A needle-flame resistant flame-retardant PC / ABS alloy material and its preparation method

Abstract

This invention provides a needle-flame resistant flame-retardant PC / ABS alloy material and its preparation method, relating to the technical field of polycarbonate alloy materials. The needle-flame resistant flame-retardant PC / ABS alloy material comprises, by weight, 100 parts PC / ABS alloy and 1-15 parts modified graphene; the modified graphene is a graphene chemically grafted polysiloxane-modified maleic anhydride-grafted polymer; preferably, the polysiloxane-modified maleic anhydride-grafted polymer is chemically grafted to graphene via polysiloxane segments. The modified graphene of this invention can significantly improve the flame-retardant properties of the PC / ABS alloy, meeting both needle-flame testing and UL-94 vertical burning V-0 rating.

Description

Technical Field

[0001] This invention belongs to the technical field of polycarbonate alloy materials, and relates to a needle flame resistant flame-retardant PC / ABS alloy material and its preparation method. Background Technology

[0002] PC / ABS alloys combine the excellent heat resistance and mechanical strength of polycarbonate (PC) with the good processability of ABS resin, achieving a complementary effect between the two materials. They are widely used in various fields such as automobiles and electronic equipment. However, PC / ABS has the drawback of poor flame retardancy, posing certain safety hazards during application. Furthermore, when the ABS content in the PC / ABS alloy is high, its impact resistance is also insufficient.

[0003] Graphene exhibits flame-retardant properties in polycarbonate, primarily through the formation of physical barriers, improved heat resistance, free radical capture, and catalytic char formation. Simultaneously, the dispersibility of graphene significantly impacts its flame-retardant effect; generally, better graphene dispersibility leads to better performance, including flame retardant properties. CN109486155A discloses a graphene-modified halogen-free flame-retardant PC / ABS material. This method involves first adding graphene to a heated and molten halogen-free flame retardant to obtain a homogeneous graphene solution, which is then added to PC to prepare PC graphene flame-retardant masterbatch. However, due to the high agglomeration force of graphene, it cannot be well dispersed, resulting in a weak flame-retardant effect. CN110511554A discloses a halogen-free flame-retardant nitrogen-phosphorus-silicon modified graphene / polycarbonate / ABS alloy material, which is a halogen-free flame retardant formed by in-situ polymerization and grafting of octaaminopropyl cage-type silsesquioxane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide onto the surface of graphene oxide. However, due to the high cost of both octaaminopropyl cage-type silsesquioxane and graphene, the cost of the obtained halogen-free flame retardant is also very high.

[0004] There are various methods for testing flame retardancy, among which the needle flame test and the UL-94 vertical burning test (to achieve a V-0 rating) are more demanding. These two tests have different requirements and their results are not equivalent. However, there are few reports of PC / ABS alloys meeting both the needle flame retardancy test requirements and the UL-94 vertical burning test V-0 rating after flame retardancy enhancement, as the results of these two methods can be contradictory. To achieve vertical flame retardancy, organic products typically have anti-dripping agents (such as PTFE) added to promote charring and prevent flame dripping during combustion, thus achieving a V-0 rating. However, excessive amounts of anti-dripping agents can cause the molten organic product to shrink during combustion, leading to burn-through and failing to meet the needle flame retardancy requirements. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a needle-flame resistant flame-retardant PC / ABS alloy material and its preparation method.

[0006] The technical solution of the present invention is as follows:

[0007] A needle flame retardant PC / ABS alloy material, the raw material components, by weight, include 100 parts PC / ABS alloy and 1-15 parts modified graphene;

[0008] The modified graphene is a graphene chemically grafted polysiloxane-modified maleic anhydride graft polymer.

[0009] Preferably, the polysiloxane-modified maleic anhydride graft polymer is obtained by chemically grafting polysiloxane segments onto the graphene.

[0010] Preferably, the method for preparing the modified graphene includes:

[0011] Polysiloxane-modified graphene was obtained by reacting graphene oxide with diamino-terminated polysiloxane.

[0012] The modified graphene is obtained by reacting the polysiloxane-modified graphene with the maleic anhydride graft polymer.

[0013] More preferably, the weight ratio of the graphene oxide to the diamino-terminated polysiloxane is 1:0.1-10.

[0014] More preferably, the structure of the double-terminated amino polysiloxane is shown in formula (1).

[0015] NH2R 1 SiMe2(OSiMeR 2 ) n OSiMe2R 1 NH2(1)

[0016] Among them, R 1 Selected from C2-C6 divalent alkyl groups or substituted C3-C10 divalent alkyl groups, R 2 Selected from C1-C12 alkyl, aromatic and their derivatives, cycloalkyl and their derivatives, Me represents methyl, n = 5-100.

[0017] More preferably, the graphene oxide and the diamino-terminated polysiloxane are further reduced after reaction, and the reducing agent used for the reduction is selected from one or a combination of two or more of sodium borohydride, hydrogen, glucose, hydrazine hydrate, dimethylhydrazine and ascorbic acid and its salts.

[0018] More preferably, the weight ratio of the polysiloxane-modified graphene to the maleic anhydride graft polymer is 1:0.2-3.

[0019] More preferably, the grafting rate of the maleic anhydride grafted polymer is 1-10 wt%.

[0020] More preferably, the maleic anhydride-grafted polymer is selected from one or a combination of two or more of maleic anhydride-grafted ABS, maleic anhydride-grafted EVA, maleic anhydride-grafted SEBS, maleic anhydride-grafted SAN, and maleic anhydride-grafted POE.

[0021] Preferably, the raw material components further include one or a combination of two or more of the following: 0.5-5 parts of phosphorus-based flame retardant, 0.1-1 parts of antioxidant, 0.1-1 parts of UV stabilizer, and 0-0.1 parts of anti-dripping agent.

[0022] A method for preparing the needle-flame resistant flame-retardant PC / ABS alloy material according to any of the above embodiments involves mixing the raw material components evenly, adding them to a screw extruder for melt extrusion, and molding (e.g., cooling and pelletizing) to obtain the needle-flame resistant flame-retardant PC / ABS alloy material.

[0023] The beneficial effects of this invention are:

[0024] (1) The modified graphene of this invention combines the flame-retardant properties of graphene and polysiloxane structures. Furthermore, through chemical bonding, its performance is more stable and it exhibits better flame-retardant properties. It also meets the requirements of needle flame retardancy testing and the UL-94 vertical burning V0 rating, and there is no dripping combustion even with a very low amount of anti-dripping agent. The modified graphene also contains a maleic anhydride grafted polymer structure, which gives the modified graphene good compatibility with PC / ABS, allowing the flame-retardant properties of the modified graphene to be better utilized.

[0025] (2) The modified graphene of the present invention, combined with phosphorus-based flame retardant, can further improve the flame retardant effect and further enhance the flame retardant performance of PC / ABS. Detailed Implementation

[0026] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0027] To improve the effect of graphene as a flame retardant, this invention proposes a needle flame resistant flame retardant PC / ABS alloy material, the raw material components of which, by weight, include 100 parts PC / ABS alloy and 1-15 parts modified graphene.

[0028] There are no particular restrictions on the weight ratio of PC to ABS in PC / ABS alloys; typically, the ratio can be 85:15 to 97:3. PC / ABS alloys can be produced by blending PC and ABS resins, for example, by obtaining PC and ABS resins separately from the market and then mixing them. To improve the impact resistance of needle flame retardant PC / ABS alloys, compatibilizers and / or toughening agents can be added, such as maleic anhydride-grafted ABS (ABS-g-MAH) or maleic anhydride-grafted PE (PE-g-MAH). The amount of compatibilizer can be 1-5% of the weight of the PC / ABS alloy.

[0029] The modified graphene mentioned above is a graphene chemically grafted with a polysiloxane-modified maleic anhydride graft polymer, that is, a polysiloxane-modified maleic anhydride graft polymer is then grafted onto graphene.

[0030] In some embodiments, the polysiloxane-modified maleic anhydride graft polymer is obtained by chemically grafting polysiloxane segments onto graphene.

[0031] The modified graphene of the present invention has the following characteristics: (1) Both graphene and polysiloxane have flame retardant properties and can work together to enhance flame retardant performance, further improving flame retardant performance; (2) Maleic anhydride graft polymer has good compatibility with PC / ABS alloy, which can improve the compatibility between modified graphene and PC / ABS alloy and improve the dispersion of graphene in PC / ABS alloy; (3) Polysiloxane segments with good flexibility and low temperature resistance are well dispersed in PC / ABS alloy through maleic anhydride graft polymer, further improving the impact resistance and low temperature resistance of PC / ABS alloy.

[0032] For example, the weight parts of modified graphene can be 1 part, 3 parts, 5 parts, 6 parts, 8 parts, 10 parts, 12 parts, 13 parts, 15 parts, etc., without any particular restrictions. Furthermore, the weight parts of modified graphene can be 3-15 parts.

[0033] In some embodiments, the method for preparing modified graphene includes:

[0034] Polysiloxane-modified graphene was obtained by reacting graphene oxide with diamino-terminated polysiloxane.

[0035] Modified graphene is obtained by reacting polysiloxane-modified graphene with maleic anhydride graft polymer.

[0036] Graphene oxide (GO) has abundant active groups such as hydroxyl, epoxy, and carboxyl groups on its surface, which can react with primary amino groups. In this invention, after reacting a diamino-terminated polysiloxane with GO, the resulting polysiloxane-modified graphene still contains amino groups at the other end of the polysiloxane segments. These amino groups can further react with maleic anhydride graft polymers, thereby chemically bonding graphene, polysiloxane, and maleic anhydride graft polymer together to achieve synergistic effects.

[0037] In some embodiments, the weight ratio of graphene oxide to diamino-terminated polysiloxane is 1:0.1-10. For example, the weight ratio can be any value from 1:0.1, 1:0.3, 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, etc., without particular limitation. If the weight of diamino-terminated polysiloxane is too small, there will be fewer primary amines remaining after the reaction with GO, which is not conducive to the subsequent reaction with maleic anhydride grafted polymer. Furthermore, from the perspective of improving reaction efficiency and saving raw materials, the weight ratio of graphene oxide to diamino-terminated polysiloxane can be 1:0.3-3. There are no particular restrictions on graphene oxide; for example, the Hummers process for GO can be used.

[0038] In some embodiments, the structure of the double-terminated amino polysiloxane is shown in formula (1).

[0039] NH2R 1 SiMe2(OSiMeR 2 ) n OSiMe2R 1 NH2(1)

[0040] Among them, R 1 Selected from C2-C6 divalent alkyl groups or substituted C3-C10 divalent alkyl groups, R 2 Selected from C1-C12 alkyl, aromatic and their derivatives, cycloalkyl and their derivatives, Me represents methyl, n = 5-100. The average degree of polymerization n of the diamino-terminated polysiloxane is within the above range, and the diamino-terminated polysiloxane has good reactivity and performance. Further, n = 10-70. For example, a diamino-terminated polysiloxane can be diaminopropyl polydimethylsiloxane (R in formula (1) above). 2 (R is methyl), diaminopropylmethylphenyl polysiloxane (in formula (1) above) 2 It is a combination of methyl and phenyl, such as phenyl content 5-20 mol%), and diaminopropyl methylpropyl polysiloxane (R in formula (1) above) 2This can be a combination of methyl and propyl groups, such as propyl content 5-50 mol%. There are no particular restrictions on the source of the diamino-terminated polysiloxane; it can be obtained directly from the market or prepared using existing techniques, as is known to those skilled in the art. For example, 1,3-diaminopropyl-1,1,3,3-tetramethyldisiloxane can be used as a capping agent, along with siloxane cyclic compounds (such as octamethylcyclotetrasiloxane D4, tetramethyltetraphenylcyclotetrasiloxane D4). Ph (e.g., methylpropyl dimethoxysilane) and / or dialkoxysilanes (e.g., methylpropyl dimethoxysilane) undergo ring-opening polymerization at a certain temperature (e.g., 110-120℃) with tetramethylammonium siloxane (commonly known as ammonium styrene or alkali styrene) as a catalyst. After the reaction, the temperature is raised to a higher temperature (e.g., 135-140℃) to decompose and destroy the catalyst, and then low-boiling substances are removed under reduced pressure to obtain the final product. The average degree n can be determined or adjusted according to conditions such as the molar ratio of the end-capping agent and the siloxane ring.

[0041] Graphene oxide contains some defects in its structure, which can be reduced through reduction. In some embodiments, graphene oxide is further reduced after reacting with a diamino-terminated polysiloxane. The reducing agent used for reduction is selected from one or a combination of two or more of sodium borohydride, hydrogen, glucose, hydrazine hydrate, dimethylhydrazine, and ascorbic acid and its salts. Reduction can be performed using a reducing agent, whether the graphene is modified with polysiloxane or after reacting with a maleic anhydride graft polymer. The reduction reaction of graphene oxide is known to those skilled in the art; for example, it can be achieved by reacting an excess of reducing agent (e.g., a weight ratio of reducing agent to graphene oxide of 2-5:1) in an organic solvent (e.g., 80-100°C) for several hours (e.g., several hours to tens of hours).

[0042] Maleic anhydride-grafted polymers refer to polymers to which maleic anhydride monomers are grafted via free radical polymerization or other methods. Maleic anhydride grafted onto polymers generally functions as a compatibilizer and toughening agent. In some embodiments, the weight ratio of polysiloxane-modified graphene to maleic anhydride-grafted polymer is 1:0.2-3. For example, the weight ratio can be 1:0.2, 1:0.3, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.7, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.5, 1:2.7, 1:2.8, 1:3, etc. To further enhance the effectiveness of the maleic anhydride-grafted polymer, the weight ratio of polysiloxane-modified graphene to maleic anhydride-grafted polymer can be 1:0.5-2. Maleic anhydride grafted onto polymers exhibits good compatibility with polycarbonate. Furthermore, the maleic anhydride groups can chemically react with hydroxyl and carboxyl groups in polycarbonate, allowing modified graphene to form chemical bonds with polycarbonate / ABS.

[0043] In some embodiments, the grafting rate of the maleic anhydride-grafted polymer is 1-10 wt%. The grafting rate of the maleic anhydride-grafted polymer refers to the ratio of the weight of maleic anhydride monomer successfully grafted onto the polymer backbone after the grafting reaction to the initial polymer weight. For example, the grafting rate can be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, etc. Further, the grafting rate of the maleic anhydride-grafted polymer can be 1-6 wt%.

[0044] In some embodiments, the maleic anhydride grafted polymer is selected from one or more combinations of maleic anhydride grafted ABS, maleic anhydride grafted EVA, maleic anhydride grafted SEBS, maleic anhydride grafted SAN, and maleic anhydride grafted POE, all of which are commercially available.

[0045] In some embodiments, the raw material components further include one or a combination of two or more of the following: 0.5-5 parts of phosphorus-based flame retardant, 0.1-1 parts of antioxidant, 0.1-1 parts of UV stabilizer, and 0-0.1 parts of anti-dripping agent.

[0046] A further discovery in this invention is that adding phosphorus-based flame retardants can further improve flame retardant performance. There are no particular limitations on phosphorus-based flame retardants; they can be directly obtained from the market, such as triethyl phosphate, resorcinol bis(diphenyl phosphate) RDP, DOPO and its derivatives, etc., which are organophosphorus flame retardants. There are no particular limitations on antioxidants; they can be antioxidants 1010, antioxidant 168, etc. There are no particular limitations on UV stabilizers; they can be UV327, UV328, UV-P, etc. For anti-dripping agents, they can be polytetrafluoroethylene micropowder, organosilicon resin micropowder, silicone rubber micropowder, etc.

[0047] On the other hand, this invention proposes a method for preparing the needle-flame resistant flame-retardant PC / ABS alloy material as described in any of the above embodiments. The raw material components are mixed evenly, added to a screw extruder for melt extrusion, and then shaped (e.g., cold-cut, pelletized) to obtain the needle-flame resistant flame-retardant PC / ABS alloy material. The method for preparing the needle-flame resistant flame-retardant PC / ABS alloy material of this invention can be performed according to conventional PC / ABS alloy material processing methods. For example, each raw material component is pre-dried at 90-120°C until the moisture content does not exceed 0.1 wt% (e.g., 0.02 wt%, 0.05 wt%, etc.), the melting temperature can be 210-260°C, and the nozzle temperature can be 250°C.

[0048] The PC / ABS alloy material obtained by this invention has good flame retardant properties and impact resistance, and can be used in automotive parts, electronic products, medical devices, aerospace and other fields.

[0049] The technical solution of the present invention will be further described and explained below based on various preparation examples and embodiments.

[0050] Preparation Examples 1-3: Preparation of Modified Graphene

[0051] Preparation Example 1

[0052] Add 1 part Hummers GO to 1000 parts butyl acetate, sonicate for 30 min, add 1 part diaminopropyl polydimethylsiloxane (n = 47.2 in formula (1) above), continue sonication for 10 min, stir at room temperature for 1 h, heat to 55 °C and react for 2 h, centrifuge at 8000 rpm for 30 min, collect the solid, and dry in an oven at 50 °C overnight to obtain polysiloxane modified GO.

[0053] One part of the above-mentioned polysiloxane-modified GO and 0.5 parts of maleic anhydride-grafted ABS (grafting rate 1.6 wt%) were dried at 110℃ to a water content of no more than 0.1 wt%. After being mixed evenly, they were transferred to a twin-screw extruder and melt-extruded at 210℃-240℃. After cooling and pelletizing, modified graphene particles were obtained.

[0054] Preparation Example 2

[0055] Add 1 part Hummers GO to 1000 parts butyl acetate, sonicate for 30 min, add 0.5 parts diaminopropyl polydimethylsiloxane (n = 30.5 in the above formula (1)), continue sonication for 10 min, stir at room temperature for 1 h, heat to 55 °C and react for 2 h, add 5 parts sodium borohydride reducing agent, heat to 90 °C and react for 12 h, cool to no more than 50 °C, centrifuge at 8000 rpm for 30 min, collect the solid, and dry in an oven at 50 °C overnight to obtain polysiloxane modified GO.

[0056] One part of the above-mentioned polysiloxane-modified GO and one part of maleic anhydride-grafted ABS (grafting rate 1.2wt%) were dried at 110℃ to a water content of no more than 0.1wt%. After being mixed evenly, they were transferred to a twin-screw extruder and melt-extruded at 210℃-240℃. After cooling and pelletizing, modified graphene particles were obtained.

[0057] Preparation Example 3

[0058] Add 1 part Hummers GO to 1000 parts butyl acetate, sonicate for 30 min, add 2 parts diaminopropyl polydimethylsiloxane (n = 65.8 in formula (1) above), continue sonication for 10 min, stir at room temperature for 1 h, heat to 60 °C and react for 2.5 h, centrifuge at 8000 rpm for 30 min, collect the solid, and dry in an oven at 50 °C overnight to obtain polysiloxane modified GO.

[0059] One part of the above-mentioned polysiloxane-modified GO and two parts of maleic anhydride-grafted ABS (grafting rate 1.6 wt%) were dried at 110°C until the water content did not exceed 0.1 wt%, and then transferred to a twin-screw extruder for melt extrusion at 210°C-240°C. After cooling and pelletizing, modified graphene particles were obtained.

[0060] Example 1

[0061] The raw material composition of the PC / ABS alloy material in this embodiment consists of 1800 parts of PC resin, 200 parts of ABS resin, and 20 parts of modified graphene obtained in Preparation Example 1.

[0062] PC resin was dried at 110°C until the water content was less than 0.1 wt%, and ABS resin and modified graphene were dried at 90°C until the water content was less than 0.1 wt%. After the raw materials were dried and mixed evenly, they were fed into a twin-screw extruder with a melt temperature of 210-260°C and a nozzle temperature of 250°C to obtain a PC / ABS alloy material.

[0063] Example 2

[0064] The difference between this embodiment and Embodiment 1 is that in Embodiment 1, the modified graphene was increased from 20 parts to 70 parts. The remaining steps remain unchanged.

[0065] Example 3

[0066] The difference between this embodiment and Embodiment 1 is that in Embodiment 1, the modified graphene was increased from 20 parts to 200 parts. The remaining steps remain unchanged.

[0067] Example 4

[0068] The difference between this embodiment and Embodiment 3 is that in Embodiment 3, the raw material components also included 40 parts of flame retardant DOPO. The remaining steps remain unchanged.

[0069] Example 5

[0070] The difference between this embodiment and Embodiment 1 is that in Embodiment 1, the modified graphene was increased from 20 parts to 300 parts. The remaining steps remain unchanged.

[0071] Comparative Example 1

[0072] The difference between this comparative example and Example 2 is that in Example 2, the modified graphene was replaced with 70 parts of flame retardant DOPO. The remaining steps remained unchanged.

[0073] Comparative Example 2

[0074] The difference between this comparative example and Example 3 is that in Example 3, the modified graphene was replaced with 200 parts of flame retardant DOPO. The remaining steps remained unchanged.

[0075] Comparative Example 3

[0076] The difference between this comparative example and Example 5 is that in Example 5, the modified graphene was replaced with 300 parts of flame retardant DOPO. The remaining steps remained unchanged.

[0077] Flame retardant performance test

[0078] Needle flame retardancy test: The test is conducted according to the method of GB / T 5169.5-2020. The thickness of the color plate made of PC / ABS alloy material is 1mm. After burning for 60s, observe the burning condition of the color plate, whether the color plate is perforated or cracked, and whether the gauze is ignited.

[0079] UL-94 Flame Retardant Rating Test: The test is conducted according to the UL-94 flammability test standard. The sample thickness is 1.2 mm, and the flame is applied to the test sample for 60 seconds each time.

[0080] Limiting oxygen index (LOI): Tested according to the method of GB / T 2406.2-2009.

[0081] The results are shown in Table 1 below.

[0082] Table 1 Flame retardant performance test results

[0083]

[0084] As shown in Table 1 above, the modified graphene of this invention exhibits good flame retardant effect on PC / ABS alloys. With a dosage of 1%-15%, the flame retardant performance of the PC / ABS alloy material improves with increasing modified graphene dosage, simultaneously meeting both needle flame retardant requirements and UV-94 flame retardant rating requirements. Comparative studies of Examples 4, 5, and 3 show that the combination of modified graphene and DOPO significantly improves the limiting oxygen index and flame retardant performance of the material.

[0085] Example 6

[0086] The raw material composition of the PC / ABS alloy material in this embodiment consists of 1900 parts PC resin, 100 parts ABS resin, 40 parts ABS-g-MAH, 160 parts modified graphene obtained in Preparation Example 2, 20 parts flame retardant DOPO, 10 parts antioxidant 168, 8 parts UV stabilizer UV327 and 1 part anti-dripping agent polytetrafluoroethylene micro powder.

[0087] The PC / ABS alloy material of this embodiment was prepared according to the preparation method of Example 1, wherein ABS-g-MAH was dried at 90°C until the water content was less than 0.1 wt%.

[0088] Example 7

[0089] The difference between this embodiment and Example 6 is that in Example 6, the modified graphene obtained in Preparation Example 2 is replaced with an equal weight of the modified graphene obtained in Preparation Example 3. The remaining steps remain unchanged.

[0090] Example 8

[0091] The difference between this embodiment and Embodiment 6 is that in Embodiment 6, the flame retardant DOPO is replaced with an equal weight of the flame retardant RDP. The remaining steps remain unchanged.

[0092] Example 9

[0093] The difference between this embodiment and Embodiment 6 is that, in Embodiment 6, the flame retardant DOPO is not added. The remaining steps remain unchanged.

[0094] Comparative Example 4

[0095] The difference between this comparative example and Example 6 is that in Example 6, the modified graphene was replaced with an equal weight of Hummers GO treated with trimethyloxysilane. The remaining steps remained unchanged.

[0096] Comparative Example 5

[0097] The difference between this comparative example and Example 6 is that in Example 6, the modified graphene was replaced with an equal weight of the polysiloxane-modified GO from Preparation Example 2. The remaining steps remained unchanged. Significant incompatibility was found in the obtained PC / ABS alloy material, mainly due to the incompatibility between the polysiloxane segments and the PC / ABS alloy.

[0098] Blank example

[0099] The modified graphene obtained in Preparation Example 2 was not added in Example 6.

[0100] Performance test results

[0101] Needle flame retardant performance: Tested according to the above-mentioned needle flame retardant performance test method.

[0102] Impact strength: Tested at 23℃ according to the method of GB / T21189-2007.

[0103] Low temperature resistance: The impact strength at -30℃ was tested according to the above-mentioned impact strength test method.

[0104] The results are shown in Table 2 below.

[0105] Table 2 Performance Test Results

[0106]

[0107] As can be seen from the data in Table 2 above, the modified graphene of the present invention has both flame-retardant and toughening effects on PC / ABS alloys, which can improve the flame-retardant and impact resistance of PC / ABS alloy materials, and also has a significant effect on improving the low-temperature resistance of PC / ABS alloy materials.

[0108] As described above, the basic principles, main features, and advantages of the present invention have been shown and described. Those skilled in the art should understand that the present invention is not limited to the above embodiments, which are merely preferred embodiments and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made in accordance with the scope of the patent and the description should still fall within the scope of the present invention. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A needle-flame resistant flame-retardant PC / ABS alloy material, characterized in that, The raw material components, by weight, include 100 parts PC / ABS alloy and 1-15 parts modified graphene; The modified graphene is a graphene chemically grafted polysiloxane-modified maleic anhydride graft polymer. The polysiloxane-modified maleic anhydride graft polymer is chemically grafted onto the graphene via polysiloxane segments. The maleic anhydride grafted polymer is selected from one or a combination of two or more of maleic anhydride grafted ABS, maleic anhydride grafted EVA, maleic anhydride grafted SEBS, maleic anhydride grafted SAN, and maleic anhydride grafted POE. The method for preparing the modified graphene includes: Polysiloxane-modified graphene was obtained by reacting graphene oxide with diamino-terminated polysiloxane. The modified graphene is obtained by reacting the polysiloxane-modified graphene with the maleic anhydride graft polymer.

2. The needle-flame resistant flame-retardant PC / ABS alloy material according to claim 1, characterized in that, The weight ratio of the graphene oxide to the double-terminated amino polysiloxane is 1:0.1-10.

3. The needle-flame resistant flame-retardant PC / ABS alloy material according to claim 1 or 2, characterized in that, The structure of the double-terminated amino polysiloxane is shown in formula (1) below. NH2R 1 Sime2(OSiMeR) 2 ) n OSiMe2R 1 NH2(1) Among them, R 1 Selected from C2-C6 divalent alkyl groups or substituted C3-C10 divalent alkyl groups, R 2 Selected from C1-C12 alkyl, aromatic, and cycloalkyl groups, with Me representing methyl and n=5-100.

4. The needle-flame resistant flame-retardant PC / ABS alloy material according to claim 1, characterized in that, The graphene oxide and the double-terminated amino polysiloxane are then reduced, and the reducing agent used for the reduction is selected from one or a combination of two or more of sodium borohydride, hydrogen, glucose, hydrazine hydrate, dimethylhydrazine, ascorbic acid and ascorbate.

5. The needle-flame resistant flame-retardant PC / ABS alloy material according to claim 1, characterized in that, The weight ratio of the polysiloxane-modified graphene to the maleic anhydride graft polymer is 1:0.2-3.

6. The needle-flame resistant flame-retardant PC / ABS alloy material according to claim 1, characterized in that, The grafting rate of the maleic anhydride-grafted polymer is 1-10 wt%.

7. The needle-flame resistant flame-retardant PC / ABS alloy material according to claim 1, characterized in that, The raw material components also include one or a combination of two or more of the following: 0.5-5 parts of phosphorus-based flame retardant, 0.1-1 parts of antioxidant, 0.1-1 parts of UV stabilizer, and 0-0.1 parts of anti-dripping agent.

8. A method for preparing the needle-flame resistant flame-retardant PC / ABS alloy material according to any one of claims 1-7, characterized in that, The raw material components are mixed evenly, added to a screw extruder for melt extrusion, and shaped to obtain the needle flame retardant PC / ABS alloy material.

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