Halogen-free flame-retardant PC / ABS composite material with high recovery ratio

Abstract

The invention relates to a halogen-free flame-retardant PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene) composite material with a high recovery ratio, which comprises the following components in parts by mass: 30-50 parts 5 to 25 parts by mass of ABS; 30 to 58.2 parts by mass of PC / ABS; 5-15 parts by mass of a flame retardant; 0.2 to 0.8 part by mass of an antioxidant; 0.3 to 0.8 part by mass of a flow modifier; 0.3 to 1.2 parts by mass of an anti-dripping agent; the environment-friendly PC / ABS composite material has the beneficial effects that the material does not contain dangerous halogen compounds, the risk of secondary pollution can be reduced when the material is recycled, a high-proportion recycled material (greater than or equal to 30%) is used, so that the material has higher environment-friendly performance, and the material takes PC / ABS as a main body, so that the production cost is reduced, and the environment-friendly PC / ABS composite material is suitable for industrial production. Wherein the proportion of the added PC / ABS crushed material is larger than or equal to 30%, the PC / ABS material has certain mechanical performance and flame retardance (1.0 mm V-0) and also has high impact strength (larger than 40 kJ / m < 2 >), the application range of the PC / ABS material can be effectively widened, and PC / ABS is PIR, is a water gap, an auxiliary board, a defective product and the like generated during injection molding of a product in a factory and is few in impurity and more stable in quality.

Description

[Technical field]

[0001] The invention relates to the technical field of polycarbonate composite materials, in particular to a halogen-free flame-retardant PC / ABS composite material with a high recycling ratio. [Background technology]

[0002] In the manufacturing process of many products, plastic material is one of the most commonly used materials. However, the plastic waste generated in the process of plastic production needs to go through multiple treatments before it can be used again. Therefore, it is necessary to develop a material that can directly use PIR (post-industrial recycled materials) to reduce the generation of plastic waste in the production process.

[0003] PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene copolymer) is a general term for PC and ABS plastics that are blended and modified in different proportions. The purpose is to make the modified material have the advantages of both, such as the temperature resistance and high mechanical properties of PC and the easy molding and processing characteristics of ABS. However, due to the essential characteristics of PC and ABS materials, it is difficult to achieve flame retardancy, high impact strength and high heat deformation temperature.

[0004] Traditional materials are difficult to be widely used because of their low recycling ratio and poor physical properties. In addition, since the composition of PC / ABS materials is relatively complex, including PC, ABS and other additives, they are easily disturbed by impurities during the recycling process, affecting the quality of the materials. In addition, the cost and performance of recycled materials are also a key issue. Therefore, it is urgent and in line with market trends to develop a PC / ABS material with a high recycling ratio and good performance.

[0005] In view of this, it is necessary to provide a halogen-free flame-retardant PC / ABS composite material with a high recycling rate to solve the above problems. [Summary of the invention]

[0006] The object of the present invention is to provide a halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, which can be directly prepared from recycled PC / ABS (PIR) plastics to obtain a PC / ABS composite material with a high recycling ratio and has the characteristics of flame retardancy and high impact strength.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] A halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, wherein every 100 parts by weight of the finished material comprises the following components in parts by weight:

[0009] Polycarbonate, 30-50 parts by mass;

[0010] ABS, 5-25 parts by mass;

[0011] PC / ABS, 30-58.2 parts by mass;

[0012] Flame retardant, 5 to 15 parts by weight;

[0013] Antioxidant, 0.2-0.8 parts by weight;

[0014] Flow modifier, 0.3-0.8 parts by mass;

[0015] Anti-dripping agent, 0.3-1.2 parts by mass;

[0016] Toughening agent, 1 to 10 parts by weight.

[0017] The polycarbonate selected is PIR (Post Industrial Recycled), and its recycled content is 90-99%.

[0018] The rubber content of the selected ABS is not less than 12% (12% to 65%), and the particle size is not less than 100nm (100 to 1000nm).

[0019] The selected PC / ABS is PIR (Post Industrial Recycled), which can be the nozzle material (referring to the remaining part when the product is produced) generated when the factory injects the product, the secondary brand (referring to the material whose performance of the product does not meet the requirements in a certain aspect), the defective product (referring to the finished product and semi-finished product with serious defects or tolerance that does not meet the design standard requirements generated during the production process), etc. The PC / ABS can be flame retardant or non-flame retardant, with a halogen content of less than 300PPm and an impact strength of more than 15kJ / ㎡, and it can be a compound of one or more PC / ABS (PIR).

[0020] The flame retardant selected can be a combination of one or more of hypophosphite flame retardants, phosphate flame retardants, sulfonate flame retardants, silicone flame retardants, etc. and their derivatives.

[0021] The selected antioxidant can be one or a combination of hindered phenol, hindered amine, and phosphite antioxidants.

[0022] The selected flow modifier is calcium stearate or PETS (pentaerythritol stearate), ethylene bis stearamide (EBS), RH-313 (polyurethane slip agent) or silicone oil.

[0023] The anti-dripping agent selected is PTFE, which can be a coated type or an uncoated type, or a mixture.

[0024] The selected toughening agent can be one or a combination of more than one of core-shell acrylate-PMMA toughening agents, core-shell acrylate-SAN toughening agents, core-shell silicone-PMMA toughening agents, core-shell silicone-SAN toughening agents, cross-linked methacrylate-methyl methacrylate toughening agents, butadiene-styrene-methyl methacrylate toughening agents, and silicone rubber-methyl methacrylate toughening agents.

[0025] A product, characterized in that the product is mainly made of PC / ABS and a halogen-free flame-retardant PC / ABS composite material with a high recycling ratio is prepared by using processing aids.

[0026] The beneficial effects of the present invention are:

[0027] 1. The material of the present invention does not contain dangerous halogen compounds, and the risk of secondary pollution can be reduced when it is recycled and reused.

[0028] 2. The material of the present invention uses a high proportion of recycled materials (≥30%), making it more environmentally friendly.

[0029] 3. The material of the present invention is mainly composed of PC / ABS, which reduces the production cost. The proportion of PC / ABS crushed material added is ≥30%. In addition to having certain mechanical properties and flame retardancy (1.0mm V-0), it also has a higher impact strength (greater than 40kJ / ㎡), which can effectively increase its application range.

[0030] 4. The material PC / ABS (PIR) of the present invention is the sprue, secondary brand, defective product, etc. produced when the factory injects the product, and has less impurities and more stable quality. [Specific implementation method]

[0031] To further illustrate the technical means and effects adopted by the present invention, the following is a detailed description in conjunction with the embodiments of the present invention.

[0032] The present invention provides a halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, which is characterized in that it comprises the following components in parts by weight:

[0033] Polycarbonate, 30-50 parts by mass;

[0034] ABS, 5-25 parts by mass;

[0035] PC / ABS, 30-58.2 parts by mass;

[0036] Flame retardant, 5 to 15 parts by weight;

[0037] Antioxidant, 0.2-0.8 parts by weight;

[0038] Flow modifier, 0.3-0.8 parts by mass;

[0039] Anti-dripping agent, 0.3-1.2 parts by mass;

[0040] Toughening agent, 1 to 10 parts by weight.

[0041] The polycarbonate used is PIR (Post Industrial Recycled), and its recycled content is 90-99%.

[0042] The rubber content of the selected ABS is not less than 12% (12% to 65%), and the particle size is not less than 100nm (100 to 1000nm).

[0043] The selected PC / ABS is PIR (Post Industrial Recycled), which can be the nozzle material (referring to the remaining part when the product is produced) generated when the factory injects the product, the secondary brand (referring to the material whose performance in a certain aspect of the product does not meet the requirements), the defective product (referring to the finished product and semi-finished product with serious defects or tolerance that does not meet the design standard requirements generated during the production process), etc. The PC / ABS can be flame retardant or non-flame retardant, with a halogen content of less than 300PPm and an impact strength of more than 15kJ / ㎡, and it can be a compound of one or more PC / ABS (PIR).

[0044] Among them, the selected flame retardant can be a hypophosphite flame retardant (such as vinyl aluminum hypophosphite flame retardant, vinyl hypophosphite), a phosphate flame retardant (such as 1,3-phenylene phosphate (2,6-methylphenyl) tetraester, tetraphenyl bisphenol A diphosphate and its derivative flame retardant (BDP), tetraphenyl resorcinol diphosphate and its derivative flame retardant, triphenyl phosphate flame retardant), a sulfonate flame retardant (such as potassium benzenesulfonylbenzenesulfonate (KSS), potassium perfluorobutyl sulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB)), an organosilicon flame retardant (such as polysilicon borane and its derivative flame retardant, cross-linked polydimethylsiloxane (PDMS)), etc. and their derivatives. One or more of the compounding and use.

[0045] The antioxidant selected may be one or a combination of hindered phenol, hindered amine, and phosphite antioxidants.

[0046] Wherein, the selected flow modifier is calcium stearate or PETS (pentaerythritol stearate), ethylene bis stearamide (EBS), RH-313 (polyurethane slip agent) or silicone oil.

[0047] Wherein, the selected anti-dripping agent is PTFE, which can be a coated type or an uncoated type or a mixture.

[0048] Among them, the selected toughening agent can be one or more of the following: core-shell acrylate-PMMA toughening agent, core-shell acrylate-SAN toughening agent, core-shell silicone-PMMA toughening agent, core-shell silicone-SAN toughening agent, cross-linked methacrylate-methyl methacrylate toughening agent, butadiene-styrene-methyl methacrylate toughening agent, silicone rubber-methyl methacrylate toughening agent.

[0049] Comparative Example 1

[0050] A halogen-free flame-retardant PC / ABS composite material with a high recycling ratio comprises the following components in parts by mass: 43.6 parts of polycarbonate, 20 parts of ABS, 30 parts of PC / ABS, 0.5 parts of an anti-dripping agent, 0.3 parts of a colorant, 5 parts of a flame retardant-2, 0 parts of a toughening agent, 0.3 parts of an antioxidant, and 0.3 parts of a flow modifier.

[0051] Specifically, the selected polycarbonate is bisphenol A linear polycarbonate, wherein 43.6 parts of the polycarbonate are PIR.

[0052] 30 parts of PC / ABS are crushed materials PIR.

[0053] 0.5 parts of the anti-dripping agent is encapsulated PTFE.

[0054] 0.3 parts of the colorant is carbon black powder.

[0055] 5 parts of flame retardant-2 are phosphate flame retardants.

[0056] 0.3 parts of antioxidant is hindered amine antioxidant.

[0057] 0.3 parts of the flow improver is ethylene bis stearamide flow improver.

[0058] When preparing the halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, the components of corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded into granules. The processing machine selected is a twin-screw extruder, and the processing temperature is 280-290°C.

[0059] Example 2

[0060] A halogen-free flame-retardant PC / ABS composite material with a high recycling ratio comprises the following components in parts by weight: 38.4 parts of polycarbonate, 14 parts of ABS, 40 parts of PC / ABS, 0.5 parts of an anti-dripping agent, 0.3 parts of a colorant, 5 parts of a flame retardant-2, 1 part of a toughening agent, 0.3 parts of an antioxidant, and 0.5 parts of a flow modifier.

[0061] Specifically, the selected polycarbonate is bisphenol A linear polycarbonate, wherein 38.4 parts of the polycarbonate is PIR.

[0062] 40 parts of PC / ABS are crushed material PIR.

[0063] 0.5 parts of the anti-dripping agent is encapsulated PTFE.

[0064] 0.3 parts of the colorant is carbon black powder.

[0065] 5 parts of flame retardant-2 are phosphate flame retardants.

[0066] 0.3 parts of antioxidant is hindered amine antioxidant.

[0067] 0.5 parts of the flow improver is ethylene bis stearamide flow improver.

[0068] When preparing the halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, the components of corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded into granules. The processing machine selected is a twin-screw extruder, and the processing temperature is 280-290°C.

[0069] Example 3

[0070] A halogen-free flame-retardant PC / ABS composite material with a high recycling ratio comprises the following components in parts by weight: 30.4 parts of polycarbonate, 10 parts of ABS, 50 parts of PC / ABS, 0.5 parts of an anti-dripping agent, 0.3 parts of a colorant, 1 part of a flame retardant-1, 5 parts of a flame retardant-2, 2 parts of a toughening agent, 0.3 parts of an antioxidant, and 0.5 parts of a flow modifier.

[0071] Specifically, the selected polycarbonate is bisphenol A linear polycarbonate, wherein 30.4 parts of the polycarbonate is PIR.

[0072] 50 parts of PC / ABS are crushed materials PIR.

[0073] 0.5 parts of the anti-dripping agent is encapsulated PTFE.

[0074] 0.3 parts of the colorant is carbon black powder.

[0075] 1 part of flame retardant-1 is a hypophosphite flame retardant.

[0076] 5 parts of flame retardant-2 are phosphate flame retardants.

[0077] 0.3 parts of antioxidant is hindered amine antioxidant.

[0078] 0.3 parts of the flow improver is ethylene bis stearamide flow improver.

[0079] When preparing the halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, the components of corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded into granules. The processing machine selected is a twin-screw extruder, and the processing temperature is 280-290°C.

[0080] After the above implementation, the same components were used for the re-implementation. Comparative Example 1, Example 2, and Example 3 were melt-extruded and granulated. Then, the particles in each example were injection-molded into standard test specimens on an injection molding machine. The mechanical properties of the obtained materials were tested according to the standard. The test results are shown in Table 1:

[0081] Table 1 Test results

[0082]

[0083] From the test results of Comparative Example 1, Example 2 and Example 3, it can be seen that the present invention uses PC / ABS as the main body and utilizes processing aids to achieve the preparation of a halogen-free flame-retardant PC / ABS composite material with a high recovery ratio.

[0084] The beneficial effects of the present invention are:

[0085] 1. The material of the present invention does not contain dangerous halogen compounds, and the risk of secondary pollution can be reduced when it is recycled and reused.

[0086] 2. The material of the present invention uses a high proportion of recycled materials (≥30%), making it more environmentally friendly.

[0087] 3. The material of the present invention is mainly composed of PC / ABS, which reduces the production cost. The proportion of PC / ABS crushed material added is ≥30%. In addition to having certain mechanical properties and flame retardancy (1.0mm V-0), it also has a higher impact strength (greater than 40kJ / ㎡), which can effectively increase its application range.

[0088] 4. The material PC / ABS (PIR) of the present invention is the sprue, secondary brand, defective product, etc. produced when the factory injects the product, and has less impurities and more stable quality.

[0089] It should be pointed out that the present invention is not limited to the above-mentioned implementation modes, and any simple modifications, equivalent changes and modifications made to the above-mentioned embodiments by any technician familiar with the profession based on the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A halogen-free flame-retardant PC / ABS composite material with a high recycling ratio, characterized in that: The composition comprises the following components in parts by weight: Polycarbonate, 30-50 parts by mass; ABS, 5-25 parts by mass; PC / ABS, 30-58.2 parts by mass; Flame retardant, 5 to 15 parts by weight; Antioxidant, 0.2-0.8 parts by weight; Flow modifier, 0.3-0.8 parts by mass; Anti-dripping agent, 0.3-1.2 parts by mass; Toughening agent, 1 to 10 parts by weight.

2. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The polycarbonate selected is PIR (Post Industrial Recycled), and its recycled content is 90-99%.

3. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The rubber content of the selected ABS is not less than 12% (12% to 65%), and the particle size is not less than 100nm (100 to 1000nm).

4. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected PC / ABS is PIR (Post Industrial Recycled), which may be sprue material, secondary brand, defective product, etc. produced when the factory injects products. The PC / ABS may be flame retardant or non-flame retardant, with a halogen content of less than 300 PPm and an impact strength of more than 15 kJ / ㎡. It may be a compound of one or more PC / ABS (PIR).

5. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The flame retardant selected can be a combination of one or more of hypophosphite flame retardants, phosphate flame retardants, sulfonate flame retardants, silicone flame retardants, etc. and their derivatives.

6. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected antioxidant can be one or a combination of hindered phenol, hindered amine, and phosphite antioxidants.

7. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected flow modifier is calcium stearate or PETS (pentaerythritol stearate), ethylene bis stearamide (EBS), RH-313 (polyurethane slip agent) or silicone oil.

8. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The anti-dripping agent selected is PTFE, which can be a coated type or an uncoated type, or a mixture.

9. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected toughening agent can be one or a combination of more than one of core-shell acrylate-PMMA toughening agents, core-shell acrylate-SAN toughening agents, core-shell silicone-PMMA toughening agents, core-shell silicone-SAN toughening agents, cross-linked methacrylate-methyl methacrylate toughening agents, butadiene-styrene-methyl methacrylate toughening agents, and silicone rubber-methyl methacrylate toughening agents.

10. The halogen-free flame-retardant PC / ABS composite material with a high recycling ratio as claimed in claim 1, characterized in that: The processing machine selected is a twin-screw extruder, and the processing temperature is 280-290°C.

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