Halogen-free flame-retardant PC / ABS alloy material as well as preparation method and application thereof

Abstract

The invention relates to a halogen-free flame-retardant PC / ABS alloy material as well as a preparation method and application thereof. The halogen-free flame-retardant PC / ABS alloy material is prepared from the following components in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 1-3 parts of modified graphene oxide, 7-11 parts of a halogen-free flame retardant composition, 0.3 part of an anti-dripping agent and 1 part of other auxiliaries. The COFs material and the styrene-maleic anhydride copolymer synergistically modified graphene oxide are added into the PC / ABS alloy material, the modified graphene oxide serves as a compatilizer and a flame retardant at the same time, and the COFs material and the styrene-maleic anhydride copolymer coating the surface of the modified graphene oxide are used for improving the compatibility of PC and ABS materials; meanwhile, the COFs material and the graphene oxide have flame retardant performance, formation of a carbon layer is promoted in the material combustion process, so that the COFs material and the graphene oxide form a synergistic effect with the halogen-free flame retardant, the flame retardant performance of the PC / ABS alloy material is further improved, and the PC / ABS alloy material can be applied to automobile interior and exterior halogen-free flame-retardant thin-wall products.

Description

Technical Field

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

[0002] In practical applications, in order to improve the comprehensive performance of polycarbonate (PC), PC is often blended with other polymers to prepare PC alloys, including PC / ABS, PC / PET, PC / PMMA and PC / PA. Among them, PC / ABS alloy has the largest usage and the widest application range. ABS can improve the processing performance, weather resistance and mechanical properties of PC, and reduce the material cost. PC / ABS alloy has been widely used in the fields of electronic appliances, automotive interiors and building materials.

[0003] ABS is a terpolymer containing three monomers: acrylonitrile, butadiene, and styrene. PC / ABS has a typical sea-island structure, with PC as the continuous phase and ABS as the dispersed phase. PC has good interfacial compatibility with the styrene-acrylonitrile component in ABS, allowing ABS to toughen PC. However, the three components in ABS are highly flammable materials, so ABS is extremely easy to burn, and it will produce a lot of black smoke and toxic gases when burning. After being blended with PC to make PC / ABS alloy, the flame retardant properties of PC will also be seriously deteriorated, especially for thin-walled products, the flame retardant properties are even worse. In addition, the interfacial compatibility between ABS and PC will directly affect the mechanical properties of the material, so it is very necessary to perform flame retardant and volume-increasing modifications on PC / ABS alloy. Summary of the invention

[0004] Based on this, the purpose of the present invention is to provide a halogen-free flame-retardant PC / ABS alloy material and a preparation method and application thereof. The halogen-free flame-retardant PC / ABS alloy material of the present invention has high flame retardant properties, and the flame retardant grade can reach V-0 (UL94) at a thickness of 1.6 mm, while ensuring the high mechanical properties of the material, and can be applicable to the field of thin-wall flame-retardant PC / ABS alloy materials.

[0005] To achieve the above object, the present invention adopts the following technical solutions: The present invention first provides a halogen-free flame-retardant PC / ABS alloy material, which is prepared from the following components in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 1-3 parts of modified graphene oxide, 7-11 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent and 1 part of other auxiliary agents.

[0006] The present invention adds graphene oxide synergistically modified by COFs material and styrene-maleic anhydride copolymer to PC / ABS alloy material, wherein the modified graphene oxide acts as a compatibilizer and a flame retardant at the same time, and the compatibility of PC and ABS materials is improved by using COFs material and styrene-maleic anhydride copolymer coated on the surface of the modified graphene oxide. Meanwhile, the COFs material and graphene oxide have flame retardant properties, and promote the formation of a carbon layer during the combustion process of the material, thereby forming a synergistic effect with the halogen-free flame retardant, and further improving the flame retardant properties of the PC / ABS alloy material.

[0007] As a further improvement of the above solution of the present invention, the modified graphene oxide is obtained by synergistically modifying graphene oxide with COFs material and styrene-maleic anhydride copolymer.

[0008] As a further improvement of the above scheme of the present invention, the preparation method of the modified graphene oxide includes: after 2,5-dimethylterephthaloyl hydrazide, (4-formaldehyde benzene)-1,3,5-triazine, o-dichlorobenzene and n-butanol are uniformly mixed, acetic acid, graphene oxide and styrene-maleic anhydride copolymer are added, and then vacuumization and heating reaction are carried out; after the reaction is completed, the COFs material and the styrene-maleic anhydride copolymer are cooled to room temperature to obtain graphene oxide co-coated, that is, modified graphene oxide.

[0009] As a further improvement of the above scheme of the present invention, the mass ratio of 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol, acetic acid, graphene oxide and styrene-maleic anhydride copolymer is preferably 67:79:3:2:60:5000-10000:200-400; And / or, the vacuuming is to evacuate to a vacuum degree of -0.1MPa to -0.09MPa, and the heating reaction is carried out at 110-130°C for 70-80h.

[0010] As a further improvement of the above solution of the present invention, the halogen-free flame retardant composition is obtained by compounding melamine, a phosphate-based halogen-free flame retardant and a flame-retardant carbon-forming agent.

[0011] As a further improvement of the above solution of the present invention, the ABS resin is a copolymer of acrylonitrile, butadiene and styrene, wherein the mass percentage of butadiene is 40-70%.

[0012] As a further improvement of the above solution of the present invention, the anti-dripping agent is a polytetrafluoroethylene material; And / or, the other auxiliary agent is at least one of an antioxidant, a lubricant, and a UV resistant agent.

[0013] The present invention also provides a method for preparing the halogen-free flame-retardant PC / ABS alloy material as described above, which comprises the following steps: mixing PC resin, ABS resin, modified graphene oxide, halogen-free flame retardant composition, anti-dripping agent and other additives in proportion, adding the mixture into an extruder from a main feed port, and performing melting, extrusion, granulation, cooling and drying to obtain the halogen-free flame-retardant PC / ABS alloy material.

[0014] As a further improvement of the above scheme of the present invention, the temperatures of each zone of the extruder are: 180°C in zone 1, 230°C in zone 2, 240°C in zone 3, 240°C in zone 4, 240°C in zone 5, 240°C in zone 6, and 235°C in the die head; the screw speed of the extruder is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0015] The present invention also provides a use of the above-mentioned halogen-free flame-retardant PC / ABS alloy material in the preparation of highly flame-retardant thin-walled products.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention introduces modified graphene oxide into PC / ABS alloy material. The modified graphene oxide is obtained by synergistically modifying graphene oxide with COFs material and styrene-maleic anhydride copolymer. The in-situ grown COFs material has polarity and adsorption effect, and provides a carrier for the deposition of styrene-maleic anhydride copolymer on the surface of graphene oxide. At the same time, the styrene-maleic anhydride copolymer contains chemical functional groups, which can form covalent bonds with silanol groups on the surface of graphene oxide, and provide crosslinking points for the in-situ growth of COFs material on graphene oxide. The modified graphene oxide and styrene-maleic anhydride copolymer play a synergistic role, thereby greatly improving the surface activity of graphene oxide; in PC / ABS alloy materials, modified graphene oxide acts as a compatibilizer and flame retardant at the same time, and the COFs material and styrene-maleic anhydride copolymer coated on the surface of modified graphene oxide are used to improve the compatibility of PC and ABS materials. At the same time, COFs material and graphene oxide have flame retardant properties, which promote the formation of carbon layer during the combustion process of the material, thereby forming a synergistic effect with the halogen-free flame retardant, and further improving the flame retardant properties of PC / ABS alloy materials.

[0017] 2. The halogen-free flame retardant of the present invention is a composition of melamine, a phosphate halogen-free flame retardant and a flame retardant carbon-forming agent, wherein melamine provides a gas source for the flame retardant material, the phosphate halogen-free flame retardant provides an acid source for the flame retardant material, and the flame retardant carbon-forming agent provides a carbon source for the flame retardant material. The three act synergistically and have a higher flame retardant effect at a lower addition amount.

[0018] 3. The halogen-free flame-retardant PC / ABS alloy material prepared by the present invention can be recycled and reused, meeting the development needs of green and recycled materials for automobiles. DETAILED DESCRIPTION

[0019] For ease of understanding of the present invention, the present invention will be described more fully 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.

[0020] 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.

[0021] The specific information of the raw materials used in the following examples and comparative examples is as follows: (1) PC resin: brand: Teijin AD-5503, melt index: 54 cm 3 / 10min, the manufacturer is Teijin Co., Ltd. of Japan; (2) ABS resin: brand ABS PA-757K, melt flow rate (200°C / 5.0kg) is 1.8g / 10min, manufacturer is Hengshui Diyi Petrochemical Co., Ltd.; (3) Modified graphene oxide: homemade, homemade method is: weigh 67g of 2,5-dimethylterephthaloyl hydrazide and 79g of (4-formylphenyl)-1,3,5-triazine in a glass bottle, then add 3g of o-dichlorobenzene and 2g of n-butanol and mix evenly, drop 6g of acetic acid with a concentration of 6 mol / L, then add 5kg of graphene oxide and 200g of styrene-maleic anhydride copolymer to obtain a mixture; add the mixture into a rotary vacuum drying oven, then evacuate to a vacuum degree of less than -0.09MPa, heat to 120℃ and react at 120℃ for 80h, then cool to room temperature to obtain a graphene oxide material co-coated with COFs and styrene-maleic anhydride copolymer, which is the modified graphene oxide; Among them, 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol and acetic acid are all conventional chemical reagents; graphene oxide, with a thickness of 0.55-1.2 nm, a diameter of 0.5-3 μm, and a layer number of 1-5, was purchased from Zhongke Leiming (Beijing) Technology Co., Ltd.; styrene-maleic anhydride copolymer was purchased from MacLean Chemical Reagent Co., Ltd.; (4) The halogen-free flame retardant composition is prepared by compounding melamine, bis(diphenyl phosphate) and pentaerythritol in a mass ratio of 2:5:3, wherein melamine is industrial grade and purchased from Sinopharm Chemical Reagent Co., Ltd.; bisphenol A bis(diphenyl phosphate) is purchased from Maclean Chemical Reagent Co., Ltd.; pentaerythritol, industrial grade, is purchased from Sinopharm Chemical Reagent Co., Ltd.; (5) Anti-dripping agent: polytetrafluoroethylene, model FR-2600, manufactured by Dongguan Zhenming Chemical Co., Ltd.; (6) Other additives are prepared by mixing antioxidant, lubricant and UV resistant agent in a mass ratio of 1:1:1.

[0022] The above raw materials are all conventional commercially available materials.

[0023] The above raw materials are only for illustrating the sources and components of the raw materials used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be realized by using other similar reagents or reagents provided by other suppliers.

[0024] Example 1 This embodiment provides a halogen-free flame-retardant PC / ABS alloy material, which includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 3 parts of modified graphene oxide, 7 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent, and 1 part of other additives.

[0025] The preparation method of the halogen-free flame-retardant PC / ABS alloy material of the present embodiment comprises the following steps: PC resin, ABS resin, modified graphene oxide, halogen-free flame retardant composition, anti-dripping agent, and other additives are placed in a high mixer in proportion and mixed for 5 minutes, and then added to a twin-screw extruder from the main feed port, and the halogen-free flame-retardant PC / ABS alloy material is obtained by melting, extruding, granulating, cooling, and drying. In the present embodiment, the temperature of each zone of the barrel of the twin-screw extruder is: 180°C in zone 1, 230°C in zone 2, 240°C in zone 3, 240°C in zone 4, 240°C in zone 5, 240°C in zone 6, and 235°C in die head; the screw speed of the twin-screw extruder is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

[0026] Example 2 This embodiment adopts the same implementation method as Example 1, and the difference from Example 1 is that the halogen-free flame retardant PC / ABS alloy material of this embodiment includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 3 parts of modified graphene oxide, 8 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent, and 1 part of other additives.

[0027] Example 3 This embodiment adopts the same implementation method as Example 1, and the difference from Example 1 is that the halogen-free flame retardant PC / ABS alloy material of this embodiment includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 3 parts of modified graphene oxide, 11 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent, and 1 part of other additives.

[0028] Example 4 This embodiment adopts the same implementation method as Example 1, and the difference from Example 1 is that the halogen-free flame retardant PC / ABS alloy material of this embodiment includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 2 parts of modified graphene oxide, 11 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent, and 1 part of other additives.

[0029] Example 5 This embodiment adopts the same implementation method as Example 1, and the difference from Example 1 is that the halogen-free flame retardant PC / ABS alloy material of this embodiment includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 1 part of modified graphene oxide, 11 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent, and 1 part of other additives.

[0030] Comparative Example 1 This comparative example adopts the same implementation as Example 1, and the difference from Example 1 is that the PC / ABS alloy material of this comparative example includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, and 1 part of other additives.

[0031] Comparative Example 2 This comparative example adopts the same implementation as Example 1, and the difference from Example 1 is that the halogen-free flame retardant PC / ABS alloy material of this comparative example includes the following component raw materials in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 7 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent, and 1 part of other additives.

[0032] The amounts of the raw materials used in the above examples and comparative examples are shown in Table 1.

[0033] Table 1 Amount of each raw material used in the examples and comparative examples (parts by mass)

[0034] Test Case The PC / ABS alloy materials prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were subjected to tensile performance tests, bending performance tests and combustion performance tests, respectively. The test results are shown in Table 2.

[0035] Table 2 Performance test results

[0036] According to the results in Table 2, we can see that: Compared with Comparative Examples 1-2, Examples 1-5 show that the limiting oxygen index of the PC / ABS alloy material is significantly improved by adding modified graphene oxide in Examples 1-5, and the flame retardant grade reaches V-0 at a thickness of 1.6 mm, and the tensile and impact properties of the material are improved; it is illustrated that the modified graphene oxide of the present application can improve the flame retardant properties of the PC / ABS alloy material, and at the same time improve the mechanical properties of the PC / ABS alloy material, and the PA / ABS alloy material of the present application can be applied to the field of thin-walled flame retardant materials; It can be seen from the test results of Comparative Examples 1 and 2 that: in Comparative Example 1, when no halogen-free flame retardant composition is added, the flame retardant performance of the PC / ABS alloy material is poor, the limiting oxygen index is low, and dripping occurs during combustion, which does not meet the vertical combustion level; while after the halogen-free flame retardant composition is added to Comparative Example 2, the limiting oxygen index of the material is significantly improved, but there is still a drop phenomenon during combustion, the flame retardant level is V-2, and the tensile properties and impact properties are seriously reduced; This illustrates that the synergistic effect of the components in the halogen-free flame retardant composition of the present application can improve the flame retardant properties of the PC / ABS alloy material.

[0037] 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.

[0038] 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 halogen-free flame-retardant PC / ABS alloy material, characterized in that: The invention is prepared from the following components in parts by mass: 80 parts of PC resin, 20 parts of ABS resin, 1-3 parts of modified graphene oxide, 7-11 parts of halogen-free flame retardant composition, 0.3 parts of anti-dripping agent and 1 part of other auxiliary agents.

2. The halogen-free flame-retardant PC / ABS alloy material according to claim 1, characterized in that: The modified graphene oxide is obtained by synergistically modifying graphene oxide with COFs material and styrene-maleic anhydride copolymer.

3. The halogen-free flame-retardant PC / ABS alloy material according to claim 2, characterized in that: The preparation method of the modified graphene oxide comprises: uniformly mixing 2,5-dimethylterephthaloyl hydrazide, (4-formaldehyde benzene)-1,3,5-triazine, o-dichlorobenzene and n-butanol, adding acetic acid, graphene oxide and styrene-maleic anhydride copolymer, and then vacuumizing and heating for reaction; after the reaction is completed, cooling to room temperature to obtain graphene oxide co-coated with COFs material and styrene-maleic anhydride copolymer, namely the modified graphene oxide.

4. The halogen-free flame-retardant PC / ABS alloy material according to claim 3, characterized in that: The mass ratio of the 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol, acetic acid, graphene oxide and styrene-maleic anhydride copolymer is preferably 67:79:3:2:60:5000-10000:200-400; And / or, the vacuuming is to evacuate to a vacuum degree of -0.1MPa to -0.09MPa, and the heating reaction is carried out at 110-130°C for 70-80h.

5. The halogen-free flame-retardant PC / ABS alloy material according to claim 1, characterized in that: The halogen-free flame retardant composition is obtained by compounding melamine, a phosphate-based halogen-free flame retardant and a flame-retardant carbon-forming agent.

6. The halogen-free flame-retardant PC / ABS alloy material according to claim 1, characterized in that: The ABS resin is a copolymer of acrylonitrile, butadiene and styrene, wherein the mass percentage of butadiene is 40-70%.

7. The halogen-free flame-retardant PC / ABS alloy material according to claim 1, characterized in that: The anti-dripping agent is a polytetrafluoroethylene material; And / or, the other auxiliary agent is at least one of an antioxidant, a lubricant, a UV resistant agent, and a pigment.

8. A method for preparing the halogen-free flame-retardant PC / ABS alloy material according to any one of claims 1 to 7, characterized in that: It includes the following steps: PC resin, ABS resin, modified graphene oxide, halogen-free flame retardant composition, anti-dripping agent and other additives are mixed in proportion, added into the extruder from the main feeding port, and melted, extruded, granulated, cooled and dried to obtain a halogen-free flame retardant PC / ABS alloy material.

9. The method for preparing the halogen-free flame-retardant PC / ABS alloy material according to claim 8, characterized in that: The temperatures of each zone of the extruder are: 180°C for zone 1, 230°C for zone 2, 240°C for zone 3, 240°C for zone 4, 240°C for zone 5, 240°C for zone 6, and 235°C for the die head; the screw speed of the extruder is 500r / min, the melt pressure is 1.0 MPa, and the vacuum degree is -0.06MPa.

10. Use of the halogen-free flame-retardant PC / ABS alloy material as claimed in any one of claims 1 to 9 in the preparation of highly flame-retardant thin-walled products.

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