, when the content of anthraquinone compounds is too high, both the flame retardancy and IPT decrease.

[0030] As can be seen from Comparative Example 3, IPT is low when the IPT functional filler is not contained.

[0031] As can be seen from Comparative Example 4, when the content of the IPT functional filler is too high, the flame retardancy and IPT performance will be reduced.

Claims

1. A flame retardant polycarbonate composite material, characterized in that: By weight, it includes the following components: Polycarbonate 80-90 parts; 5-12 parts of brominated flame retardant; 0.2-2 parts of anthraquinone compounds; IPT functional filler 0.5-3 parts; The IPT functional filler is selected from at least one of kaolin, titanium dioxide and quartz.

2. The flame retardant polycarbonate composite material according to claim 1, characterized in that: The anthraquinone compound is selected from at least one of 1-nitroanthraquinone, 2,6-dibromoanthraquinone, 14H-anthra[2.1.9-MNA]thioxanthen-14-one, 2-hydroxymethylanthraquinone, alizarin, alizarin-2-methyl ether, rhamnolide, rhamnolide methyl ether, 2,5,7-trihydroxyrhamnolide, and 1,4,6,8-tetrahydroxy-3-methylanthraquinone.

3. The flame retardant polycarbonate composite material according to claim 1, characterized in that: The IPT functional filler is selected from quartz; the kaolin is selected from calcined kaolin.

4. The flame retardant polycarbonate composite material according to claim 1, characterized in that: The average particle size of the IPT functional filler is in the range of 0.1-6 μm.

5. The flame retardant polycarbonate composite material according to claim 1, characterized in that: The brominated flame retardant is selected from at least one of decabromodiphenylethane, brominated epoxy, brominated polycarbonate, brominated polystyrene and bromotriazine; preferably brominated polystyrene.

6. The flame retardant polycarbonate composite material according to claim 1, characterized in that: The melt flow rate of the polycarbonate is 10-30 g / 10 min, and the test conditions are: 300° C. / 1.2 kg.

7. The flame retardant polycarbonate composite material according to claim 1, characterized in that: By weight, it also includes 0-2 parts of an anti-dripping agent; the anti-dripping agent is selected from polytetrafluoroethylene.

8. The flame retardant polycarbonate composite material according to claim 1, characterized in that: The invention also includes 0-3 parts of auxiliary agents by weight, wherein the auxiliary agents are selected from at least one of antioxidants, lubricants, toughening agents and release agents.

9. The method for preparing the flame retardant polycarbonate composite material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components uniformly according to the proportion, extruding and granulating through a twin-screw extruder to obtain a flame-retardant polycarbonate composite material.

10. Use of the flame retardant polycarbonate composite material according to any one of claims 1 to 8, characterized in that: Used to prepare electronic and electrical accessories.