Flame-retardant ABS composite material and preparation method thereof

Abstract

The invention discloses a flame-retardant ABS (Acrylonitrile Butadiene Styrene) composite material and a preparation method thereof. The flame-retardant ABS composite material is prepared from the following components in parts by weight: 80-100 parts of ABS, 18-24 parts of a flame retardant and 0.1-0.5 part of an antioxidant, and the flame retardant is a Ni-MOF / MPP (Methyl Phosphate) / praseodymium oxide compound. The invention also discloses a preparation method of the ABS composite material. According to the Ni-MOF / MPP / praseodymium oxide compound, Ni-MOF serves as a framework, melamine polyphosphate (MPP) and praseodymium oxide are laid on the framework, the praseodymium oxide reacts with polyphosphoric acid decomposed by the MPP, the polyphosphoric acid is inhibited from being decomposed to release P2O5 through generation spectrum phosphate, the charring capacity of a flame-retardant system is improved, and a stable expanded carbon layer is formed. The flame retardant property of the ABS composite material can be obviously improved, so that the ABS composite material can be used in the field of automobile household appliance materials and has an extremely good application prospect.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to a flame-retardant ABS composite material and a preparation method thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene resin (ABS) is a widely used polymer polyester resin. ABS has the advantages of good fatigue resistance, heat resistance, and excellent dimensional stability. However, in some specific application fields, such as electronic and electrical equipment, automobiles, aerospace and other fields, the flame retardant performance of ABS is very high, which will limit the application of ABS composite materials in some specific fields. Specifically: in the field of electronic and electrical equipment, such as computers, televisions, mobile phones and other products, since electronic equipment will generate heat and current during operation, if a fire occurs, it may cause serious losses and safety risks. Therefore, for the ABS materials used in these devices, it is required to have good flame retardant properties to reduce the occurrence of fire and the spread of fire. Generally speaking, the flame retardant WR02 is added to improve the flame retardant properties of ABS materials. However, according to the UL 94 standard, the flame retardant performance of the material can only reach V2 level, which still does not meet the flame retardant performance requirements of ABS materials in the fields of electronic and electrical equipment, automobiles, aerospace and other fields.

[0003] In view of these shortcomings, the present invention innovatively synthesizes a novel flame retardant ABS composite material, which has good flame retardant properties. This ABS composite material has not been reported so far, which has very important practical significance for expanding the application field of ABS composite materials. Summary of the invention

[0004] In view of this, the present invention provides a flame retardant ABS composite material and a preparation method thereof, which has good flame retardant properties and solves the technical problem of limited flame retardant properties of ABS in the prior art.

[0005] The objective of the present invention is achieved through the following technical solutions:

[0006] A flame retardant ABS composite material and a preparation method thereof, which comprises the following components in parts by weight:

[0007] ABS 80-100 copies

[0008] Flame retardant 18-24 parts

[0009] Antioxidant 0.1-0.5 parts

[0010] The flame retardant is a Ni-MOF / MPP / praseodymium oxide composite.

[0011] The preparation method of the Ni-MOF / MPP / praseodymium oxide composite comprises the following steps:

[0012] (1) adding nickel nitrate, terephthalic acid, and N,N-dimethylformamide to a solvent aqueous solution, heating for reaction, cooling the reaction solution to room temperature, and drying to obtain Ni-MOF;

[0013] (2) Ni-MOF, melamine polyphosphate, and praseodymium oxide are added to deionized water for reaction, and the reaction solution is dried to obtain a Ni-MOF / MPP / praseodymium oxide composite.

[0014] Preferably, the mass ratio of nickel nitrate, terephthalic acid and N,N-dimethylformamide in step (1) is (28-32): (10-14); (12-16).

[0015] The heating reaction in step (1) refers to reacting at 120-140° C. for 10-16 hours;

[0016] After the reaction solution is cooled to room temperature, it is first filtered and washed, and then dried at 40-60°C for 6-8h to obtain Ni-MOF;

[0017] The solvent is anhydrous ethanol, ether or acetone.

[0018] Preferably, the mass ratio of the Ni-MOF, melamine polyphosphate (MPP), and praseodymium oxide is (30-40): (28-32): (24-28).

[0019] The reaction in step (2) is carried out at 60-80° C. for 12-16 hours;

[0020] After the reaction solution is cooled to room temperature, it is first filtered and washed, and then dried at 70-90° C. for 6-8 hours to obtain a Ni-MOF / MPP / praseodymium oxide composite.

[0021] In a further embodiment, the antioxidant is one or a mixture of tris(2,4-di-tert-butyl)phenyl phosphite (Irganox 168), 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol (Irganox 565) and N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) (Irganox 1098).

[0022] The second object of the present invention is to provide a method for preparing the flame retardant ABS composite material, which comprises the following steps:

[0023] (1) Weigh 80-100 parts of ABS, 18-24 parts of flame retardant, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture;

[0024] (2) Extruding the mixture obtained in step (1) from an extruder and granulating it to obtain an ABS composite material.

[0025] Preferably, the twin-screw extruder in step (2) comprises six temperature zones arranged in sequence, with the temperature of zone one being 200-220°C, the temperature of zone two being 240-260°C, the temperature of zone three being 240-260°C, the temperature of zone four being 240-260°C, the temperature of zone five being 240-260°C, the temperature of zone six being 240-260°C, the temperature of the die head being 240-260°C, and the screw speed being 200-280 r / min.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The flame retardant in the present application is a Ni-MOF (metal organic framework) / MPP (melamine polyphosphate) / praseodymium oxide composite flame retardant, and its flame retardant mechanism is as follows: the flame retardant is based on Ni-MOF as the framework, melamine polyphosphate (MPP) and praseodymium oxide are laid on it, praseodymium oxide reacts with polyphosphoric acid decomposed from MPP, and generates phosphates to inhibit the decomposition of polyphosphoric acid to release P 2 O 5 , improve the charring ability of the flame retardant system and form a stable expanded char layer.

[0028] Therefore, the addition of Ni-MOF / MPP / praseodymium oxide composite in this application can significantly improve the flame retardant properties of ABS composite materials, making the flame retardancy of the material reach V0 level, and can be used in the field of automotive and household appliance materials, with excellent application prospects. DETAILED DESCRIPTION

[0029] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0031] The raw materials used in the following examples are as follows:

[0032] ABS (model 750A), Daqing Petrochemical;

[0033] Deionized water, Xiamen Aoquan Environmental Protection Technology Co., Ltd.;

[0034] Nickel nitrate, Shandong Changyao New Materials Co., Ltd.;

[0035] Terephthalic acid, Shandong Poly Chemical Co., Ltd.;

[0036] N,N-dimethylformamide, Shandong Chenyu Chemical Co., Ltd.;

[0037] Anhydrous ethanol, Shanghai Fangye Chemical Co., Ltd.;

[0038] Acetone, Jinan Wenzhu Chemical Co., Ltd.;

[0039] Melamine polyphosphate (MPP), Jiangsu Xinsu New Materials Co., Ltd.;

[0040] Praseodymium oxide, Shandong Desheng New Materials Co., Ltd.;

[0041] Antioxidants (models Irganox 168, Irganox 565, Irganox 1098), BASF;

[0042] Flame retardant WR02, Suzhou Anhongtai New Materials Co., Ltd.

[0043] Preparation Example 1

[0044] (1) Add 280 g of nickel nitrate, 100 g of terephthalic acid, 500 g of anhydrous ethanol, and 120 g of N,N-dimethylformamide to 900 g of deionized water, react at 120° C. for 10 h, and cool to room temperature to obtain solution A;

[0045] (2) Solution A was filtered, washed, and dried at 40° C. for 6 h to obtain Ni-MOF.

[0046] (3) 300 g Ni-MOF, 280 g melamine polyphosphate (MPP), and 240 g praseodymium oxide were added to 700 g deionized water, reacted at 60 ° C for 12 h, and cooled to room temperature to obtain solution B;

[0047] (4) Solution B was filtered, washed, and dried at 70° C. for 6 h to obtain a Ni-MOF / MPP / praseodymium oxide composite flame retardant M1.

[0048] Example 1

[0049] (1) Weigh 80 parts of ABS, 18 parts of flame retardant M1, and 0.1 parts of Irganox 168, mix and stir evenly to obtain a mixture;

[0050] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material P1.

[0051] The twin-screw extruder comprises six temperature zones arranged in sequence, with the temperature of zone one at 200°C, the temperature of zone two at 240°C, the temperature of zone three at 240°C, the temperature of zone four at 240°C, the temperature of zone five at 240°C, the temperature of zone six at 240°C, the head temperature at 240°C, and the screw speed at 200r / min.

[0052] Preparation Example 2

[0053] (1) 320 g of nickel nitrate, 140 g of terephthalic acid, 700 g of ether, and 160 g of N,N-dimethylformamide were added to 1.1 kg of deionized water, reacted at 140° C. for 16 h, and cooled to room temperature to obtain solution A;

[0054] (2) Solution A was filtered, washed, and dried at 60° C. for 8 h to obtain Ni-MOF.

[0055] (3) 400 g Ni-MOF, 320 g melamine polyphosphate (MPP), and 280 g praseodymium oxide were added to 900 g deionized water, reacted at 80 ° C for 16 h, and cooled to room temperature to obtain solution B;

[0056] (4) Solution B was filtered, washed, and dried at 90° C. for 8 h to obtain a Ni-MOF / MPP / praseodymium oxide composite flame retardant M2.

[0057] Example 2

[0058] (1) Weigh 100 parts of ABS, 24 parts of flame retardant M2, 0.1 parts of antioxidant Irganox 1098, 0.2 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 565, mix and stir evenly to obtain a mixture;

[0059] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material P2.

[0060] The twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one at 220°C, the temperature of zone two at 260°C, the temperature of zone three at 260°C, the temperature of zone four at 260°C, the temperature of zone five at 260°C, the temperature of zone six at 260°C, the head temperature at 260°C, and the screw speed at 280r / min.

[0061] Preparation Example 3

[0062] (1) 300 g of nickel nitrate, 120 g of terephthalic acid, 600 g of acetone, and 140 g of N,N-dimethylformamide were added to 1.0 kg of deionized water, reacted at 130° C. for 13 h, and cooled to room temperature to obtain solution A;

[0063] (2) Solution A was filtered, washed, and dried at 50° C. for 7 h to obtain Ni-MOF.

[0064] (3) 350 g Ni-MOF, 300 g melamine polyphosphate (MPP), and 260 g praseodymium oxide were added to 800 g deionized water, reacted at 70 ° C for 14 h, and cooled to room temperature to obtain solution B;

[0065] (4) Solution B was filtered, washed, and dried at 80° C. for 7 h to obtain a Ni-MOF / MPP / praseodymium oxide composite flame retardant M3.

[0066] Example 3

[0067] (1) Weigh 90 parts of ABS, 21 parts of flame retardant M3, 0.1 parts of antioxidant Irganox 168, and 0.2 parts of antioxidant Irganox 1098, mix and stir evenly to obtain a mixture;

[0068] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material P3.

[0069] The twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one at 215°C, the temperature of zone two at 255°C, the temperature of zone three at 255°C, the temperature of zone four at 255°C, the temperature of zone five at 255°C, the temperature of zone six at 255°C, the head temperature at 255°C, and the screw speed at 245r / min.

[0070] Preparation Example 4

[0071] (1) 315 g of nickel nitrate, 135 g of terephthalic acid, 615 g of ether, and 155 g of N,N-dimethylformamide were added to deionized water, reacted at 135° C. for 15 h, and cooled to room temperature to obtain solution A;

[0072] (2) Filtering, washing, and drying at 58°C for 7 h to obtain Ni-MOF;

[0073] (3) 325 g Ni-MOF, 315 g melamine polyphosphate (MPP), and 275 g praseodymium oxide were added to deionized water, reacted at 77 ° C for 15 h, and cooled to room temperature to obtain solution B;

[0074] (4) Solution B was filtered, washed, and dried at 85° C. for 6 h to obtain a Ni-MOF / MPP / praseodymium oxide composite flame retardant M4.

[0075] Example 4

[0076] (1) Weigh 85 parts of ABS, 22 parts of flame retardant M4, 0.1 parts of antioxidant Irganox565, and 0.2 parts of antioxidant Irganox1098, mix and stir evenly to obtain a mixture;

[0077] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material P4.

[0078] The twin-screw extruder includes six temperature zones arranged in sequence, with zone one at 215°C, zone two at 245°C, zone three at 245°C, zone four at 245°C, zone five at 245°C, zone six at 245°C, die head temperature at 245°C, and screw speed at 245r / min.

[0079] Preparation Example 5

[0080] (1) 305 g of nickel nitrate, 135 g of terephthalic acid, 555 g of ether, and 155 g of N,N-dimethylformamide were added to 998 g of deionized water, reacted at 135° C. for 15.5 h, and cooled to room temperature to obtain solution A;

[0081] (2) Filtering, washing, and drying at 48° C. for 7.5 h to obtain Ni-MOF;

[0082] (3) 335 g Ni-MOF, 315 g melamine polyphosphate (MPP), and 275 g praseodymium oxide were added to 888 g deionized water, reacted at 75 ° C for 14.5 h, and cooled to room temperature to obtain solution B;

[0083] (4) Solution B was filtered, washed, and dried at 85° C. for 7.5 h to obtain a Ni-MOF / MPP / praseodymium oxide composite flame retardant M5.

[0084] Example 5

[0085] (1) Weigh 95 parts of ABS, 23 parts of flame retardant M5, 0.1 parts of antioxidant Irganox 1098, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0086] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material P5.

[0087] The twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one at 215°C, the temperature of zone two at 255°C, the temperature of zone three at 255°C, the temperature of zone four at 255°C, the temperature of zone five at 255°C, the temperature of zone six at 255°C, the head temperature at 255°C, and the screw speed at 255r / min.

[0088] Comparative Example 1

[0089] (1) Weigh 95 parts of ABS, 0.1 parts of antioxidant Irganox 1098, and 0.1 parts of antioxidant Irganox 168, mix and stir evenly to obtain a mixture;

[0090] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material D1.

[0091] The twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one at 215°C, the temperature of zone two at 255°C, the temperature of zone three at 255°C, the temperature of zone four at 255°C, the temperature of zone five at 255°C, the temperature of zone six at 255°C, the head temperature at 255°C, and the screw speed at 255r / min.

[0092] Comparative Example 2

[0093] (1) Weigh 95 parts of ABS, 23 parts of flame retardant WR02, 0.1 parts of antioxidant Irganox1098, and 0.1 parts of antioxidant Irganox168, mix and stir evenly to obtain a mixture;

[0094] (2) The mixed material obtained in step (1) is extruded from an extruder and granulated to obtain an ABS composite material D2.

[0095] The twin-screw extruder includes six temperature zones arranged in sequence, with the temperature of zone one at 215°C, the temperature of zone two at 255°C, the temperature of zone three at 255°C, the temperature of zone four at 255°C, the temperature of zone five at 255°C, the temperature of zone six at 255°C, the head temperature at 255°C, and the screw speed at 255r / min.

[0096] The ABS composite materials prepared in the above Examples 1-5 and Comparative Examples 1-2 were made into test strips using an injection molding machine. The test data are shown in the following table:

[0097]

[0098] It can be seen from the above table that the flame retardant properties of the composite materials prepared in Examples 1 to 5 are better than those of Comparative Examples 1 to 2. This indicates that the ABS composite materials prepared by the method provided by the present invention have excellent flame retardant properties and can expand the application fields of the ABS composite materials.

[0099] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0100] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A flame retardant ABS composite material, characterized in that: It is composed of the following components by weight: ABS 80-100 copies Flame retardant 18-24 parts Antioxidant 0.1-0.5 parts The flame retardant is a Ni-MOF / MPP / praseodymium oxide composite.

2. The flame retardant ABS composite material according to claim 1, characterized in that: The preparation method of the Ni-MOF / MPP / praseodymium oxide composite comprises the following steps: (1) adding nickel nitrate, terephthalic acid, and N,N-dimethylformamide to a solvent aqueous solution, heating for reaction, cooling the reaction solution to room temperature, and drying to obtain Ni-MOF; (2) Ni-MOF, melamine polyphosphate, and praseodymium oxide are added to deionized water for reaction, and the reaction solution is dried to obtain a Ni-MOF / MPP / praseodymium oxide composite.

3. The flame retardant ABS composite material according to claim 2, characterized in that: The mass ratio of the nickel nitrate, terephthalic acid and N,N-dimethylformamide is (28-32): (10-14); (12-16).

4. The flame retardant ABS composite material according to claim 2, characterized in that: The heating reaction in step (1) refers to reacting at 120-140° C. for 10-16 hours; After the reaction solution is cooled to room temperature, it is first filtered and washed, and then dried at 40-60° C. for 6-8 hours to obtain Ni-MOF.

5. The flame retardant ABS composite material according to claim 2, characterized in that: The solvent is anhydrous ethanol, ether or acetone.

6. The flame retardant ABS composite material according to claim 2, characterized in that: The mass ratio of the Ni-MOF, melamine polyphosphate (MPP) and praseodymium oxide is (30-40):(28-32):(24-28).

7. The flame retardant ABS composite material according to claim 2, characterized in that: The reaction in step (2) is carried out at 60-80° C. for 12-16 hours; After the reaction solution is cooled to room temperature, it is first filtered and washed, and then dried at 70-90° C. for 6-8 hours to obtain a Ni-MOF / MPP / praseodymium oxide composite.

8. The flame retardant ABS composite material according to claim 1, characterized in that: The antioxidant is one or a mixture of tris(2,4-di-tert-butyl)phenyl phosphite, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol and N,N'-hexane-1,6-diylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)).

9. A method for preparing a flame retardant ABS composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Weigh 80-100 parts of ABS, 18-24 parts of flame retardant, and 0.1-0.5 parts of antioxidant, mix and stir evenly to obtain a mixture; (2) Extruding the mixture obtained in step (1) through a twin-screw extruder to form granules, thereby obtaining an ABS composite material.

10. The preparation method according to claim 9, characterized in that: In step (2), the twin-screw extruder includes six temperature zones arranged in sequence, wherein the temperature of zone one is 200-220°C, the temperature of zone two is 240-260°C, the temperature of zone three is 240-260°C, the temperature of zone four is 240-260°C, the temperature of zone five is 240-260°C, the temperature of zone six is ​​240-260°C, the head temperature is 240-260°C, and the screw speed is 200-280r / min.

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