A pc / abs composite material based on recycled plastic and a preparation method thereof

Abstract

The application discloses a PC / ABS composite material based on recycled plastic and a preparation method thereof, and belongs to the technical field of high polymer materials, and comprises the following raw materials in parts by weight: 45-55 parts of recycled PC resin, 15-30 parts of ABS resin, 3-5 parts of a flame retardant, 5-8 parts of nano silicon dioxide, and 0.3-1 part of an antioxidant; the flame retardant is prepared into an intermediate in a synthesis process, the intermediate structure has a carbon skeleton of pentaerythritol and a six-membered spiro ring structure, has excellent thermal stability and charring property, and the introduced phosphate structure can endow the intermediate with flame retardant property; carbon-carbon double bonds on the intermediate react with phosphorus-hydrogen bonds on DOPO, and then the flame retardant is prepared; the introduced DOPO can be used as a flame retardant, and the flame retardant molecules formed through the reaction can endow the composite material with excellent thermal stability and flame retardance through the cooperation of the intermediate and DOPO.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a PC / ABS composite material based on recycled plastic and a preparation method thereof. BACKGROUND

[0002] PC / ABS, polycarbonate and acrylonitrile-butadiene-styrene copolymer and mixture, is a thermoplastic plastic made of polycarbonate (Polycarbonate) and polyacrylonitrile (ABS) alloy, which combines the excellent properties of the two materials, the forming property of ABS material and the mechanical property, impact strength and temperature resistance, ultraviolet (UV) resistance of PC, which can be widely used in automobile interior parts, business machines, communication equipment, household appliances and lighting equipment.

[0003] When PC / ABS alloy is used to manufacture electronic components, the material is often required to have flame retardant properties, for which people usually use the method of adding flame retardant to improve the flame retardant properties of the material. The flame retardants commonly used in flame-retardant PC / ABS alloy mainly include halogen-based flame retardants such as decabromodiphenyl ether (or octabromodiphenyl ether), tetrabromobisphenol A, and bromine-containing carbonate oligomer. On the one hand, the use of halogen-containing flame retardants has safety and environmental protection problems, and on the other hand, the corrosive gas (HCl, HBr, etc.) produced by the thermal cracking of halogen-containing flame retardant materials may damage the key components in electronic / electrical equipment even at very low concentrations, causing the entire equipment to malfunction. The addition of inorganic flame retardants has a greater impact on the toughness of ABS flame-retardant materials, which seriously affects the mechanical properties of the material. SUMMARY

[0004] In order to solve the above technical problems, the present application provides an environmentally friendly composite material PCABS based on recycled plastic and a preparation method thereof.

[0005] The object of the present application can be achieved by the following technical solutions:

[0006] A PC / ABS composite material based on recycled plastic, comprising the following raw materials by weight: 45-55 parts of recycled PC resin, 15-30 parts of ABS resin, 3-5 parts of flame retardant, 5-8 parts of nano-silicon dioxide, and 0.3-1 part of antioxidant;

[0007] The flame retardant is prepared by the following steps:

[0008] Step S1, add pentaerythritol and dimethyl allylphosphonate into chlorobenzene, stir at a uniform speed and add tetramethylammonium chloride, heat to 150-170℃, stir at a uniform speed and react for 2-4h, then distill under reduced pressure to prepare the intermediate, control the amount ratio of pentaerythritol, dimethyl allylphosphonate and chlorobenzene to be 0.1-0.2mol:0.2-0.5mol:150-200mL, and the amount of tetramethylammonium chloride to be 3-5% of the weight of dimethyl allylphosphonate;

[0009] In step S1, tetramethylammonium chloride is used as a catalyst, chlorobenzene is used as a solvent, and pentaerythritol and dimethyl allylphosphonate are reacted to prepare the intermediate, and the reaction process is as shown below:

[0010]

[0011] The intermediate prepared in step S1 has both the carbon skeleton of pentaerythritol and the six-membered spiro ring structure, has excellent thermal stability and carbonization performance, and the introduced phosphate structure can endow the intermediate with flame retardant performance.

[0012] Step S2, add DOPO and the intermediate into N,N-dimethylformamide, pass in nitrogen, stir at a uniform speed and heat to 120-140℃, keep warm for 4-6h, then cool to room temperature to prepare the flame retardant, control the amount ratio of DOPO, the intermediate and N,N-dimethylformamide to be 0.2-0.4mol:0.1-0.2mol:100mL.

[0013] In step S2, the carbon-carbon double bond on the intermediate reacts with the phosphorus-hydrogen bond on DOPO to further prepare the flame retardant, and the reaction process is as shown below:

[0014]

[0015] The flame retardant has both the carbon skeleton of pentaerythritol and the six-membered spiro ring structure, has excellent thermal stability and carbonization performance, and the introduced DOPO itself can be used as a flame retardant, and the flame retardant molecules formed by the reaction can endow the composite material with excellent thermal stability and flame retardance through the cooperation of the intermediate and DOPO.

[0016] Further, the antioxidant is antioxidant 1010 or antioxidant 168.

[0017] Further, the molecular weight of the recycled PC resin is 30000-40000g / mol, and the glass transition temperature is 140-150℃.

[0018] Further, the ABS resin is a graft copolymer composed of acrylonitrile, butadiene and styrene, and the weight average molecular weight is 120000-150000.

[0019] A preparation method of a PC / ABS composite material based on recycled plastic, comprising the following steps:

[0020] After the recycled PC resin, ABS resin, flame retardant, nano-silicon dioxide and antioxidant are uniformly mixed, the PC / ABS composite material is prepared by extruding and granulating through a double-screw extruder.

[0021] Further, the extrusion temperature of the double-screw extruder is: the temperature of the first zone is 225-240 DEG C, the temperature of the second zone is 240-250 DEG C, the temperature of the third zone is 250-260 DEG C, the temperature of the fourth zone is 255-265 DEG C, the temperature of the fifth zone is 260-270 DEG C, the temperature of the sixth zone is 260-270 DEG C, the temperature of the seventh zone is 255-270 DEG C, the temperature of the eighth zone is 255-260 DEG C, the temperature of the ninth zone is 255-260 DEG C, and the temperature of the tenth zone is 255-260 DEG C, and the screw rotation speed is 250-550 r / min.

[0022] The application has the beneficial effects that: the application prepares a composite material based on recycled PC resin, takes recycled PC resin and ABS resin as the matrix, adds nano-silicon dioxide to improve the mechanical properties of the composite material, synthesizes a flame retardant, first prepares an intermediate, the structure of the prepared intermediate has both the carbon skeleton of pentaerythritol and the six-membered spiro ring structure, has excellent thermal stability and carbonization property, and the introduced phosphate structure can endow the intermediate with flame retardant property, then the carbon-carbon double bond on the intermediate reacts with the phosphorus-hydrogen bond on DOPO, and further a flame retardant is prepared, the introduced DOPO itself can be used as a flame retardant, and the flame retardant molecules formed by the reaction can endow the composite material with excellent thermal stability and flame retardancy in a way of cooperation of the intermediate and DOPO. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application. Embodiment 1

[0024] A PC / ABS composite material based on recycled plastic, comprising the following raw materials by weight: 45 parts of recycled PC resin, 15 parts of ABS resin, 3 parts of flame retardant, 5 parts of nano-silicon dioxide, and 0.3 parts of antioxidant.

[0025] After the recycled PC resin, ABS resin, flame retardant, nano-silicon dioxide and antioxidant are uniformly mixed, the PC / ABS composite material is prepared by extruding and granulating through a double-screw extruder.

[0026] The extrusion temperature of the double screw extruder is: the temperature of the first zone is 225-240℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 250-260℃, the temperature of the fourth zone is 255-265℃, the temperature of the fifth zone is 260-270℃, the temperature of the sixth zone is 260-270℃, the temperature of the seventh zone is 255-270℃, the temperature of the eighth zone is 255-260℃, the temperature of the ninth zone is 255-260℃, the temperature of the tenth zone is 255-260℃, and the screw rotation speed is 250-550 r / min.

[0027] The antioxidant is antioxidant 1010.

[0028] The flame retardant is prepared by the following steps:

[0029] Step S1, pentaerythritol and dimethyl allyl phosphonate are added into chlorobenzene, uniform stirring and adding tetramethylammonium chloride, heating to 150℃, uniform stirring and reaction for 2h, then reduced pressure distillation, the intermediate is prepared, the amount ratio of pentaerythritol, dimethyl allyl phosphonate and chlorobenzene is controlled to be 0.1mol:0.2mol:150mL, and the amount of tetramethylammonium chloride is 3% of the weight of dimethyl allyl phosphonate;

[0030] Step S2, DOPO and the intermediate are added into N,N-dimethylformamide, nitrogen is introduced, uniform stirring and heating to 120℃, keeping the temperature for 4h, then cooling to room temperature, the flame retardant is prepared, the amount ratio of DOPO, the intermediate and N,N-dimethylformamide is controlled to be 0.2mol:0.1mol:100mL.

[0031] The molecular weight of the recycled PC resin is 30000-40000g / mol, and the glass transition temperature is 140-150℃.

[0032] The ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the weight average molecular weight is 120000-150000. Example 2

[0033] A PC / ABS composite material based on recycled plastic, comprising the following raw materials by weight: 50 parts of recycled PC resin, 20 parts of ABS resin, 4 parts of flame retardant, 6 parts of nano silicon dioxide, and 0.5 parts of antioxidant.

[0034] The recycled PC resin, ABS resin, flame retardant, nano silicon dioxide and antioxidant are uniformly mixed, then extruded and granulated by a double screw extruder to prepare a PC / ABS composite material.

[0035] The extrusion temperature of the double screw extruder is: the temperature of the first zone is 225-240℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 250-260℃, the temperature of the fourth zone is 255-265℃, the temperature of the fifth zone is 260-270℃, the temperature of the sixth zone is 260-270℃, the temperature of the seventh zone is 255-270℃, the temperature of the eighth zone is 255-260℃, the temperature of the ninth zone is 255-260℃, the temperature of the tenth zone is 255-260℃, and the screw rotation speed is 250-550 r / min.

[0036] The antioxidant is antioxidant 1010.

[0037] The flame retardant is prepared by the following steps:

[0038] Step S1, pentaerythritol and dimethyl allyl phosphonate are added into chlorobenzene, and tetramethylammonium chloride is added while stirring uniformly, and the temperature is raised to 160℃, and after stirring uniformly and reacting for 3h, the intermediate is prepared by distillation under reduced pressure, and the amount ratio of pentaerythritol, dimethyl allyl phosphonate and chlorobenzene is controlled to be 0.15mol:0.3mol:180mL, and the amount of tetramethylammonium chloride is 4% of the weight of dimethyl allyl phosphonate;

[0039] Step S2, DOPO and the intermediate are added into N,N-dimethylformamide, nitrogen is introduced, and the temperature is raised to 130℃ while stirring uniformly, and the reaction is kept for 5h, and after the reaction is completed, the temperature is lowered to room temperature, and the flame retardant is prepared, and the amount ratio of DOPO, the intermediate and N,N-dimethylformamide is controlled to be 0.3mol:0.1mol:100mL.

[0040] The molecular weight of the recycled PC resin is 30000-40000g / mol, and the glass transition temperature is 140-150℃.

[0041] The ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the weight average molecular weight is 120000-150000. Example 3

[0042] A PC / ABS composite material based on recycled plastic, comprising the following raw materials by weight: 52 parts of recycled PC resin, 25 parts of ABS resin, 4 parts of flame retardant, 7 parts of nano silicon dioxide, and 0.8 parts of antioxidant.

[0043] The recycled PC resin, ABS resin, flame retardant, nano silicon dioxide and antioxidant are uniformly mixed, and then extruded and granulated by a double screw extruder to prepare a PC / ABS composite material.

[0044] The extrusion temperature of the double screw extruder is: the temperature of the first zone is 225-240℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 250-260℃, the temperature of the fourth zone is 255-265℃, the temperature of the fifth zone is 260-270℃, the temperature of the sixth zone is 260-270℃, the temperature of the seventh zone is 255-270℃, the temperature of the eighth zone is 255-260℃, the temperature of the ninth zone is 255-260℃, the temperature of the tenth zone is 255-260℃, and the screw rotation speed is 250-550 r / min.

[0045] The antioxidant is antioxidant 1010 or antioxidant 168.

[0046] The flame retardant is prepared by the following steps:

[0047] In step S1, pentaerythritol and dimethyl allyl phosphonate are added into chlorobenzene, and tetramethylammonium chloride is added under uniform stirring, and the temperature is raised to 170℃, and uniform stirring is carried out and the reaction is carried out for 4h, and then the intermediate is prepared by distillation under reduced pressure, and the amount ratio of pentaerythritol, dimethyl allyl phosphonate and chlorobenzene is controlled to be 0.2mol:0.4mol:180mL, and the amount of tetramethylammonium chloride is 3-5% of the weight of dimethyl allyl phosphonate;

[0048] In step S2, DOPO and the intermediate are added into N,N-dimethylformamide, nitrogen is introduced, uniform stirring is carried out, and the temperature is raised to 130℃, and the reaction is carried out for 5h, and then the temperature is lowered to room temperature after the reaction is completed, and the flame retardant is prepared, and the amount ratio of DOPO, the intermediate and N,N-dimethylformamide is controlled to be 0.4mol:0.2mol:100mL.

[0049] The molecular weight of the recycled PC resin is 30000-40000g / mol, and the glass transition temperature is 140-150℃.

[0050] The ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, and the weight average molecular weight is 120000-150000. Example 4

[0051] A PC / ABS composite material based on recycled plastic comprises the following raw materials by weight: 55 parts of recycled PC resin, 30 parts of ABS resin, 5 parts of flame retardant, 8 parts of nano silicon dioxide, and 1 part of antioxidant.

[0052] The recycled PC resin, ABS resin, flame retardant, nano silicon dioxide and antioxidant are uniformly mixed, and then extruded and granulated by a double screw extruder to prepare the PC / ABS composite material.

[0053] The extrusion temperature of the double screw extruder is: the temperature of the first zone is 225-240℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 250-260℃, the temperature of the fourth zone is 255-265℃, the temperature of the fifth zone is 260-270℃, the temperature of the sixth zone is 260-270℃, the temperature of the seventh zone is 255-270℃, the temperature of the eighth zone is 255-260℃, the temperature of the ninth zone is 255-260℃, the temperature of the tenth zone is 255-260℃, and the screw rotation speed is 250-550 r / min.

[0054] The antioxidant is antioxidant 168.

[0055] The flame retardant is prepared by the following steps:

[0056] In step S1, pentaerythritol and dimethyl allyl phosphonate are added into chlorobenzene, and tetramethylammonium chloride is added while stirring uniformly, and the temperature is raised to 170℃, and after stirring uniformly and reacting for 4h, the reaction product is distilled under reduced pressure, the amount ratio of pentaerythritol, dimethyl allyl phosphonate and chlorobenzene is controlled to be 0.2mol:0.5mol:200mL, and the amount of tetramethylammonium chloride is 5% of the weight of dimethyl allyl phosphonate;

[0057] In step S2, DOPO and the intermediate product are added into N,N-dimethylformamide, nitrogen is introduced, and the temperature is raised to 140℃ while stirring uniformly, and the reaction is maintained for 4-6h, and after the reaction is completed, the temperature is lowered to room temperature, and the flame retardant is prepared, and the amount ratio of DOPO, the intermediate product and N,N-dimethylformamide is controlled to be 0.4mol:0.2mol:100mL.

[0058] The molecular weight of the recycled PC resin is 30000-40000g / mol, and the glass transition temperature is 140-150℃.

[0059] The ABS resin is a graft copolymer composed of acrylonitrile, butadiene and styrene, and the weight average molecular weight is 120000-150000.

[0060] Comparative Example 1

[0061] In this comparative example, aluminum hydroxide is used as the flame retardant, and the rest is the same as in Example 1, and the preparation method is as follows:

[0062] A PC / ABS composite material based on recycled plastic comprises the following raw materials by weight: 45 parts of recycled PC resin, 15 parts of ABS resin, 3 parts of aluminum hydroxide, 5 parts of nano silicon dioxide, and 0.3 parts of antioxidant.

[0063] The recycled PC resin, ABS resin, aluminum hydroxide, nano silicon dioxide and antioxidant are mixed uniformly, and then extruded and granulated by a double screw extruder to prepare a PC / ABS composite material.

[0064] The extrusion temperature of the double screw extruder is: the temperature of the first zone is 225-240℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 250-260℃, the temperature of the fourth zone is 255-265℃, the temperature of the fifth zone is 260-270℃, the temperature of the sixth zone is 260-270℃, the temperature of the seventh zone is 255-270℃, the temperature of the eighth zone is 255-260℃, the temperature of the ninth zone is 255-260℃, the temperature of the tenth zone is 255-260℃, and the screw rotation speed is 250-550 r / min.

[0065] Comparative Example 2

[0066] This comparative example uses an intermediate as a flame retardant, and the rest is the same as Example 1. The preparation method is as follows:

[0067] A PC / ABS composite material based on recycled plastics includes the following raw materials by weight: 45 parts of recycled PC resin, 15 parts of ABS resin, 3 parts of intermediate, 5 parts of nano-silicon dioxide, and 0.3 parts of antioxidant.

[0068] The recycled PC resin, ABS resin, intermediate, nano-silicon dioxide, and antioxidant are mixed uniformly, then extruded and granulated by a double screw extruder to produce a PC / ABS composite material.

[0069] The extrusion temperature of the double screw extruder is: the temperature of the first zone is 225-240℃, the temperature of the second zone is 240-250℃, the temperature of the third zone is 250-260℃, the temperature of the fourth zone is 255-265℃, the temperature of the fifth zone is 260-270℃, the temperature of the sixth zone is 260-270℃, the temperature of the seventh zone is 255-270℃, the temperature of the eighth zone is 255-260℃, the temperature of the ninth zone is 255-260℃, the temperature of the tenth zone is 255-260℃, and the screw rotation speed is 250-550 r / min.

[0070] The properties of the composite materials prepared in Examples 1-4 and Comparative Examples 1-2 were detected, and the results are shown in Table 1 below:

[0071] Flame retardant performance: experimental standard GB / T2406-2009.

[0072] Mechanical properties: tested according to the provisions of GB / T 1040.2-2006 "Determination of tensile properties of plastics - Part 2: test conditions for moulded and extruded plastics".

[0073] Table 1

[0074]

[0075] As can be seen from Table 1, the composite materials prepared in Examples 1-4 of the present application have good flame retardant properties while maintaining excellent toughness, indicating that the intermediate structure prepared has both the carbon skeleton of pentaerythritol and the six-membered spiro ring structure, has excellent thermal stability and charring property, and the introduced phosphate structure can endow the intermediate with flame retardant properties, and then the carbon-carbon double bond on the intermediate reacts with the phosphorus-hydrogen bond on DOPO, and further a flame retardant is prepared, the introduced DOPO itself can be used as a flame retardant, and the flame retardant molecules formed by the reaction can endow the composite material with excellent thermal stability and flame retardant property in a synergistic manner with DOPO, and have little effect on the toughness of the composite material.

[0076] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the concept of the present application or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. A PC / ABS composite material based on recycled plastic, characterized in that, The raw materials include the following parts by weight: 45-55 parts recycled PC resin, 15-30 parts ABS resin, 3-5 parts flame retardant, 5-8 parts nano silica, and 0.3-1 parts antioxidant. The flame retardant is prepared by the following steps: Step S1: Add pentaerythritol and dimethyl allylphosphonate to chlorobenzene, stir at a constant speed and add tetramethylammonium chloride, heat to 150-170℃, stir at a constant speed and react for 2-4 hours, then distill under reduced pressure to obtain the intermediate. Step S2: Add DOPO and the intermediate to N,N-dimethylformamide, purge with nitrogen, stir at a constant speed and heat to 120-140℃, keep the temperature for 4-6 hours, and cool to room temperature after the reaction is complete to obtain the flame retardant. In step S1, the ratio of pentaerythritol, dimethyl allylphosphonate, and chlorobenzene is controlled to be 0.1-0.2 mol: 0.2-0.5 mol: 150-200 mL, and the amount of tetramethylammonium chloride is 3-5% of the weight of dimethyl allylphosphonate. The ratio of DOPO, intermediate, and N,N-dimethylformamide should be controlled at 0.2-0.4 mol: 0.1-0.2 mol: 100 mL.

2. The PC / ABS composite material based on recycled plastic according to claim 1, characterized in that, The antioxidant is antioxidant 1010 or antioxidant 168.

3. The PC / ABS composite material based on recycled plastic according to claim 1, characterized in that, The recycled PC resin has a molecular weight of 30,000-40,000 g / mol and a glass transition temperature of 140-150℃.

4. The PC / ABS composite material based on recycled plastic according to claim 1, characterized in that, The ABS resin is a graft copolymer composed of acrylonitrile-butadiene-styrene, with a weight-average molecular weight of 120,000-150,000.

5. The method for preparing PC / ABS composite material based on recycled plastic according to claim 1, characterized in that, Includes the following steps: The recycled PC resin, ABS resin, flame retardant, nano silica and antioxidant are mixed evenly and then extruded and granulated by a twin-screw extruder to obtain PC / ABS composite material.

6. The method for preparing PC / ABS composite material based on recycled plastic according to claim 5, characterized in that, The extrusion temperatures of the twin-screw extruder are as follows: Zone 1: 225-240℃; Zone 2: 240-250℃; Zone 3: 250-260℃; Zone 4: 255-265℃; Zone 5: 260-270℃; Zone 6: 260-270℃; Zone 7: 255-270℃; Zone 8: 255-260℃; Zone 9: 255-260℃; Zone 10: 255-260℃; and the screw speed is 250-550 r / min.

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