A high-toughness halogen-free flame-retardant ABS composition and its preparation method

Abstract

The present invention belongs to the technical field of polymer materials, and discloses a high-toughness halogen-free flame-retardant ABS composition, which is made of the following raw materials in parts by weight: ABS resin: 60-80 parts; toughening agent: 5-15 parts; hyperbranched polyol: 0.1-0.5 part; flame retardant: 5-15 parts; at least part of the flame retardant is a phosphorus-containing flame retardant. It realizes that excellent heat-resistant flame-retardant performance meets the standard and does not significantly deteriorate the mechanical properties of the material, significantly improves the commercial value of the ABS modified material and expands its scope of use. The second object of the present invention is to provide a preparation method of the above-mentioned high-toughness halogen-free flame-retardant ABS composition.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a high-toughness halogen-free flame-retardant ABS composition and a preparation method thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene copolymer is a terpolymer composed of acrylonitrile, butadiene and styrene, abbreviated as ABS. It has excellent impact resistance, heat resistance, low-temperature resistance, chemical resistance and electrical properties, and also has the characteristics of easy processing, stable product size, good surface gloss, etc. It is easy to paint and color, and can also be subjected to secondary processing such as surface metal spraying, electroplating, welding, hot pressing and bonding. It is widely used in industrial fields such as machinery, automobiles, electronic appliances, instruments, textiles and construction, and is a thermoplastic engineering plastic with extremely wide uses. However, the oxygen index of ABS resin is only 18%, which belongs to flammable products. When used in fields such as electronic appliances, it needs to be flame-retardant modified to meet the requirements of the safety flame-retardant performance level.

[0003] At present, the flame-retardant modification of ABS on the market mainly includes tetrabromobisphenol A, decabromodiphenylethane, decabromodiphenyl ether, brominated epoxy resin, etc. These generally easily affect the processing fluidity, affect the strength, and cause pollution. Usually, halogen-containing flame-retardant ABS products will produce a large amount of thick black smoke and a large amount of toxic and harmful gases when burning. Therefore, the halogen-freeization of materials will become the mainstream direction in the future market.

[0004] However, it is very difficult for the currently commonly used phosphorus-based flame retardants, nitrogen-based flame retardants or inorganic flame retardants to achieve UL94 V0 level. Because a relatively large amount of flame retardant is required to reach the V0 level, which seriously deteriorates the mechanical properties of the materials. ABS materials cannot be coordinated among flame-retardant modification, heat-resistant modification and strength modification, which severely restricts the use range of ABS modified materials.

[0005] For ABS flame-retardant plates, the mechanical strength of ABS can be improved by a toughening agent. The following comparative documents can be seen:

[0006] D1: CN114479400A discloses a PC / ABS alloy material, including PC resin, ABS resin, an interfacial compatibilizer, a composite flame retardant and modified aluminum nitride, etc. The composite flame retardant includes a phosphate ester flame retardant, graphene and polytetrafluoroethylene. This high-efficiency composite flame retardant not only has excellent flame-retardant performance, but also the simultaneous introduction of graphene and modified aluminum nitride can form a high-thermal-conductivity network structure, improving the heat dissipation performance;

[0007] The specification describes: A PC / ABS alloy material, including PC resin, ABS resin, an interfacial compatibilizer, a composite flame retardant, and modified aluminum nitride, wherein the composite flame retardant includes the following components by weight: 5-12 parts of a phosphate ester flame retardant; 0.1-6 parts of graphene; 0.05-2 parts of polytetrafluoroethylene; and / or the modified aluminum nitride is modified aluminum nitride coupled with a silane coupling agent, and / or the particle size of the modified aluminum nitride is 0.5-30 μm.

[0008] The molar ratio of acrylonitrile, butadiene, and styrene in the ABS resin is (15-25):(5-50):(35-65), and / or the melt flow rate (220 °C, 10 kg) of the ABS resin is 5-50 g / 10 min.

[0009] The interfacial compatibilizer is selected from at least one of styrene-maleic anhydride polymer, styrene-acrylonitrile-maleic anhydride polymer, ethylene-methyl acrylate-maleic anhydride copolymer, ethylene-butyl acrylate-maleic anhydride copolymer, ethylene-stearyl acrylate-maleic anhydride copolymer, ethylene-glycidyl acrylate-maleic anhydride copolymer, and maleic anhydride graft-modified polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-vinyl acetate copolymer, and ABS.

[0010] D2: CN114806068A provides a high-strength and high-rigidity environmentally friendly weather-resistant ABS resin, which is prepared from raw materials comprising the following weight percentages: ABS resin: 70-87%, weather-resistant enhancer: 8-20%, toughening agent: 3-12%, lubricant: 0.5-2.0%, antioxidant: 0.3-0.5%, heat stabilizer: 0.5-1.0%. The weather-resistant enhancer is a nano-cellulose aerogel weather-resistant enhancer encapsulated by AS resin grafted PBL latex particles, which greatly improves the interfacial compatibility with the ABS resin during melt blending, promotes the good dispersion and stress transfer of the weather-resistant enhancer in the ABS resin, realizes the strengthening effect of the ABS resin, and the nano-cellulose aerogel is green and environmentally friendly. Using its ultraviolet shielding effect, it delays the aging process of the ABS material, improves its weather resistance in outdoor products, and solves the problem of difficult to balance the weather resistance and mechanical properties of the material, effectively optimizing the comprehensive performance of the material.

[0011] It can be seen that in the prior art, for the improvement of the mechanical properties of ABS, the combination of ABS and a toughening agent is a common technique.

[0012] In the improvement of the flame retardant performance of ABS resin, most environmentally friendly flame retardant materials use halogen-free flame retardant materials.

[0013] However, the halogen-free flame retardant materials mainly based on phosphorus-based materials have poor distribution performance in ABS resin, resulting in the deterioration of the mechanical properties of ABS.

[0014] In the prior art, optional ways to enhance dispersion include: core-shell structures such as microcapsule-coated red phosphorus, and using silicone as a dispersant.

[0015] In "Research on the Synthesis of Hyperbranched Polymers with Succinic Anhydride and Diethanolamine", Journal of Fushun Petroleum Institute, No. 6, 2003, written by Zhao Chongfeng et al.; it is recorded in this literature that hyperbranched polymers have not been taken seriously because they lack excellent mechanical properties and cannot be used as conventional structural materials. The truly groundbreaking work was completed by scholars such as Kim and Frechet around 1990; these polymers have good solubility, which has finally made the condensation reaction between AB monomers, which has been neglected for decades, become one of the research hotspots in polymer chemistry in the past decade.

[0016] In the prior art, the research on hyperbranched in flame retardant materials has just started;

[0017] Based on this, the technical problem to be solved in this case is: how to improve the strength and flame retardant performance of ABS materials. Summary of the Invention

[0018] Aiming at the deficiencies of the prior art, the first object of the present invention is to provide a halogen-free flame retardant ABS composition that fully balances flame retardancy, heat resistance and strength. The present invention provides a high-toughness halogen-free flame retardant ABS composition, which achieves excellent heat-resistant flame retardant performance and does not significantly deteriorate the mechanical properties of the material, significantly improves the commercial value of the ABS modified material and expands its scope of use.

[0019] The second object of the present invention is to provide a preparation method of the above-mentioned high-toughness halogen-free flame retardant ABS composition.

[0020] To achieve the first object of the invention, the present invention adopts the following technical scheme: a high-toughness halogen-free flame retardant ABS composition is made from the following raw materials in parts by weight:

[0021] ABS resin: 60 - 80 parts;

[0022] Toughening agent: 5 - 15 parts;

[0023] Hyperbranched polyol: 0.1 - 0.5 part;

[0024] Flame retardant: 5 - 15 parts;

[0025] At least part of the flame retardant is a phosphorus-containing flame retardant.

[0026] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the phosphorus-containing flame retardant is one or more of black phosphorus, microencapsulated red phosphorus, hypophosphite, phosphinate, ammonium polyphosphate, ammonium dihydrogen phosphate, melamine polyphosphate, triphenyl phosphate, triethyl phosphate, triisopropylphenyl phosphate, trioctyl phosphate, tolyldiphenyl phosphate, and melamine phosphate.

[0027] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the flame retardant further includes one or more of melamine, melamine cyanurate, dicyandiamide, zinc borate, magnesium hydroxide, and aluminum hydroxide.

[0028] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the flame retardant consists of a phosphorus-containing flame retardant and melamine cyanurate; the ratio of the phosphorus-containing flame retardant to melamine cyanurate is 4 - 12:2.

[0029] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the flame retardant consists of a phosphorus-containing flame retardant, melamine cyanurate, and zinc borate; the ratio of the phosphorus-containing flame retardant, melamine cyanurate, and zinc borate is 4 - 12:2:2 - 5.

[0030] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the ABS resin is an acrylonitrile-butadiene-styrene graft maleic anhydride copolymer.

[0031] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the toughening agent is one or more of ABS high rubber powder, POE elastomer, EMA elastomer, thermoplastic polyurethane elastomer, and ethylene-vinyl acetate copolymer.

[0032] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, the hyperbranched polyol is a hyperbranched polyol prepared from succinic anhydride and diethanolamine as polymerization units; the molar ratio of succinic anhydride to diethanolamine in the hyperbranched polyol is 1:1 - 1.2.

[0033] In the above-mentioned high-toughness halogen-free flame-retardant ABS composition, it further includes an antioxidant and a processing aid. The antioxidant consists of a hindered phenol main antioxidant 2,6-di-tert-butyl-4-methylphenol and a phosphite auxiliary antioxidant poly(dipropylene glycol) phenyl phosphite, and the processing aid is a mixture of one or more of ethylene bisstearamide, polyester wax, magnesium stearate, calcium stearate, silicone oil, and white oil.

[0034] Meanwhile, the present invention also discloses a preparation method of a high-toughness halogen-free flame-retardant ABS composition as described above, including the following operating steps:

[0035] S1. Weigh each component;

[0036] S2. After the components are fully physically mixed, they are extruded and granulated using a twin-screw extruder;

[0037] S3. Compression molding the pellets.

[0038] The physical mixing is carried out at a high-speed mixer speed of 900 to 1200 r / min for 6 to 10 minutes; the screw diameter of the twin-screw extruder is 24 to 36 mm, and the temperature of each extrusion section is controlled by a ten-stage temperature control method, and the temperature of each section is 195 to 200°C, 200 to 205°C, 210 to 220°C, 210 to 215°C, 220 to 230°C, 220 to 225°C, 210 to 220°C, 200 to 205°C, 190 to 200°C and 200 to 210°C.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] 1. The present invention adopts a combination of hyperbranched polyol and flame retardant, so that the flame retardant can show excellent dispersion performance, achieving a dual guarantee of board strength and flame retardant performance;

[0041] Based on its principle, the present invention adopts phosphorus-containing flame retardant; the flame retardant performance of phosphorus-containing flame retardant is better than other inorganic flame retardants such as zinc borate and nano aluminum hydroxide, but the dispersion performance is poor. By combining with hyperbranched polyols, the dispersion performance of phosphorus-containing flame retardant in resin can be improved;

[0042] At the same time, the hyperbranched polyol can evenly disperse the flame retardant and provide water vapor to build a flame retardant environment when the flame retardant is carbonized by heat. At the same time, it can accelerate carbonization to form a carbonized layer to prevent further combustion.

[0043] 2. The present invention adopts a compound of hyperbranched polyol, phosphorus-containing flame retardant and melamine cyanurate, which can further improve the flame retardant performance and further reduce the influence of the phosphorus-containing flame retardant on the strength of the board;

[0044] Melamine cyanurate has a rich hydrogen bond network structure and good heat resistance. During the carbonization process, it can form a honeycomb carbonization layer to prevent further combustion.

[0045] Melamine cyanurate and hyperbranched polyol have excellent compatibility, which can minimize the influence of phosphorus flame retardant and melamine cyanurate compounded flame retardant on the mechanical properties of the board and maintain good flame retardant properties.

[0046] 3. The present invention uses a combination of hyperbranched polyol, phosphorus-containing flame retardant, melamine cyanurate, and zinc borate. The dispersion performance of zinc borate itself is much better than that of the phosphorus-containing flame retardant. At the same time, the flame retardant mechanism of zinc borate lies in its ability to promote carbon formation and form a glass layer. Therefore, when a small amount of zinc borate is added, the flame retardant performance of the board is significantly improved; moreover, zinc borate can cooperate well with hyperbranched polyol, and while maintaining good dispersion performance, it can promote the hyperbranched polyol attached near the flame retardant to accelerate carbon formation and form an isolation layer.

[0047] 5. The halogen-free flame-retardant ABS composition provided by the present invention adopts a combination of ABS and toughening agent to improve the mechanical properties of the board. At the same time, the addition of hyperbranched polyol can reduce the influence of the flame retardant on the mechanical properties of the board; the reason is that hyperbranched polyol has good compatibility with ABS and has good dispersion for the phosphorus-containing flame retardant, zinc borate, and melamine cyanurate, which can greatly reduce the influence of the flame retardant on the mechanical properties of the board; further preferably, when the ABS used is ABS-g-MAH, the anhydride will carry out a chain extension reaction with hyperbranched polyol.

[0048] 6. The components of the flame retardant used in the present invention produce a synergistic effect and fit well with the graft-modified ABS resin and other components used in the present invention, enabling good coordination among the flame retardant modification, heat resistance modification, and strength modification of the ABS material, which will significantly improve the commercial value of the ABS modified material and expand its scope of use. Specific Embodiments

[0049] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0050] For those not specifying specific experimental steps or conditions in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments not specifying the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase. In the experiments, various properties of the materials are measured according to GB (national standard). Unless otherwise specified, the parts of the components are all in parts by weight.

[0051] Preparation Example 1 of Hyperbranched Polyol

[0052] It is prepared by referring to the preparation method of hyperbranched polyol recorded in "Research on the Synthesis of Hyperbranched Polymers with Succinic Anhydride and Diethanolamine";

[0053] The polymer used in this example is not the esterification product in "Research on the Synthesis of Hyperbranched Polymers with Succinic Anhydride and Diethanolamine", but a polyol intermediate product;

[0054] The preparation steps are as follows:

[0055] Weigh 4 g of diolamine, and weigh a certain amount of succinic anhydride according to a molar ratio of 1 and place it in a three-necked flask. Then dissolve it with 30 mL of DMAc, and react with magnetic stirring at room temperature for 1 h. Add a small amount of catalyst p-toluenesulfonic acid and an appropriate amount (about 50 mL) of azeotropic water-carrying agent to the reaction system, stir and start to slowly heat the reaction until reflux occurs, continue to stir the reaction, and separate the water generated by the reaction by condensing and refluxing through a water separator. When no water droplets are generated, this step of the reaction ends, and hyperbranched polyol 1 is obtained.

[0056] Before adding it to the subsequent examples, the solution of the above hyperbranched polyol 1 is subjected to vacuum distillation to obtain a relatively viscous solution with a solid content of approximately 20 - 25%. The hyperbranched polyol mentioned in the examples refers to the net content of the hyperbranched polyol.

[0057] Preparation case 2 of hyperbranched polyol

[0058] It is generally the same as case 1, except that the molar ratio of diolamine to succinic anhydride is 1.1:1, and hyperbranched polyol 2 is obtained.

[0059] Preparation case 3 of hyperbranched polyol

[0060] It is generally the same as case 1, except that the molar ratio of diolamine to succinic anhydride is 1.2:1, and hyperbranched polyol 3 is obtained.

[0061] Example 1

[0062] The preparation of a high-tough halogen-free flame-retardant ABS composition includes the following operating steps:

[0063] 77 parts by weight of ABS (Zhenjiang Qimei PA-747, melt index 1.1 g / 10 min), 15 parts by weight of TPU (BASF B70A15W, Shore hardness Shore A 75), 5 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA flame retardant (Shandong Taixing New Materials Co., Ltd.), 0.3 part by weight of hyperbranched polyol 1, 1 part by weight of EBS (Indonesia P400), 0.1 part by weight of antioxidant 1010 (German BASF Irganox 1010), 0.2 part by weight of antioxidant 168 (German BASF Irganox 168).

[0064] After the mixture of all the above components is thoroughly physically mixed, it is extruded and pelletized using a twin-screw extruder with a screw diameter of 36 mm (the same hereinafter). Among them, a ten-segment temperature control method is adopted to control the temperature of each extrusion segment, and the temperatures of each segment are 195 °C, 200 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, and 200 °C respectively. After forming by injection molding or pressing plate process, various performance tests are carried out.

[0065] Example 2

[0066] 71 parts by weight of ABS (Jiangsu Zhenjiang Qimei PA-747, melt index 1.1 g / 10 min), 8 parts by weight of EMA (Westlake, USA, SP1330), 10 parts by weight of TPU (BASF B70A15W, Shore hardness Shore A 75), 8 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 0.4 part by weight of hyperbranched polyol 1, 1 part by weight of EBS (Indonesia P400), 0.1 part by weight of antioxidant 1010 (BASF Irganox 1010, Germany), 0.2 part by weight of antioxidant 168 (BASF Irganox 168, Germany).

[0067] After the mixture of all the above components is thoroughly physically mixed, it is extruded and pelletized using a twin-screw extruder with a screw diameter of 36 mm (the same hereinafter). Among them, a ten-segment temperature control method is adopted to control the temperature of each extrusion segment, and the temperatures of each segment are 195 °C, 200 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, and 200 °C respectively. After forming by injection molding or pressing plate process, various performance tests are carried out.

[0068] Example 3

[0069] 63 parts by weight of ABS (Jiangsu Zhenjiang Qimei PA-747, melt index 1.1 g / 10 min), 12 parts by weight of EMA (Westlake, USA, SP1330), 10 parts by weight of TPU (BASF B70A15W, Shore hardness Shore A 75), 12 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 0.5 part by weight of hyperbranched polyol 1, 1 part by weight of EBS (Indonesia P400), 0.1 part by weight of antioxidant 1010 (BASF Irganox 1010, Germany), 0.2 part by weight of antioxidant 168 (BASF Irganox 168, Germany).

[0070] After the mixture of all the above components is fully physically mixed, it is extruded and pelletized using a twin-screw extruder with a screw diameter of 36 mm (the same hereinafter). Among them, a ten-section temperature control method is adopted to control the temperature of each extrusion section, and the temperatures of each section are 195 °C, 200 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, and 200 °C respectively. After molding by injection molding or pressing plate process, various performance tests are carried out.

[0071] Example 4

[0072] Generally the same as Example 2, the difference is that the formula is as follows:

[0073] 71 parts by weight of ABS (Zhenjiang Qimei PA-747, melt index 1.1 g / 10 min), 8 parts by weight of EMA (Westlake, USA, SP1330), 10 parts by weight of TPU (BASF B70A15W, Shore hardness Shore A 75), 8 parts by weight of microencapsulated red phosphorus, 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 0.4 parts by weight of hyperbranched polyol 1, 1 part by weight of EBS (Indonesia P400), 0.1 part by weight of antioxidant 1010 (BASF Irganox 1010, Germany), 0.2 part by weight of antioxidant 168 (BASF Irganox 168, Germany).

[0074] Example 5

[0075] Generally the same as Example 2, the difference is that the formula is as follows:

[0076] 71 parts by weight of ABS (acrylonitrile-butadiene-styrene graft maleic anhydride copolymer), 8 parts by weight of EMA (Westlake, USA, SP1330), 10 parts by weight of TPU (BASF B70A15W, Shore hardness Shore A 75), 8 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 0.4 parts by weight of hyperbranched polyol 1, 1 part by weight of EBS (Indonesia P400), 0.1 part by weight of antioxidant 1010 (BASF Irganox 1010, Germany), 0.2 part by weight of antioxidant 168 (BASF Irganox 168, Germany).

[0077] Example 6

[0078] Generally the same as Example 2, the difference is that the formula is as follows:

[0079] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 7 parts by weight of black phosphorus (self-made), 1.5 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 1.5 parts by weight of zinc borate, 0.4 parts by weight of hyperbranched polyol 1, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0080] Example 7

[0081] Generally the same as Example 2, except that the formulation is as follows:

[0082] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 6 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 2 parts by weight of zinc borate, 0.4 parts by weight of hyperbranched polyol 1, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0083] Example 8

[0084] Generally the same as Example 2, except that the formulation is as follows:

[0085] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 8 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 2 parts by weight of zinc borate, 0.4 parts by weight of hyperbranched polyol 1, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0086] Example 9

[0087] Generally the same as Example 2, except that the formulation is as follows:

[0088] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 7 parts by weight of black phosphorus (self-made), 1.5 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 1.5 parts by weight of zinc borate, 0.4 parts by weight of hyperbranched polyol 2, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0089] Example 10

[0090] Generally the same as Example 2, the difference is that the formulation is as follows:

[0091] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 7 parts by weight of black phosphorus (self-made), 1.5 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 1.5 parts by weight of zinc borate, 0.4 parts by weight of hyperbranched polyol 3, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0092] Example 11

[0093] Generally the same as Example 2, the difference is that the formulation is as follows:

[0094] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 10 parts by weight of black phosphorus (self-made), 0.4 parts by weight of hyperbranched polyol 1, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0095] Example 12

[0096] Generally the same as Example 2, the difference is that the formulation is as follows:

[0097] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 8 parts by weight of black phosphorus (self-made), 2 parts by weight of zinc borate, 0.4 part by weight of hyperbranched polyol 1, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0098] Comparative Example 1

[0099] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 8 parts by weight of black phosphorus (self-made), 2 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0100] The mixtures of all the above components were physically mixed thoroughly and then pelletized by a twin-screw extruder with a screw diameter of 36 mm (the same hereinafter). Among them, a ten-stage temperature control method was used to control the temperature of each extrusion section, and the temperatures of each section were 195 °C, 200 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, and 200 °C respectively. After molding by injection molding or pressing plate process, various performance tests were carried out.

[0101] Comparative Example 2

[0102] Generally the same as Example 2, except that the formulation is as follows:

[0103] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore hardness A 75), 7 parts by weight of black phosphorus (self-made), 1.5 parts by weight of MCA (Shandong Taixing New Materials Co., Ltd.), 1.5 parts by weight of zinc borate, 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0104] Comparative Example 3

[0105] 71 parts by weight of ABS (PA-747 from Zhenjiang Qimei, melt index 1.1 g / 10 min), 8 parts by weight of EMA (SP1330 from Westlake, USA), 10 parts by weight of TPU (B70A15W from BASF, Shore A hardness 75), 1 part by weight of EBS (P400 from Indonesia), 0.1 part by weight of antioxidant 1010 (Irganox 1010 from BASF, Germany), 0.2 part by weight of antioxidant 168 (Irganox 168 from BASF, Germany).

[0106] After the mixture of all the above components was physically mixed thoroughly, it was extruded and pelletized using a twin-screw extruder with a screw diameter of 36 mm (the same hereinafter). Among them, a ten-zone temperature control method was used to control the temperature of each extrusion zone, and the temperatures of each zone were 195 °C, 200 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, 210 °C, and 200 °C respectively. After forming by injection molding or pressing plate process, various performance tests were carried out.

[0107] Performance test experiment

[0108] The samples obtained from the above Examples 1-11 and Comparative Examples 1-2 were processed into test specimens according to the standard experimental requirements, and their performances were tested according to the following test standards. The results are shown in Table 1.

[0109] 1. Tensile yield strength

[0110] Detected according to the test standard ISO 527-2;

[0111] 2. IZod notched impact strength

[0112] Detected according to the test standard ISO179-1993;

[0113] 3. Flexural modulus

[0114] Tested according to the national standard ISO-178-2010;

[0115] 4. Flame retardant grade

[0116] Detected according to the national standard ANSI / UL-94-1985 standard;

[0117] Table 1

[0118]

[0119]

[0120] Result analysis

[0121] 1. From the comparison between Example 2 and Example 5, it can be seen that the chain extension reaction can occur between the ABS with maleic anhydride medium and hyperbranched polyol, and the tensile yield strength and IZod notched impact strength of the obtained sheet are both significantly improved; this indicates that the ABS with maleic anhydride medium is more practical in products that pay more attention to the strength of the sheet.

[0122] 2. From Example 2 and Examples 6 - 10, it can be found that when using a ternary composite flame retardant, although the mechanical properties of the sheet are not improved, most of the flame retardant properties are enhanced. This shows that zinc borate can cooperate well with hyperbranched polyol. While maintaining good dispersion performance, it can promote the hyperbranched polyol attached near the flame retardant to accelerate carbonization and form an isolation layer.

[0123] 3. From the comparison between Example 2 and Comparative Examples 1 - 3, it can be found that after adding a flame retardant to the ABS, the mechanical properties of the sheet are inferior to those of Example 2 and Example 6. This indicates that the ABS sheet lacking hyperbranched polyol and containing a flame retardant cannot pass the UL 94 1.0 mm flame retardant test; at the same time, Comparative Example 3 shows that using hyperbranched polyol alone has an improving effect on the sheet properties.

[0124] This also provides a new direction for the improvement of the material properties of ABS by hyperbranched polyol.

[0125] The applicant declares that the present invention uses the above examples to illustrate the process method of the present invention, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of the raw materials selected for the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A high-toughness halogen-free flame-retardant ABS composition, characterized in that, It is made from the following raw materials in parts by weight: 71 parts by weight of ABS; 8 parts by weight of EMA; 10 parts by weight of TPU; 7 parts by weight of black phosphorus; 1.5 parts by weight of MCA; 1.5 parts by weight of zinc borate; 0.4 parts by weight of hyperbranched polyol; 1 part by weight of EBS; 0.1 part by weight of antioxidant 1010; 0.2 part by weight of antioxidant 168; The preparation method of the hyperbranched polyol is as follows: Weigh 4g of diolamine, weigh succinic anhydride according to the molar ratio of diolamine to succinic anhydride of 1.1:1 and place it in a three-necked flask, then dissolve it with 30 mL of DMAc, and react under magnetic stirring at room temperature for 1h; Add a small amount of catalyst p-toluenesulfonic acid and 50 mL of azeotropic water-carrying agent to the reaction system, stir and start to slowly heat the reaction until reflux occurs, continue to stir the reaction, and separate the water generated by the reaction through a water separator by condensing and refluxing the reaction phase. When no water droplets are generated, the reaction ends to obtain the hyperbranched polyol.

2. A preparation method of the high-toughness halogen-free flame-retardant ABS composition according to claim 1, characterized in that, It includes the following operation steps: S1. Weigh each component; S2. After fully physically mixing each component, extrude and pelletize with a twin-screw extruder; S3. Compress and mold the pellets.

3. The preparation method of the high-toughness halogen-free flame-retardant ABS composition according to claim 2, characterized in that, The physical mixing is carried out at a rotation speed of 900 - 1200 r / min in a high-speed mixer for 6 - 10 min; The screw diameter of the twin-screw extruder is 24 - 36 mm, and the temperature of each extrusion section is controlled by a ten-section temperature control method. The temperatures of each section are 195 - 200 °C, 200 - 205 °C, 210 - 220 °C, 210 - 215 °C, 220 - 230 °C, 220 - 225 °C, 210 - 220 °C, 200 - 205 °C, 190 - 200 °C, and 200 - 210 °C respectively.

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