High-weather-resistant, cold-resistant and high-flame-retardant polycarbonate material and preparation method thereof

Abstract

The invention discloses a high-weather-resistant cold-resistant high-flame-retardant polycarbonate material and a preparation method thereof. The material is prepared from the following raw materials in percentage by mass: 85-93% of PC resin, 0.5-3% of a flame retardant, 3-6% of a high-silicon-content flexibilizer, 0.3-0.6% of an anti-hydrolysis agent, 0.3-0.6% of an ultraviolet light absorber, 0.1-0.5% of an anti-dripping agent and 0.1-0.5% of a release agent. 0.1 to 0.3 percent of an antioxidant 168; the preparation method comprises the following steps: drying and mixing the raw materials, then carrying out blending granulation, and finally carrying out extrusion, water cooling, grain-sized dicing and sieving so as to obtain the product. The product disclosed by the invention not only has high weather resistance and high flame retardance, but also has good low-temperature impact resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastic preparation, and more particularly to a highly weather-resistant, cold-resistant and highly flame-retardant polycarbonate material and a preparation method thereof. Background Art

[0002] In recent years, new energy vehicle technology and the market have developed rapidly. Compared to traditional fuel-powered vehicles, new energy vehicles still have shortcomings such as shorter driving range and difficulty charging, resulting in a strong dependence on charging stations. Plastics, after modification, possess excellent flame retardancy, weather resistance, low-temperature resistance, and aging resistance. Therefore, modified plastics account for a high proportion of charging equipment, especially in its casing materials. Charging stations and their accompanying charging guns are electrical devices used outdoors, directly exposed to the elements and subject to the effects of the natural environment. To ensure that charging stations can function properly in extreme weather conditions such as low temperatures and reduce the possibility of fires and other emergencies, the Technical Specification for Non-Metallic Materials for Electric Vehicle Charging Equipment Enclosures (CQC 1305) sets strict requirements for equipment materials' moisture resistance, UV resistance, and glow-wire flammability index. Highly weather-resistant and cold-resistant, highly flame-retardant polycarbonate materials are suitable for applications requiring stringent weather resistance, flame retardancy, and low-temperature toughness, such as new energy vehicle battery casings, outdoor LED lampshades, and 5G base station components.

[0003] Polycarbonate, with its numerous performance advantages, has been widely used in electronics, automotive, pharmaceutical, food packaging, sports, and other fields. However, polycarbonate exhibits poor weather resistance, poor low-temperature performance at -40°C, and poor hydrolysis resistance, making it generally unsuitable for outdoor use. Sulfonic acid flame retardants are commonly used in polycarbonate, achieving a flame retardancy of 1.5mm V-0 at relatively low addition levels. However, sulfonate flame retardants degrade after immersion in hot water at 70°C for 168 hours. Therefore, sulfonate flame retardants should not be used for long-term outdoor use. Summary of the Invention

[0004] The present invention aims to address the existing problem of polypropylene materials struggling to balance high weather resistance, flame retardancy, and low-temperature impact properties. The present invention provides a highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material and a preparation method thereof. The polycarbonate material can be used outdoors for long periods of time, exhibits excellent flame retardancy, and exhibits good hydrolysis resistance.

[0005] In order to achieve the above object of the invention, the specific technical solutions of the present invention are as follows:

[0006] A highly weather-resistant and cold-resistant highly flame-retardant polycarbonate material, comprising the following raw materials in the following mass percentages:

[0007] Polycarbonate resin (PC resin for short) 85-93%;

[0008] Flame retardant: 0.5 - 3%;

[0009] Toughening agent with high silicon content: 3 - 6%;

[0010] Ultraviolet absorber: 0.2 - 0.6%;

[0011] Drip retardant: 0.1 - 0.5%;

[0012] Hydrolysis resistant agent: 0.3 - 0.6%

[0013] Release agent: 0.1 - 0.5%;

[0014] Antioxidant 168: 0.1 - 0.3%;

[0015] Antioxidant 1010: 0.1 - 0.3%.

[0016] Furthermore, in the described high weather - resistant, cold - resistant and high - flame - retardant polycarbonate material, the polycarbonate resin includes bisphenol A aromatic polycarbonate resin; the relative molecular weight of the polycarbonate resin is 28000 - 33000.

[0017] Furthermore, in the described high weather - resistant, cold - resistant and high - flame - retardant polycarbonate material, the flame retardant is one or a combination of two of organosilicon / phenoxyphosphazene copolymer or octaphenylcyclotetrasiloxane; the molecular formula of the organosilicon / phenoxyphosphazene copolymer is as follows:

[0018]

[0019] Wherein R1, R2, R3, and R4 are independently selected from C1 - C20 alkyl, C1 - C20 phenyl, C1 - C20 alkoxy, C1 - C20 phenoxy, C1 - C20 phenyl - containing alkoxy, or C1 - C20 phenyl - containing alkane.

[0020] Furthermore, in the described high weather - resistant, cold - resistant and high - flame - retardant polycarbonate material, the toughening agent with high silicon content is the Japanese Zhongyuan silicon - based toughening agent MR - 01.

[0021] Furthermore, in the described weather - resistant, cold - resistant and high - flame - retardant polycarbonate material, the drip retardant is polytetrafluoroethylene coated with a copolymer of styrene and acrylonitrile.

[0022] Furthermore, in the described high weather - resistant, cold - resistant and high - flame - retardant polycarbonate material, the hydrolysis resistant agent is bis(2,6) - diisopropylcarbodiimide.

[0023] Further, in the described highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, the ultraviolet absorber is one or both of 2-(2'-hydroxy-3,5-dicumylphenyl) benzotriazole and 2,2'-methylenebis(4-tert-octyl-6-benzotriazole phenol).

[0024] Further, in the described highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, the release agent is silicone.

[0025] A preparation method of the highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material as described above includes the following steps:

[0026] a. Weigh the toughening agent with high silicon content, flame retardant, anti-dripping agent, anti-hydrolysis agent, antioxidant, ultraviolet absorber, and release agent according to the ratio, and mix them evenly through a powder mixer to obtain mixture 1;

[0027] b. Weigh the polycarbonate resin and mixture 1 obtained in step a according to the ratio, and then mix them evenly to obtain mixture 2;

[0028] c. The mixture 2 obtained in step b is melt blended and pelletized in a twin-screw extruder to obtain mixture 3; d. The mixture 3 obtained in step c is extruded, cooled by passing through water, and pelletized and sieved to obtain the product.

[0029] Further, in the preparation method of the highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, the polycarbonate resin, toughening agent with high silicon content, flame retardant, anti-dripping agent, ultraviolet absorber, and release agent are fully dried and reserved before mixing.

[0030] Compared with the prior art, the positive effects of the present invention are reflected in:

[0031] Through reasonable ratio design, the present invention uniformly mixes a silicon-based toughening agent with a phosphorus-silicon copolymer or a high-phenyl-content siloxane (octaphenylcyclotetrasiloxane), then uniformly mixes it with the PC resin and then pelletizes it. After the subsequent process, a material with cold resistance and low-temperature resistance is obtained, which increases the low-temperature performance and flame retardancy of the polycarbonate material. At the same time, bis(2,6)-diisopropylcarbodiimide is added to improve the hydrolysis resistance of the polycarbonate, and adding an ultraviolet absorber can improve the ultraviolet resistance of the polycarbonate. Specific embodiments

[0032] All the features disclosed in this specification, or all the steps in the disclosed methods or processes, except for mutually exclusive features and / or steps, can be combined in any way.

[0033] Any feature disclosed in this specification (including claims and abstract), unless specifically described, can be replaced by other equivalent or similar-purpose alternative features. That is, unless specifically described, each feature is just an example in a series of equivalent or similar features.

[0034] The features and properties of the present invention will be further described in detail below in conjunction with embodiments.

[0035] The test methods and requirements for the materials in the following embodiments are carried out according to the following standards:

[0036] 1. Weather resistance test method: After soaking in hot water at 70 °C for 168 hours, test according to GB / T 11547-2008; it is required that the notched Izod impact strength of the polycarbonate material at room temperature remains above 50% of the original performance, and the flame retardancy rating remains unchanged.

[0037] 2. Test method for notched Izod impact strength at -40 °C: After placing at -40 °C for 2 h, immediately test according to GB / T1843-2008. It is required that the notched Izod impact strength of the polycarbonate material ≥ 45 KJ / cm 2 。

[0038] 3. Test method for notched Izod impact strength at 23 °C: Place at a temperature of 23 °C for 24 h, and immediately test according to GB / T1843-2008. For polycarbonate materials, it is required that the notched Izod impact ≥ 50 KJ / cm 2 [[ID=1⑨]]。

[0039] 4. Heat distortion temperature (1.8 MPa): Test according to GB / T 1634-2004.

[0040] 5. Resistance to ultraviolet rays (xenon lamp 1000 h aging) test: Test according to GB / T 16422.2-2014. It is required that the flame retardancy rating of the polycarbonate material remains unchanged, and the retention rate of the notched Izod impact strength at room temperature during the test is above 70%.

[0041] 6. Flame retardancy test: Injection mold into 1.5 mm × 12.7 mm × 127 mm specimens at 260 - 280 °C, and test according to UL-94. It is required that the polycarbonate material reaches V-0.

[0042] 7. Tensile strength and elongation at break: Test according to GB / T1040.1. It is required that the tensile strength of the polycarbonate material is greater than 55 MPa, and the elongation at break is greater than 80%.

[0043] In this application, unless otherwise specified, % represents its mass percentage content.

[0044] In the following embodiments, all raw materials are commercially available products or can be prepared by existing technologies; among them, bisphenol A aromatic polycarbonate (A1100 Wanhua Chemical); organosilicon / phenoxy polyphosphazene copolymer (prepared using the method of Example 1 in patent application number 2020111032641, invention name is low smoke density, low heat release, halogen-free flame retardant PC material, preparation method and application thereof); octaphenylcyclotetrasiloxane (FR800 Shanghai Puxin Polymer Materials Co., Ltd.); the high silicon content toughening agent is Japan Zhongyuan silicon-based toughening agent MR-01, the anti-hydrolysis agent is bis(2,6)-diisopropylcarbodiimide, anti-dripping agent (commercially available product), 2-(2'-hydroxy-3,5-dicumylphenyl)benzotriazole (UV-234), and 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol) (UV-360).

[0045] Example 1:

[0046] A highly weather-resistant and cold-resistant highly flame-retardant polycarbonate material is composed of the following raw materials in percentage by mass: 91.8% bisphenol A aromatic polycarbonate, 2% organosilicon / phenoxy polyphosphazene copolymer, 4% high-silicon content toughening agent, 0.5% anti-hydrolysis agent, 0.3% anti-dripping agent, 0.5% 2-(2'-hydroxy-3,5-dicumylphenyl)benzotriazole, 0.5% silicone, 0.2% antioxidant 1010, and 0.2% antioxidant 168.

[0047] Example 2

[0048] A highly weather-resistant and cold-resistant highly flame-retardant polycarbonate material is composed of the following raw materials in percentage by mass: 91.8% bisphenol A aromatic polycarbonate, 2% octaphenylcyclotetrasiloxane, 4% high-silicon content toughening agent, 0.5% anti-hydrolysis agent, 0.3% anti-dripping agent, 0.5% 2-(2'-hydroxy-3,5-dicumylphenyl)benzotriazole, 0.5% silicone, 0.2% antioxidant 1010, and 0.2% antioxidant 168.

[0049] Example 3

[0050] A highly weather-resistant and cold-resistant highly flame-retardant polycarbonate material is composed of the following raw materials in percentage by mass: 91.8% bisphenol A aromatic polycarbonate, 1% octaphenylcyclotetrasiloxane, 1% organosilicon / phenoxy polyphosphazene copolymer, 4% high-silicon content toughening agent, 0.5% anti-hydrolysis agent, 0.3% anti-dripping agent, 0.5% 2-(2'-hydroxy-3,5-dicumylphenyl)benzotriazole, 0.5% silicone, 0.2% antioxidant 1010, and 0.2% antioxidant 168.

[0051] Example 4

[0052] A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, which is composed of the following raw materials by mass percentage: bisphenol A aromatic polycarbonate 88.8%, octaphenylcyclotetrasiloxane 3%, high-silicon-content toughening agent 6%, hydrolysis-resistant agent 0.5%, anti-dripping agent 0.3%, 2-(2'-hydroxy-3,5-di-tert-butylphenyl) benzotriazole 0.5%, silicone 0.5%, antioxidant 1010 0.2%, antioxidant 168 0.2%.

[0053] Example 5

[0054] A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, which is composed of the following raw materials by mass percentage: bisphenol A aromatic polycarbonate 91.8%, octaphenylcyclotetrasiloxane 2%, high-silicon-content toughening agent 4%, hydrolysis-resistant agent 0.5%, anti-dripping agent 0.3%, 2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol) (UV-360) 0.5%, silicone 0.5%, antioxidant 1010 0.2%, antioxidant 168 0.2%.

[0055] Example 6

[0056] A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, which is composed of the following raw materials by mass percentage: bisphenol A aromatic polycarbonate 93.3%, octaphenylcyclotetrasiloxane 0.5%, high-silicon-content toughening agent 4%, hydrolysis-resistant agent 0.5%, anti-dripping agent 0.3%, 2-(2'-hydroxy-3,5-di-tert-butylphenyl) benzotriazole 0.5%, silicone 0.5%, antioxidant 1010 0.2%, antioxidant 168 0.2%.

[0057] Comparative Example 1

[0058] A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, which is composed of the following raw materials by mass percentage: bisphenol A aromatic polycarbonate 91.8%, high-silicon-content toughening agent 6%, hydrolysis-resistant agent 0.5%, anti-dripping agent 0.3%, 2-(2'-hydroxy-3,5-di-tert-butylphenyl) benzotriazole 0.5%, silicone 0.5%, antioxidant 1010 0.2%, antioxidant 168 0.2%.

[0059] Comparative Example 2

[0060] A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material, which is composed of the following raw materials by mass percentage: bisphenol A aromatic polycarbonate 93.55%, potassium perfluorobutanesulfonate 0.25%, high-silicon-content toughening agent 4%, hydrolysis-resistant agent 0.5%, anti-dripping agent 0.3%, 2-(2'-hydroxy-3,5-di-tert-butylphenyl) benzotriazole 0.5%, silicone 0.5%, antioxidant 1010 0.2%, antioxidant 168 0.2%.

[0061] Comparative Example 3

[0062] A highly weather-resistant, cold-resistant and highly flame-retardant polycarbonate material is composed of the following raw materials by mass percentage: 85.8% of bisphenol A aromatic polycarbonate, 2% of silicone / phenoxyphosphazene copolymer, 10% of toughening agent with high silicon content, 0.5% of hydrolysis-resistant agent, 0.3% of anti-dripping agent, 0.5% of 2-(2`-hydroxy-3,5-dicumylphenyl) benzotriazole, 0.5% of silicone, 0.2% of antioxidant 1010, and 0.2% of antioxidant 168.

[0063] Comparative Example 4

[0064] A highly weather-resistant, cold-resistant and highly flame-retardant polycarbonate material is composed of the following raw materials by mass percentage: 95.8% of bisphenol A aromatic polycarbonate, 2% of silicone / phenoxyphosphazene copolymer, 0.5% of hydrolysis-resistant agent, 0.3% of anti-dripping agent, 0.5% of 2-(2`-hydroxy-3,5-dicumylphenyl) benzotriazole, 0.5% of silicone, 0.2% of antioxidant 1010, and 0.2% of antioxidant 168.

[0065] In order to verify the technical effects of the present invention, the polycarbonate materials of Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to the above performance tests as shown in Table 1 below.

[0066] Table 1 Performance parameters of the polycarbonate materials of Examples 1 to 6 and Comparative Examples 1 to 3

[0067]

[0068]

[0069]

[0070] As can be seen from Table 1, in Comparative Example 1, no silicon-based flame retardant was added, and the flame retardancy of the material made of the toughening agent with a high silicon content could not reach 1.5 mm V-0, indicating that the flame retardancy of the polycarbonate material without adding octaphenylcyclotetrasiloxane or silicone / phenoxyphosphazene copolymer was unqualified; in Comparative Example 2, a sulfonate flame retardant was selected as the flame retardant, and the flame retardancy of the polycarbonate material was 1.5 mm V-0. However, in terms of weather resistance (the flame retardancy decreased after hot water immersion and could only reach V1, and the retention rate of the Izod impact strength also decreased to a certain extent. The toughening agent with a high silicon content greatly improved the cold resistance of polycarbonate, and at the same time improved the impact performance of the material after boiling water treatment and ultraviolet resistance to a certain extent. The polycarbonate material prepared by the present invention uses octaphenylcyclotetrasiloxane or silicone / phenoxyphosphazene copolymer as the flame retardant, selects a toughening agent with a high silicon content, and uses bis(2,6)-diisopropylcarbodiimide to improve the hydrolysis resistance of polycarbonate, so that the prepared polycarbonate material has good weather resistance and good flame retardancy. The material has a good performance retention rate after being immersed in 70°C hot water for 168 h and irradiated with ultraviolet rays for 1000 h, and at the same time maintains the heat resistance temperature of PC up to 120°C.

[0071] The above-described embodiments merely represent the specific embodiments of the present application. The description thereof is relatively specific and detailed, but it should not be construed as a limitation on the protection scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the technical solution of the present application, several modifications and improvements can be made, and these all belong to the protection scope of the present application.

[0072] This background art section is provided to generally present the context of the present invention. The work of the currently named inventors, to the extent described in this background art section, and aspects of this section that do not constitute prior art at the time of filing this application are neither expressly nor impliedly admitted to be prior art to the present invention.

Claims

1. A highly weather-resistant, cold-resistant and highly flame-retardant polycarbonate material, characterized in that, Composed of the following raw materials in mass percentages: Polycarbonate resin 85 - 93%; Flame retardant 0.5 - 3%; Toughening agent with high silicon content 3 - 6%; Ultraviolet absorber 0.2 - 0.6%; Drip retardant 0.1 - 0.5%; Hydrolysis inhibitor 0.3 - 0.6% Release agent 0.1 - 0.5%; Antioxidant 168 0.1 - 0.3%; Antioxidant 1010 0.1 - 0.3%.

2. A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material according to claim 1, characterized in that, The polycarbonate resin includes bisphenol A aromatic branched polycarbonate resin; the relative molecular weight of the polycarbonate resin is 28,000 - 33,000.

3. A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material according to claim 1, characterized in that, The flame retardant is one or a compound of two of organosilicon / phenoxy polyphosphazene copolymer or octaphenylcyclotetrasiloxane; the molecular formula of the organosilicon / phenoxy polyphosphazene copolymer is as follows: Wherein R1, R2, R3, and R4 are independently selected from C1 - C20 alkyl, C1 - C20 phenyl, C1 - C20 alkoxy, C1 - C20 phenoxy, C1 - C20 phenyl-containing alkoxy, or C1 - C20 phenyl-containing alkane.

4. According to claim 1, a high weather - resistant, cold - resistant, and highly flame - retardant polycarbonate material, wherein the toughening agent with high silicon content is the silicone - based toughening agent MR - 01 from Japan's Kaneka.

5. A high-temperature and cold-resistant high flame-retardant polycarbonate material according to claim 1, characterized in that The drip retardant is polytetrafluoroethylene coated with a copolymer of styrene and acrylonitrile.

6. A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material according to claim 1, characterized in that, The hydrolysis inhibitor is bis(2,6) - diisopropylcarbodiimide.

7. A highly weather-resistant, cold-resistant and highly flame-retardant polycarbonate material according to claim 1, characterized in that, The ultraviolet absorber is one or two of 2 - (2` - hydroxy - 3,5 - di - tert - amylphenyl)benzotriazole and 2,2` - methylenebis(4 - tert - octyl - 6 - benzotriazolylphenol).

8. A highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material according to claim 1, characterized in that, The release agent is silicone.

9. A method for preparing a highly weather-resistant, cold-resistant, and highly flame-retardant polycarbonate material according to any one of claims 1-8, characterized in that, Including the following steps: a. Weigh the toughening agent with high silicon content, flame retardant, drip retardant, hydrolysis inhibitor, antioxidant, ultraviolet absorber, and release agent according to the ratio, and mix them evenly through a powder mixer to obtain mixture 1; b. Weigh the polycarbonate resin and mixture 1 obtained in step a, and then mix them evenly to obtain mixture 2; c. The mixture 2 obtained in step b is melt - compounded and pelletized in a twin - screw extruder to obtain mixture 3; d. The mixture 3 obtained in step c is extruded, cooled by water, and granulated and sieved to obtain the product.

10. The method according to claim 9, wherein The polycarbonate resin, toughening agent with high silicon content, flame retardant, drip retardant, ultraviolet absorber, and release agent are fully dried and reserved before mixing.

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