A flame retardant ABS material and its preparation method and application

Abstract

The present invention discloses a flame retardant ABS material and a preparation method and application thereof, and relates to the technical field of polymer materials. The flame retardant ABS material of the present invention comprises the following components in parts by weight: 30 to 60 parts of ABS resin, 20 to 50 parts of chlorinated polymer, 2 to 10 parts of phosphorus nitrogen flame retardant, 2 to 10 parts of chlorinated polyethylene, 1 to 5 parts of antimony white, 1 to 6 parts of compatibilizer, 1 to 3 parts of lubricant and 0.05 to 1 part of antioxidant; the chlorine content of the chlorinated polymer is 45 to 55wt.%, the chlorine content of the chlorinated polyethylene is 30 to 35wt.%, the compatibilizer comprises PP-g-MAH and POE-g-MAH, and the lubricant comprises calcium stearate, PE wax and polyol ester. The present invention selects the amount of flame retardant and each component, and prepares an ABS material with good mechanical properties and flame retardancy without using a bromine flame retardant.

Description

Technical Field

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

[0002] Acrylonitrile-butadiene-styrene (ABS) resin has good mechanical properties and processing properties, and is widely used in the fields of automobiles, electronic appliances, etc., but the flame retardancy of ABS resin is poor, which limits its application in high-end equipment. At present, the most commonly used flame retardant modifier is bromine flame retardant, but the cost of bromine flame retardant is relatively high and it will affect the mechanical properties of ABS materials. It is necessary to provide a new flame retardant modification scheme to reduce the production cost of ABS materials while ensuring that ABS materials have good mechanical properties. Summary of the invention

[0003] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a flame-retardant ABS material and a preparation method and application thereof, wherein the ABS material has good flame retardancy and mechanical properties without adding brominated flame retardants.

[0004] To achieve the above object, the technical solution adopted by the present invention is:

[0005] A flame-retardant ABS material comprises the following components in parts by weight: 30-60 parts of ABS resin, 20-50 parts of chlorinated polymer, 2-10 parts of phosphorus-nitrogen flame retardant, 2-10 parts of chlorinated polyethylene, 1-5 parts of antimony white, 1-6 parts of compatibilizer, 1-3 parts of lubricant and 0.05-1 part of antioxidant; the chlorine content of the chlorinated polymer is 45-55wt.%, the chlorine content of the chlorinated polyethylene is 30-35wt.%, the compatibilizer comprises PP-g-MAH and POE-g-MAH, and the lubricant comprises calcium stearate, PE wax and polyol ester.

[0006] Chlorinated polymers with high chlorine content have good flame retardant properties, but compared with brominated flame retardants, more chlorinated polymers need to be added to achieve the same flame retardant properties. However, as the amount of chlorinated polymer increases, the impact resistance of ABS materials will decrease. Chlorinated polyethylene with a chlorine content of 30-35wt.% is often used as an elastomeric polymer as an impact modifier. At the same time, since chlorinated polymers contain halogen elements, they have certain flame retardancy and can be used as synergistic flame retardants. Phosphorus-nitrogen flame retardants have good flame retardancy and plasticizing effects, which can improve the processing properties of ABS materials, but their heat resistance is poor. Antimony white has certain flame retardancy and is often used as a flame retardant synergist, but the crude antimony white product generally contains other heavy metals, which is not environmentally friendly, and its dosage needs to be minimized. The use of PP-g-MAH and POE-g-MAH as compatibilizers can improve the dispersibility of flame retardants in the system and improve the interface strength, thereby significantly improving the flame retardancy and mechanical properties of ABS materials. Calcium stearate has a good lubricating effect and can reduce the friction between the material and the barrel during the preparation of ABS materials. The chemical properties of PE wax are stable, which can improve the fluidity of ABS and has a good internal lubrication effect. Polyol esters are a type of excellent internal lubricant and also have a certain antistatic effect, which is suitable for preparing plastics used in the fields of electronics and electrical appliances. The applicant of the present invention selects the ingredients of the lubricant to increase the flame retardancy and thermal stability of the ABS material while improving the processing performance, and further improves the mechanical properties of the ABS material. The present invention selects the content of the above-mentioned components so that the prepared ABS material has good flame retardancy and mechanical properties without using brominated flame retardants, providing a new solution for the preparation of flame-retardant ABS materials.

[0007] Preferably, the flame retardant ABS material comprises the following components in parts by weight: 35-50 parts of ABS resin, 30-45 parts of chlorinated polymer, 3-8 parts of phosphorus-nitrogen flame retardant, 5-8 parts of chlorinated polyethylene, 2-4 parts of antimony white, 2-5 parts of compatibilizer, 1.5-2.6 parts of lubricant and 0.05-1 part of antioxidant. When the components meet the above ratio, the flame retardancy and mechanical properties of the prepared ABS material can be further improved.

[0008] Preferably, the melt flow rate of the ABS resin at 220°C and 10kg load is 10-14g / 10min. When the melt index of the ABS resin meets the above definition, the content of butadiene is relatively high, and the ABS resin has better toughness. In addition, a large number of experiments have confirmed that the ABS resin can improve the stability of chlorinated polymers and enhance the comprehensive performance of flame-retardant ABS materials.

[0009] Preferably, in the compatibilizer, the mass ratio of PP-g-MAH to POE-g-MAH is 1 to 3:1. The addition of PP-g-MAH and POE-g-MAH can promote the compatibility between chlorinated polymers and chlorinated polyethylene and phosphorus-nitrogen flame retardants, promote the uniform dispersion of phosphorus-nitrogen flame retardants in the system, and form flame retardant synergistic sites together with chlorinated polymers and chlorinated polyethylene, so as to better play a flame retardant synergistic role; adding PP-g-MAH and POE-g-MAH at the same time according to the above ratio can improve the interface strength of the system and improve its flame retardant performance; in addition, POE-g-MAH can improve the impact resistance of the system while improving compatibility.

[0010] Preferably, the phosphorus-nitrogen flame retardant is at least one of melamine cyanurate, ammonium polyphosphate, hypophosphite, and hexaphenoxy cyclotriphosphazene. Further preferably, the phosphorus-nitrogen flame retardant is melamine cyanurate. Melamine cyanurate has good thermal stability and mechanical properties, and is suitable for preparing flame-retardant ABS materials with certain requirements for mechanical properties.

[0011] Preferably, in the lubricant, the mass ratio of calcium stearate, PE wax and polyol ester is calcium stearate: PE wax: polyol ester = 0.3-1: 0.3-0.8: 0.4-1.2. When the ratio of the three meets the above definition, the flame retardant ABS material has the best comprehensive performance.

[0012] Preferably, the antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant.

[0013] In addition, the present invention also discloses a method for preparing the flame-retardant ABS material, which comprises: uniformly mixing the components according to a proportion, adding the components into a twin-screw extruder, and melt-extruding and granulating the components at 60 to 180° C. to obtain the flame-retardant ABS material.

[0014] At the same time, the invention also discloses the application of the flame retardant ABS material in the field of household appliances.

[0015] Compared with the prior art, the present invention has the following beneficial effects: the present invention uses chlorinated polymers, phosphorus-nitrogen flame retardants and antimony white as flame retardants, and increases the dispersibility of each component in the system by adding compatibilizers POE-g-MAH, PP-g-MAH and lubricants PE wax, polyol esters and calcium stearate, thereby improving the mechanical properties of ABS materials while ensuring their flame retardancy. DETAILED DESCRIPTION

[0016] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0017] The materials used in the embodiments and comparative examples are as follows:

[0018] ABS resin 1: ABS 745N, KUMHO PETROCHEMICAL, melt flow rate measured at 220°C and 10 kg load is 10.2 g / 10 min;

[0019] ABS resin 2: ABS D-120A, Guoqiao Petrochemical Co., Ltd., melt flow rate measured at 220°C and 10kg load is 12.2g / 10min;

[0020] ABS resin 3: ABS AG10NP-AK, Taiwan Chemical Fiber Co., Ltd.; the melt flow rate measured at 220°C and 10kg load is 13.1g / 10min;

[0021] ABS resin 4: ABS DG-MG29, Tianjin Dagu Chemical Co., Ltd., melt flow rate measured at 220°C and 10kg load is 8.3g / 10min;

[0022] ABS resin 5: ABS DG-MG94, Tianjin Dagu Chemical Co., Ltd., melt flow rate measured at 220°C and 10kg load is 35g / 10min;

[0023] Compatibilizer 1: PP-g-MAH, KT-1, Shenyang Ketong Plastic Co., Ltd.;

[0024] Compatibilizer 2: POE-g-MAH, XB-1008, Guangzhou Xinbang Polymer Materials Co., Ltd.;

[0025] Compatibilizer 3: PS-g-MAH, SMA 700, Shanghai Huawen Electronic New Materials Co., Ltd.;

[0026] Chlorinated polymer 1: chlorinated polyethylene, chlorine content 45wt.%, Weifang Yaxing Chemical Co., Ltd.

[0027] Chlorinated polymer 2: chlorinated polyethylene, chlorine content 50wt.%, Weifang Yaxing Chemical Co., Ltd.

[0028] Chlorinated polymer 3: chlorinated polyethylene, chlorine content 55wt.%, Weifang Yaxing Chemical Co., Ltd.

[0029] Chlorinated polymer 4: PVC DG-700, chlorine content 56.8wt.%, Tianjin Dagu Chemical Co., Ltd.;

[0030] Phosphorus-nitrogen flame retardant 1: melamine cyanurate, commercially available;

[0031] Phosphorus-nitrogen flame retardant 2: hexaphenoxy cyclotriphosphazene, commercially available;

[0032] Phosphorus-nitrogen flame retardant 3: melamine phosphate, commercially available;

[0033] Chlorinated polyethylene 1: CPE135A, chlorine content 35wt.%, Guangdong Weilinna New Materials Technology Co., Ltd.;

[0034] Chlorinated polyethylene 2: CPE3211, chlorine content 32wt.%, Weihai Jinhong Polymer Co., Ltd.;

[0035] Chlorinated polyethylene 3: CPE130C, chlorine content 30wt.%, Weifang Yaxing Chemical Co., Ltd.

[0036] Chlorinated polyethylene 4: CPE120C, chlorine content 20wt.%, Weifang Yaxing Chemical Co., Ltd.

[0037] Antimony white: commercially available;

[0038] Lubricant 1: calcium stearate, commercially available;

[0039] Lubricant 2: PE wax, commercially available;

[0040] Lubricant 3: pentaerythritol stearate, commercially available;

[0041] Lubricant 4: ethylene bis stearic acid amide, commercially available;

[0042] Antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1, commercially available;

[0043] The phosphorus-nitrogen flame retardants 1 to 3, antimony white, lubricants 1 to 4 and antioxidants used in the examples and comparative examples are all of the same substance.

[0044] Examples 1 to 7

[0045] The embodiments of the flame-retardant ABS material of the present invention, the formulas of embodiments 1 to 7 are shown in Table 1, and the preparation method is: the components are uniformly mixed according to the ratio, and then added into a twin-screw extruder, the temperature from the feed port to the die head is 60°C, 120°C, 170°C, 170°C, 170°C, 170°C, 180°C in sequence, melt blending, extrusion granulation, to obtain the flame-retardant ABS material.

[0046] Embodiments 8 to 9

[0047] The embodiments of the flame-retardant ABS material of the present invention, embodiments 8 to 9 are different from embodiment 2 only in that the types of ABS resin are different. The ABS resins selected in embodiments 8 to 9 are ABS resin 2 and ABS resin 3, respectively.

[0048] Embodiments 10 to 11

[0049] The embodiments of the flame-retardant ABS material of the present invention, embodiments 10 to 11 are different from embodiment 2 only in that the types of phosphorus-nitrogen flame retardants are different. The phosphorus-nitrogen flame retardants selected in embodiments 10 to 11 are phosphorus-nitrogen flame retardant 2 and phosphorus-nitrogen flame retardant 3, respectively.

[0050] Embodiments 12 to 13

[0051] The embodiments of the flame-retardant ABS material of the present invention, embodiments 12 to 13 are different from embodiment 2 only in that the types of chlorinated polymers are different. The chlorinated polymers selected in embodiments 12 to 13 are chlorinated polymer 2 and chlorinated polymer 3, respectively.

[0052] Embodiments 14 to 15

[0053] The embodiments of the flame-retardant ABS material of the present invention, embodiments 14 to 15 are different from embodiment 2 only in that the types of chlorinated polyethylene are different, and the chlorinated polyethylene selected in embodiments 14 to 15 are chlorinated polyethylene 2 and chlorinated polyethylene 3, respectively.

[0054] Example 16

[0055] The embodiment of the flame-retardant ABS material of the present invention is different from the embodiment 2 only in that the amounts of PP-g-MAH and POE-g-MAH are different. In the embodiment, the weight parts of PP-g-MAH are 1 part and the weight parts of POE-g-MAH are 3 parts.

[0056] Embodiments 17-18

[0057] Embodiments 17 to 18 are flame-retardant ABS materials. The flame-retardant ABS materials are different from those of Embodiment 2 only in that different types of ABS resins are selected, namely, ABS resin 4 and ABS resin 5.

[0058] Comparative Examples 1 to 10

[0059] Comparative Examples 1-10 are flame retardant ABS materials, the formulations of which are shown in Table 1, and the preparation methods are the same as those of Examples 1-7.

[0060] Comparative Example 11

[0061] A flame retardant ABS material, wherein the flame retardant ABS material is different from that of Example 2 only in that the selected chlorinated polymer is chlorinated polymer 4.

[0062] Comparative Example 12

[0063] A flame retardant ABS material, wherein the flame retardant ABS material is different from that of Example 2 only in that the chlorinated polyethylene selected is chlorinated polyethylene 4.

[0064] Table 1 (parts by weight)

[0065]

[0066]

[0067] The properties of the flame retardant ABS materials prepared in the examples and comparative examples were tested with reference to the following standards, and the results are recorded in Table 2:

[0068] Izod notched impact strength: tested according to GB / T 1843-2008, A-type notch, 23°C, 50% humidity;

[0069] Tensile strength: tested according to GB / T 1040-2006, tensile rate 50mm / min;

[0070] 5V level and vertical burning (UL94): The samples were injection molded into 125±5mm×13.0±0.5mm×2.0±0.15mm standard burning specimens and 150±5mm×150±5mm×2.0±0.15mm standard burning square plates, and tested in a burning tester.

[0071] Table 2

[0072]

[0073]

[0074] As can be seen from Table 2, the compatibilizer used in the flame-retardant ABS material described in Comparative Examples 1 to 2 is not the PP-g-MAH and POE-g-MAH described in the present invention, and the ability to improve the interface strength is poor, and the impact resistance of the prepared flame-retardant ABS material cannot meet the standard. The lubricant used in the flame-retardant ABS material described in Comparative Examples 3 to 6 is not a compound of PE wax, polyol ester and calcium stearate, and the improvement of the dispersibility of the system is limited, so the toughness of the final product is poor. The amount of ABS resin in Comparative Example 7 exceeds the standard, and the amount of CPE in Comparative Example 8 exceeds the standard, resulting in a decrease in tensile strength. The amount of lubricant in Comparative Example 9 is too high, which will lead to poor plasticization, brittle flame-retardant ABS material, and poor toughness. In Comparative Example 10, due to the lack of a compatibilizer, the flame retardancy is insufficient. The chlorine content in the chlorinated polymer used in Comparative Example 11 is too high, the flame retardancy of the system is better, but the thermal stability is poor, resulting in a significant reduction in the toughness of the flame-retardant ABS material. The chlorine content in the chlorinated polyethylene selected in Comparative Example 12 is too low, and its compatibility with the system deteriorates, resulting in a decrease in the overall performance of the flame-retardant ABS material.

[0075] Comparing the test results of Examples 1 to 5 and Example 7, it can be seen that the components and their amounts in Examples 2 to 4 are within the preferred range, and the Izod notched impact strength of the flame retardant ABS material can reach 20 kJ / m 2Above, the tensile strength can reach more than 40MPa, and the flame retardancy can reach more than 5VA, with good mechanical properties and flame retardancy. Comparing the test results of Examples 2 to 4 and Example 6, it can be seen that when the mass ratio of calcium stearate: PE wax: polyol ester in the lubricant is not 0.3 to 1: 0.3 to 0.8: 0.4 to 1.2, the toughness of the flame retardant ABS material will be reduced. Comparing the test results of Examples 2 and 10 to 11, it can be seen that in the system described in the present invention, when the phosphorus nitrogen flame retardant is melamine cyanurate, the comprehensive performance is better. Comparing the test results of Examples 2 to 4 and Example 16, it can be seen that the ratio of PP-g-MAH and POE-g-MAH will also have a greater impact on the mechanical properties of the flame retardant ABS material. Only when the mass ratio of PP-g-MAH and POE-g-MAH meets 1 to 3: 1, can the flame retardant ABS material have good toughness and tensile strength. The melt flow rates of the ABS resin used in Examples 17 to 18 are lower and higher than 10 to 14 g / 10 min, respectively. The melt flow rate of the ABS resin is small, the rubber content is high, the processing fluidity is poor, and the dispersibility of the system deteriorates, resulting in reduced toughness and tensile strength of the flame-retardant ABS material. If the melt flow rate of the ABS resin is too high, the tensile strength of the flame-retardant ABS material will be reduced.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A flame retardant ABS material, characterized in that: The invention comprises the following ingredients in parts by weight: 30-60 parts of ABS resin, 20-50 parts of chlorinated polymer, 2-10 parts of phosphorus-nitrogen flame retardant, 2-10 parts of chlorinated polyethylene, 1-5 parts of antimony white, 1-6 parts of compatibilizer, 1-3 parts of lubricant and 0.05-1 part of antioxidant; the chlorine content of the chlorinated polymer is 45-55wt.%, the chlorine content of the chlorinated polyethylene is 30-35wt.%, the compatibilizer comprises PP-g-MAH and POE-g-MAH; the lubricant is a mixture of calcium stearate, PE wax and polyol ester.

2. The flame retardant ABS material according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 35-50 parts of ABS resin, 30-45 parts of chlorinated polymer, 3-8 parts of phosphorus-nitrogen flame retardant, 5-8 parts of chlorinated polyethylene, 2-4 parts of antimony white, 2-5 parts of compatibilizer, 1.5-2.6 parts of lubricant and 0.05-1 part of antioxidant.

3. The flame retardant ABS material according to claim 1, characterized in that: The melt flow rate of the ABS resin measured at 220° C. and 10 kg load is 10 to 14 g / 10 min.

4. The flame retardant ABS material according to claim 1, characterized in that: In the compatibilizer, the mass ratio of PP-g-MAH to POE-g-MAH is 1 to 3:

1.

5. The flame retardant ABS material according to claim 1, characterized in that: The phosphorus-nitrogen flame retardant is melamine cyanurate.

6. The flame retardant ABS material according to claim 1, characterized in that: In the lubricant, the mass ratio of calcium stearate, PE wax and polyol ester is calcium stearate:PE wax:polyol ester=0.3-1:0.3-0.8:0.4-1.

2.

7. The flame retardant ABS material according to claim 1, characterized in that: The antioxidant is at least one of a hindered phenol antioxidant and a phosphite antioxidant.

8. A method for preparing a flame retardant ABS material according to any one of claims 1 to 7, characterized in that: The method comprises: uniformly mixing the components according to a proportion, and then adding the components into a twin-screw extruder for melt extrusion and granulation to obtain the flame-retardant ABS material.

9. Use of the flame retardant ABS material according to any one of claims 1 to 7 in the field of household appliances.

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