High-transparency high-impact halogen-free flame-retardant polycarbonate modified material as well as preparation method and application thereof

Abstract

The invention relates to a high-transparency high-impact halogen-free flame-retardant polycarbonate modified material as well as a preparation method and application thereof. The material comprises the following components in parts by weight: 0-35 parts of homopolymerized polycarbonate resin; 50 to 95 parts of silicon copolymerized polycarbonate resin; 5-15 parts of a flame retardant; 0.1 to 1 part of an organic silicon synergistic flame retardant; 0.1 to 0.4 part of an auxiliary agent; the preparation method comprises the following steps: mixing the raw materials, putting the mixture into a twin-screw extruder, setting the interval temperature to be 200-250 DEG C and the rotating speed to be 200-500 rpm, and cooling and granulating to obtain the high-transparency high-impact-resistance flame-retardant polycarbonate modified material. Compared with the prior art, the transparent flame-retardant polycarbonate modified material provided by the invention has the advantages of high transparency, low haze, excellent impact resistance and excellent flame retardance.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, in particular to the field of polycarbonate modified materials, and specifically to a high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material and a preparation method and application thereof. Background Art

[0002] Polycarbonate (PC) is a highly transparent amorphous thermoplastic and one of the five major engineering plastics. In addition to its excellent transparency, polycarbonate has a relatively rigid benzene ring and a relatively flexible carbonate group, which makes polycarbonate have high rigidity, modulus, good high temperature resistance and dimensional stability, as well as excellent impact resistance. In view of these excellent properties of polycarbonate, it is widely used in many industries and products such as electronics and electrical, home appliances, office equipment, power tools, charging piles, etc. Certain specific industries such as electronics and electrical, office equipment, charging piles, etc., have different requirements on the flame retardant performance of polycarbonate modified products.

[0003] The flame retardant grade of polycarbonate itself is V2 (3.2mm), and the transmittance is about 89% (2mm), but generally speaking, adding conventional flame retardant systems will affect the transparency of polycarbonate, and some flame retardants will reduce the impact strength of polycarbonate to a certain extent. This will limit the application of polycarbonate materials in some special scenarios that require both high transparency and good flame retardant properties.

[0004] CN111117187 A discloses a high-toughness and high-transparency silicone flame-retardant polycarbonate material and a preparation method thereof, the material comprising the following raw materials in parts by weight: 90-99 parts of polycarbonate, 0.05-3 parts of silicone flame retardant, 0-0.5 parts of anti-dripping agent, 0.1-1 parts of dispersant, and 0.1-0.5 parts of antioxidant; wherein the polycarbonate is composed of polycarbonate resin powder and polycarbonate resin particles. The polycarbonate material prepared by this method has high toughness, high transparency, halogen-free, environmentally friendly and flame-retardant effects, good flame retardant dispersibility, and stable flame retardant effect, which can meet the market demand for fully transparent flame-retardant products. However, its highest flame retardant grade can only reach V0 2.0mm, so it cannot meet the application requirements of thinner-walled transparent flame retardant. Summary of the invention

[0005] The purpose of the present invention is to provide a high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material and a preparation method and application thereof.

[0006] The object of the present invention can be achieved by the following technical scheme: A high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material, comprising the following components in parts by weight:

[0007] Homopolymer polycarbonate resin 0-35 parts;

[0008] 50-95 parts of silicon copolymer polycarbonate resin;

[0009] Flame retardant 5-15 parts;

[0010] 0.1-1 part of silicone synergistic flame retardant;

[0011] Additives 0.1-0.4 parts.

[0012] Preferably, the high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material comprises the following components in parts by weight:

[0013] Homopolymer polycarbonate resin 0-25 parts;

[0014] 60-95 parts of silicon copolymer polycarbonate resin;

[0015] Flame retardant 5-15 parts;

[0016] 0.1-1 part of silicone synergistic flame retardant;

[0017] Additives 0.1-0.4 parts.

[0018] Preferably, the silicon copolymer polycarbonate resin (silicon copolymer PC resin) has an MI of 2.5 to 110 g / 10 min at 300° C. and 1.2 kg.

[0019] Preferably, the weight average molecular weight of the silicon copolymer polycarbonate resin is 18,000-38,000.

[0020] Preferably, the silicon content of the silicon copolymer polycarbonate resin is in the range of 5wt%-40wt%.

[0021] In the present invention, the silicon copolymer polycarbonate resin refers to a copolymer of polycarbonate (PC) and polydimethylsiloxane (PDMS).

[0022] Preferably, the flame retardant includes a combination of one or more phosphazene flame retardants.

[0023] Further preferably, the phosphazene flame retardant includes one or more of hexaphenoxy cyclotriphosphazene, hexachloro cyclotriphosphazene, and pentafluoro cyclotriphosphazene.

[0024] Preferably, the organosilicon synergistic flame retardant includes a methyl group, a phenyl group, an epoxy group, a hydroxyl group or a vinyl group.

[0025] Further preferably, the organosilicon synergistic flame retardant includes organosilicon containing methyl or phenyl components in different proportions, and may contain a certain branched structure or a certain content of reactive groups, such as epoxy groups, hydroxyl groups or vinyl groups.

[0026] Further preferably, the organosilicon synergistic flame retardant includes octaphenylcyclotetrasiloxane and methylphenyl organosilicon with a certain methyl content.

[0027] Preferably, the homopolymer polycarbonate resin (homopolymer PC resin) has an MI of 2.5 to 110 g / 10 min at 300° C. and 1.2 kg.

[0028] Preferably, the homopolymer polycarbonate resin has a weight average molecular weight of 18,000-38,000.

[0029] Preferably, the auxiliary agent includes an antioxidant and a lubricant.

[0030] Preferably, the high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material comprises the following components in parts by weight:

[0031] Homopolymer polycarbonate resin 0-35 parts;

[0032] 50-95 parts of silicon copolymer polycarbonate resin;

[0033] Flame retardant 5-15 parts;

[0034] 0.1-1 part of silicone synergistic flame retardant;

[0035] Antioxidant 0.05-0.2 parts;

[0036] Lubricant 0.05-0.2 parts.

[0037] Further preferably, the antioxidant includes any one of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant PEPQ, or a combination of two thereof.

[0038] Further preferably, the lubricant includes any one of a PET internal lubricant and a silicone external lubricant or a combination of the two. The lubricant may include a PET internal lubricant and a silicone external lubricant of different molecular weights.

[0039] A method for preparing the above-mentioned high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material comprises the following steps:

[0040] After all the raw materials are fully mixed, they are placed in a twin-screw extruder, the temperature interval is set to 200-250° C., the rotation speed is set to 200-500 rpm, and cooling and granulation are performed to obtain a high-transparency, high-impact and flame-retardant polycarbonate modified material.

[0041] An application of the above-mentioned high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material is to use the material in transparent parts of electronic appliances.

[0042] Preferably, the material is used to prepare a transparent outer shell of a charging pile and a transparent outer shell of a mobile phone fast charging charger.

[0043] Compared with the prior art, the present invention has the following beneficial effects:

[0044] 1. The transparent flame-retardant polycarbonate modified material provided by the present invention has high transparency, low haze, and excellent impact resistance and flame retardancy.

[0045] 2. The present invention achieves the flame retardant requirement of V01.6mm by compounding silicon copolymer polycarbonate resin and organosilicon synergistic flame retardant. Silicon copolymer polycarbonate resin can build higher charring ability and intrinsic flame retardant ability in the matrix resin dimension, and organosilicon can diffuse to the surface of the material when the material burns, further promoting charring and thus helping to improve flame retardant performance. At the same time, silicon copolymer polycarbonate can also help improve the toughness of the system.

[0046] 3. The present invention can improve toughness and enhance flame retardancy at the same time by designing the silicon content of the silicon copolymer polycarbonate resin.

[0047] 4. The present invention discloses a highly transparent and highly impact-resistant polycarbonate modified material, which uses silicon copolymer polycarbonate and silicone functional additives. The synergistic effect of the two gives the material excellent comprehensive performance, including transparency as high as 87% (2.2mm), haze as low as 3.4% (2.2mm), impact as high as 750J / m, and flame retardant performance that can reach the flame retardant level of UL94 standard V0@1.5mm. The material is very suitable for use in transparent parts of electronic appliances, such as transparent shells of charging piles, transparent shells of mobile phone fast charging chargers, etc. DETAILED DESCRIPTION

[0048] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but shall not limit the present invention in any way. It should be particularly noted that, for those of ordinary skill in the art, several expansion methods and concepts can also be carried out without departing from the conception method of the present invention. These expansion methods and concepts should all belong to the scope of protection of the present invention.

[0049] A high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material, calculated by weight, comprises the following components:

[0050] Homopolymer polycarbonate resin 0-35 parts;

[0051] 50-95 parts of silicon copolymer polycarbonate resin;

[0052] Flame retardant 5-15 parts;

[0053] 0.1-1 part of silicone synergistic flame retardant;

[0054] Antioxidant 0.05-0.2 parts;

[0055] Lubricant 0.05-0.2 parts.

[0056] The following is a detailed description with reference to specific embodiments:

[0057] The raw materials used in the examples and comparative examples of the present invention are all commercially available, but are not limited to the following materials:

[0058] The polycarbonate resin uses Mitsubishi Chemical's M7027BF; the PC-PDMS uses Wanhua Chemical's S1240T; the flame retardant uses Weihai Jinwei's hexaphenoxy cyclotriphosphazene; the silicon-based flame retardant synergist uses Japan's Shin-Etsu's OPCTS; other additives include BASF antioxidant Irgafos 168 and FACI lubricant pentaerythritol stearate PETS.

[0059] The preparation methods of the embodiments of the present invention and the comparative examples are as follows:

[0060] Step 1: After the raw materials are fully mixed according to the mass fractions described in Table 1, they are placed in a twin-screw extruder, the temperature interval is set to 200-250°C, the speed is set to 200-500rpm, and cooling and granulation are performed to obtain a high-transparency, high-impact and flame-retardant polycarbonate modified material.

[0061] Step 2: After the PC material obtained in step 1 is dried at 120°C for 4 hours, it is injection molded into a test block under the same injection molding conditions according to ASTM standards for physical property testing; at the same time, according to UL standards, it is injection molded into a test strip for vertical burning flame retardant performance testing; in addition, the material is injection molded into a 100*65*2.2mm sample plate, and the material is tested for transmittance. The specific test conditions and standards are shown in Table 1.

[0062] Table 1 Test standards and conditions

[0063]

[0064] Example 1

[0065] The present embodiment provides a highly impact-resistant and highly transparent flame-retardant PC modified material and a preparation method thereof, and the specific steps are as follows: first, the components are evenly mixed in a mixing barrel, and fed into a twin-screw extruder through the main feeding port; then, the components are blended and granulated through the extruder, and melt-extruded and granulated to obtain a highly impact-resistant and highly transparent flame-retardant PC modified material. The above-mentioned materials are melt-extruded, cooled, dried, and pelletized to obtain a sample. Specifically, the above-mentioned twin-screw extruder is a co-rotating twin-screw extruder, the aspect ratio of the screw is 40:1, the screw barrel is provided with a vacuum pumping device and a temperature control device, the interval temperature is set to 200-250°C, and the rotation speed is set to 200-500rpm.

[0066] Example 2

[0067] This embodiment is basically the same as Embodiment 1, except that the amount of the organosilicon synergistic flame retardant used in this embodiment is lower, from 0.5 parts to 0.3 parts.

[0068] Example 3

[0069] The difference between this embodiment and embodiment 1 is that in this embodiment, part of conventional homopolymer PC is used to replace part of transparent silicon copolymer PC, that is, PC-PDMS.

[0070] Comparative Example 1

[0071] The difference between this comparative example and Example 3 is that the organosilicon synergistic flame retardant is removed in this comparative example.

[0072] Comparative Example 2

[0073] The difference between this comparative example and Example 1 is that the organosilicon synergistic flame retardant is removed in this comparative example.

[0074] Table 2 Specific composition ratios of the embodiments and comparative examples

[0075]

[0076] The test results of the modified materials properties of Examples 1 to 3 and Comparative Examples 1 to 2 are shown in Table 3.

[0077] Table 3 Summary of specific performance of examples and comparative examples

[0078]

[0079]

[0080] As can be seen from the above table, the impact strength of Example 1 and Example 2 is relatively high, indicating that the system with a higher content of silicon copolymer PC has better toughness. From the comparison between Example 1 and Example 2, it can be seen that when the organosilicon synergistic flame retardant is reduced from 0.5 parts to 0.3 parts, the vertical flame retardant performance deteriorates, which is mainly reflected in the longer burning time. From the comparison between Example 1 and Comparative Example 2, it can be seen that the flame retardant performance of the system cannot pass without the organosilicon synergistic flame retardant, which is reflected in the longer burning time and the phenomenon of dripping and dripping. By comparing Example 1 and Example 3, it can be seen that as the content of silicon copolymer polycarbonate decreases, dripping occurs in the system and the instability of the flame retardant performance increases.

[0081] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and 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 present invention should be within the scope of protection of the present invention.

Claims

1. A high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material, characterized in that: It comprises the following components in parts by weight: Homopolymer polycarbonate resin 0-35 parts; 50-95 parts of silicon copolymer polycarbonate resin; Flame retardant 5-15 parts; 0.1-1 part of silicone synergistic flame retardant; Additives 0.1-0.4 parts.

2. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 1, characterized in that: The silicon copolymer polycarbonate resin has an MI of 2.5 to 110 g / 10 min under the conditions of 300° C. and 1.2 kg.

3. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 1, characterized in that: The silicon copolymer polycarbonate resin has a weight average molecular weight of 18000-38000 and a silicon content range of 5wt%-40wt%.

4. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 1, characterized in that: The flame retardant includes a combination of one or more phosphazene flame retardants; The phosphazene flame retardant includes one or more of hexaphenoxy cyclotriphosphazene, hexachloro cyclotriphosphazene, and pentafluoro cyclotriphosphazene.

5. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 1, characterized in that: The organosilicon synergistic flame retardant includes a methyl group, a phenyl group, an epoxy group, a hydroxyl group or a vinyl group.

6. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 1, characterized in that: The homopolymer polycarbonate resin has an MI of 2.5 to 110 g / 10 min and a weight average molecular weight of 18,000 to 38,000 under the conditions of 300° C. and 1.2 kg.

7. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 1, characterized in that: It comprises the following components in parts by weight: Homopolymer polycarbonate resin 0-35 parts; 50-95 parts of silicon copolymer polycarbonate resin; Flame retardant 5-15 parts; 0.1-1 part of silicone synergistic flame retardant; Antioxidant 0.05-0.2 parts; Lubricant 0.05-0.2 parts.

8. The high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 7, characterized in that: The antioxidant includes any one of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant PEPQ, or a combination of two thereof; The lubricant includes any one of a PET internal lubricant and a silicone external lubricant, or a combination of the two.

9. A method for preparing the high-transparency, high-impact, halogen-free, flame-retardant polycarbonate modified material according to any one of claims 1 to 8, characterized in that: The following steps are involved: After the raw materials are mixed, they are placed in a twin-screw extruder, the temperature interval is set to 200-250° C., the rotation speed is set to 200-500 rpm, and cooling and granulation are performed to obtain a high-transparency, high-impact and flame-retardant polycarbonate modified material.

10. An application of the high transparency, high impact resistance, halogen-free, flame-retardant polycarbonate modified material according to claim 9, characterized in that: The material is used for transparent parts of electronic appliances.

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