Halogen-free flame-retardant antistatic PC / ABS alloy and preparation method thereof

Abstract

The invention provides a halogen-free flame-retardant antistatic PC / ABS alloy and a preparation method thereof, and belongs to the technical field of materials. The flame-retardant antistatic polycarbonate composite material is prepared from the following raw materials in parts by weight: 50-70 parts of polycarbonate resin, 5-10 parts of acrylonitrile-butadiene-styrene plastic, 8-12 parts of a flame-retardant antistatic modifier, 0.3-0.5 part of an anti-dripping agent, 1-3 parts of an auxiliary agent and 0.5-1 part of a compatibilizer. The halogen-free flame-retardant antistatic PC / ABS alloy prepared by the invention effectively enhances the overall mechanical strength of a composite material, so that the composite material has better wear resistance, extrusion resistance, tensile resistance and impact resistance, meanwhile, the thermal conductivity is obviously improved, the antistatic property, oxidation resistance and radiation resistance are good, the flame retardant property is extremely good, and the halogen-free flame-retardant antistatic PC / ABS alloy has a wide application prospect.

Description

Technical Field

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

[0002] PC / ABS alloy is one of the earliest polycarbonate modified products to achieve industrial production and is an important engineering plastic alloy. PC / ABS alloy combines the advantages of PC and ABS. On the one hand, the alloy can improve the heat resistance and tensile strength of ABS. On the other hand, the alloy can reduce the melt viscosity of PC, improving processing performance. It can be used to form large-area and complex products. It can also reduce internal stress in products and improve low-temperature impact resistance. PC / ABS alloy materials have been widely used in the automotive industry and are the most suitable interior material for automobiles, especially as raw materials for dashboard brackets, covers, vents, brackets, radiator grilles, and steering column covers. Currently, PC / ABS is also widely used in industries such as computers, communication tools, and office equipment.

[0003] Flame retardancy in PC / ABS alloys has been a hot topic in PC / ABS development in recent years. While PC itself possesses a certain degree of flame retardancy (Limiting Oxygen Index (LOI) = 25), this performance decreases when blended with ABS. To meet the application requirements of PC / ABS alloys in electronics, electrical switches, and appliances, flame retardants must be added. Currently, the most common flame retardants include halogen, phosphorus, nitrogen, and inorganic oxides or hydroxides. Bromine-containing flame retardants offer the best flame retardancy, primarily due to the suppression of gas-phase processes. However, halogen-containing flame retardants release large amounts of hydrogen halide gas and smoke during combustion, leading to secondary damage. This can cause severe corrosion of equipment and facilities at the accident site, suffocation of personnel, and significant difficulties in firefighting, rescue, and evacuation. Therefore, halogen-free polymer flame retardant materials and technologies have become a major development direction. However, limitations in toxicity, thermal stability, migration, smoke generation, and dosage limits for phosphorus and nitrogen-based flame retardants limit their practical application.

[0004] Therefore, it is necessary to develop a halogen-free flame retardant and antistatic PC / ABS alloy material. Summary of the Invention

[0005] The purpose of the present invention is to provide a halogen-free flame-retardant and antistatic PC / ABS alloy and a preparation method thereof, which effectively enhances the overall mechanical strength of the composite material, makes it more resistant to wear, extrusion and stretching, and has good impact resistance. At the same time, the thermal conductivity is significantly improved, and the antistatic, anti-oxidation and anti-radiation properties are excellent, and the flame retardant properties are excellent, which has broad application prospects.

[0006] The technical solution of the present invention is achieved as follows: The invention provides a halogen-free flame-retardant and antistatic PC / ABS alloy, which is prepared from the following raw materials in parts by weight: 50-70 parts of polycarbonate resin, 5-10 parts of acrylonitrile-butadiene-styrene plastic, 8-12 parts of a flame-retardant and antistatic modifier, 0.3-0.5 parts of an anti-dripping agent, 1-3 parts of an auxiliary agent, and 0.5-1 parts of a compatibilizer. The flame-retardant and antistatic modifier is prepared by intercalating a mixture of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene with UiO-66-NH2 and MXene nanosheets, coupling phytic acid and nano-silica, depositing graphene quantum dots on the surface, and subjecting the mixture to tannic acid polymerization modification to prepare the flame-retardant and antistatic modifier.

[0007] As a further improvement of the present invention, the preparation method of the flame retardant antistatic modifier is as follows: S1. Mixing: UiO-66-NH2 and MXene nanosheets are mixed uniformly to prepare a layered mixture; S2 intercalation: 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and a base were added to toluene, the layered mixture was added, the reaction was heated with stirring, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3 coupling reaction: phytic acid, nano-silica, and sodium dihydrogen phosphate were added to water, the intercalated layered mixture was added, hydrothermal reaction was performed, centrifuged, washed, and dried to obtain a phytic acid / nano-silica @ intercalated layered mixture; S4. Deposition of graphene quantum dots: Adding a phytic acid / nanosilica@intercalated layered mixture to water, adding citric acid, heating the mixture, centrifuging, washing, and drying to obtain a graphene quantum dot / phytic acid / nanosilica@intercalated layered mixture; S5. Preparation of a flame retardant and antistatic modifier: A graphene quantum dot / phytic acid / nano-silica intercalated layered mixture was added to a Tris-HCl solution, followed by tannic acid. The mixture was heated and stirred for reaction, followed by centrifugation, washing, and drying to obtain a flame retardant and antistatic modifier.

[0008] As a further improvement of the present invention, the mass ratio of UiO-66-NH2 and MXene nanosheets in step S1 is 10:12-15, and the MXene nanosheets are Ti3C2T x Multilayer nanosheets.

[0009] As a further improvement of the present invention, the mass ratio of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene, base and layered mixture in step S2 is 3-5:4-6:10-12, the temperature of the heating and stirring reaction is 90-100° C., the time is 3-5 hours, and the base is selected from at least one of triethylamine, NaOH, and KOH.

[0010] As a further improvement of the present invention, in step S3, the mass ratio of phytic acid, nano-silica, sodium dihydrogen phosphate, and intercalated layered mixture is 2-3:1-2:0.05-0.1:7-10, and the temperature of the hydrothermal reaction is 140-160° C. and the time is 8-10 h.

[0011] As a further improvement of the present invention, in step S4, the mass ratio of the phytic acid / nano-silica@intercalated layered mixture to citric acid is 10:3-4, the heating reaction temperature is 190-210° C., and the time is 20-24 h.

[0012] As a further improvement of the present invention, the pH value of the Tris-HCl solution in step S5 is 8.5-9.5, the mass ratio of the graphene quantum dots / phytic acid / nanosilica@intercalated layered mixture and tannic acid is 10:2-3, and the temperature of the heating and stirring reaction is 40-50°C and the time is 2-4 hours.

[0013] As a further improvement of the present invention, the auxiliary agent includes antioxidant 1010 and pentaerythritol stearate in a mass ratio of 3-5:2-4, the compatibilizer is maleic anhydride grafted linear low-density polyethylene, and the anti-dripping agent is polytetrafluoroethylene.

[0014] The present invention further protects a method for preparing the above-mentioned halogen-free flame-retardant and antistatic PC / ABS alloy, comprising the following steps: heating and melting polycarbonate resin and acrylonitrile-butadiene-styrene plastic, adding a flame-retardant and antistatic modifier, an anti-dripping agent, an auxiliary agent and a compatibilizer, stirring and mixing uniformly, extruding and granulating, drying, and injection molding to obtain the halogen-free flame-retardant and antistatic PC / ABS alloy.

[0015] As a further improvement of the present invention, the heating and melting temperature is 230-240°C.

[0016] The present invention has the following beneficial effects: The present invention combines a layered metal MOF material with an active amino group and a MXeneTi3C2T3 with a hydroxyl functional group. x After the multilayer nanosheets are mixed, the flame retardant 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene is intercalated through a nucleophilic substitution reaction, which not only expands the interlayer spacing, but also builds a three-dimensional conductive network inside the composite material, improving the conductivity of the material, thereby improving the antistatic properties of the resin. At the same time, it effectively enhances the overall mechanical strength of the composite material, making it more resistant to wear, extrusion and stretching, thereby improving the service life and reliability of the material in practical applications.

[0017] Then, phytic acid is used as a bridging structure to couple the nano-silica and the intercalated layered mixture. Adding phytic acid to the resin improves the flame retardancy and mechanical properties of the resin and improves its compatibility with PC and ABS resins.

[0018] The phytic acid / nanosilica@intercalated layered mixture can adsorb citric acid on its surface by forming hydrogen bonds, and in situ generate graphene quantum dots under hydrothermal reaction conditions, which can absorb and dissipate impact energy to a certain extent, so that the material can better resist deformation and cracking when impacted, thereby improving the toughness and impact resistance of the resin. At the same time, it improves the thermal conductivity and electrical conductivity of the material, provides more channels and carriers for the migration of charges, improves the mobility of charges in the material, and can also effectively remove free radicals generated by the resin in an irradiated environment, slowing down the degradation and aging process of the resin, and improving the radiation resistance of the composite material.

[0019] After the surface of the prepared graphene quantum dots / phytic acid / nanosilica@intercalated layered mixture is modified by tannic acid polymerization, the tannic acid structure can form hydrogen bonds with PC resin, significantly improving the compatibility with PC / ABS resin, avoiding agglomeration and affecting performance, thereby better exerting the modification effect.

[0020] The halogen-free flame-retardant and antistatic PC / ABS alloy prepared by the present invention effectively enhances the overall mechanical strength of the composite material, making it more resistant to wear, extrusion and stretching, and having good impact resistance. At the same time, the thermal conductivity is significantly improved, and the antistatic, anti-oxidation and anti-radiation properties are excellent, as well as the flame retardant property, which has broad application prospects. DETAILED DESCRIPTION

[0021] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0022] UiO-66-NH2 is commercially available or homemade, and the preparation method is as follows: Zirconium tetrachloride (0.725 mmol, 0.169 g) and 2-aminoterephthalic acid (0.725 mmol, 0.132 g) were added to a mixture of DMF (38 mL) and acetic acid (2.1 mL) and homogenized by sonication at 900 W for 30 min. The mixture was then added to a polytetrafluoroethylene-lined hydrothermal reactor and placed in a 120°C constant-temperature forced-air drying oven for 24 h. After cooling, the crude product was separated by centrifugation at 8000 rpm, washed with DMF and methanol, and dried to yield 0.14 g of a yellow powder, UiO-66-NH2.

[0023] MXene Ti3C2T x The multilayer nanosheets are commercially available or homemade, and the preparation method is as follows: 2 g of LiF was weighed and added to a Teflon beaker containing 40 mL of HCl solution (9 mol / L). The mixture was stirred until the LiF was completely dissolved, and 2 g of Ti3AlC2 was slowly added. After etching at 40 ° C for 48 h, the mixture was centrifuged (3500 r / min, 7 min) and repeatedly rinsed with water until the pH was 6 to obtain the Ti3C2TX MXene phase. The phase was then dispersed in water, ultrasonicated in an ice bath for 2 h, and centrifuged again (3500 r / min, 30 min). The supernatant was collected and freeze-dried to obtain MXene Ti3C2T x Multilayer nanosheets.

[0024] Preparation Example 1 Preparation of flame retardant antistatic modifier Here’s how: S1. Mixing: 1g UiO-66-NH2 and 1.2g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Intercalation: 0.3 g of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and 0.4 g of triethylamine were added to 150 mL of toluene, 1 g of the layered mixture was added, the mixture was heated to 90 ° C, stirred for 3 h, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3. Coupling reaction: 0.2 g of phytic acid, 0.1 g of nano-silica, and 0.005 g of sodium dihydrogen phosphate were added to 100 mL of water, and 0.7 g of the intercalated layered mixture was added. The mixture was hydrothermally reacted at 140°C for 8 h, centrifuged, washed, and dried to obtain a phytic acid / nano-silica@intercalated layered mixture. S4. Deposition of graphene quantum dots: 1 g of the phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of water, followed by 0.3 g of citric acid. The mixture was heated to 190°C and stirred for 20 h. The mixture was then centrifuged, washed, and dried to obtain a graphene quantum dot / phytic acid / nanosilica@intercalated layered mixture. S5. Preparation of a flame-retardant and antistatic modifier: 1 g of the graphene quantum dots / phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of a Tris-HCl solution (pH 8.5), and 0.2 g of tannic acid was added. The mixture was heated to 40°C and stirred for 2 h. The mixture was centrifuged, washed, and dried to obtain a flame-retardant and antistatic modifier.

[0025] Preparation Example 2 Preparation of flame retardant antistatic modifier Here’s how: S1. Mixing: 1g UiO-66-NH2 and 1.5g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Intercalation: 0.5 g of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and 0.6 g of NaOH were added to 150 mL of toluene, 1.2 g of the layered mixture was added, heated to 100 ° C, stirred for 5 h, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3. Coupling reaction: 0.3 g phytic acid, 0.2 g nano-silica, and 0.01 g sodium dihydrogen phosphate were added to 100 mL of water, and 1 g of the intercalated layered mixture was added. The mixture was hydrothermally reacted at 160°C for 10 h, centrifuged, washed, and dried to obtain a phytic acid / nano-silica@intercalated layered mixture. S4. Deposition of graphene quantum dots: 1 g of the phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of water, followed by 0.4 g of citric acid. The mixture was heated to 210°C and stirred for 24 h. The mixture was then centrifuged, washed, and dried to obtain a graphene quantum dot / phytic acid / nanosilica@intercalated layered mixture. S5. Preparation of a flame-retardant and antistatic modifier: 1 g of the graphene quantum dots / phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of a Tris-HCl solution (pH 9.5), and 0.3 g of tannic acid was added. The mixture was heated to 50°C and stirred for 4 h. The mixture was centrifuged, washed, and dried to obtain a flame-retardant and antistatic modifier.

[0026] Preparation Example 3 Preparation of flame retardant antistatic modifier Here’s how: S1. Mixing: 1g UiO-66-NH2 and 1.35g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Intercalation: 0.4 g of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and 0.5 g of KOH were added to 150 mL of toluene, 1.1 g of the layered mixture was added, heated to 95 ° C, stirred for 4 h, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3. Coupling reaction: 0.25 g of phytic acid, 0.15 g of nano-silica, and 0.007 g of sodium dihydrogen phosphate were added to 100 mL of water, and 0.85 g of the intercalated layered mixture was added. The mixture was hydrothermally reacted at 150°C for 9 h, centrifuged, washed, and dried to obtain a phytic acid / nano-silica@intercalated layered mixture. S4. Deposition of graphene quantum dots: 1 g of the phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of water, followed by 0.35 g of citric acid. The mixture was heated to 200°C and stirred for 22 h. The mixture was then centrifuged, washed, and dried to obtain a graphene quantum dot / phytic acid / nanosilica@intercalated layered mixture. S5. Preparation of a flame-retardant and antistatic modifier: 1 g of the graphene quantum dots / phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of a Tris-HCl solution (pH 9), and 0.25 g of tannic acid was added. The mixture was heated to 45°C and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a flame-retardant and antistatic modifier.

[0027] Comparative Preparation Example 1 Compared with Preparation Example 3, the difference is that UiO-66-NH2 is not added in step S1.

[0028] The details are as follows: S1. Mix 2.35g of UiO-66-NH2 evenly to obtain a layered product.

[0029] Comparative Preparation Example 2 Compared with Preparation Example 3, the difference is that MXene Ti3C2T is not added in step S1. x Multilayer nanosheets.

[0030] The details are as follows: S1. 2.35g MXene Ti3C2T x The multiple layers of nanosheets are mixed evenly to obtain a layered object.

[0031] Comparative Preparation Example 3 Compared with Preparation Example 3, the difference is that step S2 is not performed.

[0032] The details are as follows: S1. Mixing: 1g UiO-66-NH2 and 1.35g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Coupling reaction: 0.25 g of phytic acid, 0.15 g of nano-silica, and 0.007 g of sodium dihydrogen phosphate were added to 100 mL of water, and 0.85 g of the layered mixture was added. The mixture was hydrothermally reacted at 150°C for 9 h, centrifuged, washed, and dried to obtain a phytic acid / nano-silica@layered mixture. S3. Deposition of graphene quantum dots: 1 g of the phytic acid / nanosilica@layered mixture was added to 100 mL of water, followed by 0.35 g of citric acid. The mixture was heated to 200°C and stirred for 22 h. The mixture was centrifuged, washed, and dried to obtain a graphene quantum dot / phytic acid / nanosilica@layered mixture. S4. Preparation of a flame-retardant and antistatic modifier: 1 g of the graphene quantum dots / phytic acid / nanosilica@layered mixture was added to 100 mL of a Tris-HCl solution (pH 9), and 0.25 g of tannic acid was added. The mixture was heated to 45°C and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a flame-retardant and antistatic modifier.

[0033] Comparative Preparation Example 4 Compared with Preparation Example 3, the difference is that step S3 is not performed.

[0034] The details are as follows: S1. Mixing: 1g UiO-66-NH2 and 1.35g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Intercalation: 0.4 g of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and 0.5 g of KOH were added to 150 mL of toluene, 1.1 g of the layered mixture was added, heated to 95 ° C, stirred for 4 h, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3. Deposition of graphene quantum dots: 1 g of the intercalated layered mixture was added to 100 mL of water, 0.35 g of citric acid was added, and the mixture was heated to 200°C with stirring for 22 h. The mixture was then centrifuged, washed, and dried to obtain a graphene quantum dot-intercalated layered mixture. S4. Preparation of a flame-retardant and antistatic modifier: 1 g of the graphene quantum dot-intercalated layered mixture was added to 100 mL of a Tris-HCl solution having a pH of 9, and 0.25 g of tannic acid was added. The mixture was heated to 45°C and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a flame-retardant and antistatic modifier.

[0035] Comparative Preparation Example 5 Compared with Preparation Example 3, the difference is that step S4 is not performed.

[0036] The details are as follows: S1. Mixing: 1g UiO-66-NH2 and 1.35g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Intercalation: 0.4 g of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and 0.5 g of KOH were added to 150 mL of toluene, 1.1 g of the layered mixture was added, heated to 95 ° C, stirred for 4 h, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3. Coupling reaction: 0.25 g of phytic acid, 0.15 g of nano-silica, and 0.007 g of sodium dihydrogen phosphate were added to 100 mL of water, and 0.85 g of the intercalated layered mixture was added. The mixture was hydrothermally reacted at 150°C for 9 h, centrifuged, washed, and dried to obtain a phytic acid / nano-silica@intercalated layered mixture. S4. Preparation of a flame-retardant and antistatic modifier: 1 g of the phytic acid / nanosilica@intercalated layered mixture was added to 100 mL of a Tris-HCl solution (pH 9), and 0.25 g of tannic acid was added. The mixture was heated to 45°C and stirred for 3 h. The mixture was centrifuged, washed, and dried to obtain a flame-retardant and antistatic modifier.

[0037] Comparative Preparation Example 6 Compared with Preparation Example 3, the difference is that step S5 is not performed.

[0038] The details are as follows: S1. Mixing: 1g UiO-66-NH2 and 1.35g MXene Ti3C2T x The multiple layers of nanosheets are mixed uniformly to obtain a layered mixture; S2. Intercalation: 0.4 g of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and 0.5 g of KOH were added to 150 mL of toluene, 1.1 g of the layered mixture was added, heated to 95 ° C, stirred for 4 h, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3. Coupling reaction: 0.25 g of phytic acid, 0.15 g of nano-silica, and 0.007 g of sodium dihydrogen phosphate were added to 100 mL of water, and 0.85 g of the intercalated layered mixture was added. The mixture was hydrothermally reacted at 150°C for 9 h, centrifuged, washed, and dried to obtain a phytic acid / nano-silica@intercalated layered mixture. S4. Deposition of graphene quantum dots: 1 g of the phytic acid / nano-silica@intercalated layered mixture was added to 100 mL of water, and 0.35 g of citric acid was added. The mixture was heated to 200°C and stirred for 22 hours. The mixture was centrifuged, washed, and dried to obtain a graphene quantum dot / phytic acid / nano-silica@intercalated layered mixture, which was a flame retardant and antistatic modifier.

[0039] Example 1 This example provides a halogen-free, flame-retardant, and antistatic PC / ABS alloy, prepared from the following raw materials, by weight: 50 parts polycarbonate resin (PC), 5 parts acrylonitrile-butadiene-styrene plastic (ABS), 8 parts of the flame-retardant and antistatic modifier prepared in Preparation Example 1, 1 part additive, 0.3 parts of polytetrafluoroethylene (PTFE), an anti-drip agent, and 0.5 parts of maleic anhydride-grafted linear low-density polyethylene. The additives include antioxidant 1010 and pentaerythritol stearate, in a mass ratio of 3:2.

[0040] The preparation method comprises the following steps: heating polycarbonate resin and acrylonitrile-butadiene-styrene plastic to 230° C. to melt, adding a flame retardant and antistatic modifier, an anti-dripping agent polytetrafluoroethylene, an auxiliary agent and a compatibilizer, stirring and mixing evenly, extruding and granulating, drying, and injection molding to obtain a halogen-free flame retardant and antistatic PC / ABS alloy.

[0041] Example 2 This example provides a halogen-free, flame-retardant, and antistatic PC / ABS alloy, prepared from the following raw materials, by weight: 70 parts polycarbonate resin, 10 parts acrylonitrile-butadiene-styrene plastic, 12 parts flame-retardant and antistatic modifier prepared in Preparation Example 2, 3 parts additives, 0.5 parts polytetrafluoroethylene (PTFE) as an anti-drip agent, and 1 part maleic anhydride-grafted linear low-density polyethylene. The additives include antioxidant 1010 and pentaerythritol stearate, in a mass ratio of 5:4.

[0042] The preparation method comprises the following steps: heating polycarbonate resin and acrylonitrile-butadiene-styrene plastic to 240°C to melt, adding a flame retardant and antistatic modifier, an anti-dripping agent polytetrafluoroethylene, an auxiliary agent and a compatibilizer, stirring and mixing evenly, extruding and granulating, drying, and injection molding to obtain a halogen-free flame retardant and antistatic PC / ABS alloy.

[0043] Example 3 This example provides a halogen-free, flame-retardant, and antistatic PC / ABS alloy, prepared from the following raw materials, by weight: 60 parts polycarbonate resin, 8 parts acrylonitrile-butadiene-styrene plastic, 10 parts flame-retardant and antistatic modifier prepared in Preparation Example 3, 0.4 parts polytetrafluoroethylene (PTFE) as an anti-drip agent, 2 parts additives, and 0.7 parts maleic anhydride-grafted linear low-density polyethylene. The additives include antioxidant 1010 and pentaerythritol stearate, in a mass ratio of 4:3.

[0044] The preparation method comprises the following steps: heating polycarbonate resin and acrylonitrile-butadiene-styrene plastic to 235° C. to melt, adding a flame retardant and antistatic modifier, an anti-dripping agent polytetrafluoroethylene, an auxiliary agent and a compatibilizer, stirring and mixing evenly, extruding and granulating, drying, and injection molding to obtain a halogen-free flame retardant and antistatic PC / ABS alloy.

[0045] Comparative Example 1 Compared with Example 3, the difference is that the flame retardant antistatic modifier is prepared by Comparative Preparation Example 1.

[0046] Comparative Example 2 Compared with Example 3, the difference is that the flame retardant antistatic modifier is prepared by Comparative Preparation Example 2.

[0047] Comparative Example 3 Compared with Example 3, the difference is that the flame retardant antistatic modifier is prepared by Comparative Preparation Example 3.

[0048] Comparative Example 4 Compared with Example 3, the difference is that the flame retardant antistatic modifier is prepared by Comparative Preparation Example 4.

[0049] Comparative Example 5 Compared with Example 3, the difference is that the flame retardant antistatic modifier is prepared by Comparative Preparation Example 5.

[0050] Comparative Example 6 Compared with Example 3, the difference is that the flame retardant antistatic modifier is prepared by Comparative Preparation Example 6.

[0051] Test Example 1 The halogen-free flame-retardant and antistatic PC / ABS alloys prepared in Examples 1-3 and Comparative Examples 1-6 were tested for thermal conductivity and flame retardancy. The results are shown in Table 1.

[0052] (1) Thermal conductivity (TC) was measured using an Elmer Pyris thermal conductivity probe and reported in Watts per Kelvin-meter (W / mK). Measurements were performed on injection-molded sheets at room temperature. (2) Limiting oxygen index (LOI): tested in accordance with GB / T 2406.2-2009, sample size 80 mm × 10 mm × 4 mm; (3) Vertical burning performance: tested in accordance with GB / T 2408-2021, sample size: 125 mm × 12.5 mm × 3.2 mm; (4) HDT (heat deformation temperature) is tested in accordance with the provisions of GB / T1634.2-2004, with a load of 1.8 MPa.

[0053] Table 1

[0054] It can be seen from the above table that the halogen-free flame-retardant and antistatic PC / ABS alloys prepared in Examples 1-3 of the present invention have good thermal conductivity, heat resistance and flame retardancy.

[0055] Test Example 2 The halogen-free flame retardant and antistatic PC / ABS alloys prepared in Examples 1-3 and Comparative Examples 1-6 were subjected to mechanical property and antistatic tests. The results are shown in Table 2.

[0056] (1) Notched impact strength is tested in accordance with the provisions of GB / T1843-2008, and the notch type is type A; (2) Tensile strength and elongation at break: measured in accordance with the provisions of GB / T 1040.2-2022, with a tensile rate of 50.00 mm / min, a 4 mm thick 1A dumbbell-shaped standard specimen, and a test temperature of 22 ± 3 °C.

[0057] (3) Antistatic performance: Surface resistivity is tested according to ASTM D257.

[0058] Table 2

[0059] It can be seen from the above table that the halogen-free flame retardant and antistatic PC / ABS alloys prepared in Examples 1-3 of the present invention have good mechanical properties.

[0060] Test Example 3 The halogen-free flame-retardant and antistatic PC / ABS alloys prepared in Examples 1-3 and Comparative Examples 1-6 were subjected to an aging resistance test.

[0061] The aging test performance retention rate is tested in accordance with the provisions of GB / T16422.3, the test method is A, the test conditions are as shown in the standard cycle number 1, and the tensile strength retention rate is measured after the test time is 500h.

[0062] The results are shown in Table 3.

[0063]

[0064] It can be seen from the above table that the halogen-free flame retardant and antistatic PC / ABS alloys prepared in Examples 1-3 of the present invention have good aging resistance.

[0065] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A halogen-free flame-retardant antistatic PC / ABS alloy, characterized in that: The invention is prepared from the following raw materials in parts by weight: 50-70 parts of polycarbonate resin, 5-10 parts of acrylonitrile-butadiene-styrene plastic, 8-12 parts of a flame retardant and antistatic modifier, 0.3-0.5 parts of an anti-dripping agent, 1-3 parts of an auxiliary agent, and 0.5-1 parts of a compatibilizer. The flame retardant and antistatic modifier is prepared by intercalating a mixture of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene with UiO-66-NH2 and MXene nanosheets, coupling phytic acid and nano-silica, depositing graphene quantum dots on the surface, and subjecting the mixture to tannic acid polymerization modification to obtain the flame retardant and antistatic modifier.

2. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 1, characterized in that: The preparation method of the flame retardant antistatic modifier is as follows: S1. Mixing: UiO-66-NH2 and MXene nanosheets were mixed to obtain a layered mixture. S2 intercalation: 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene and a base were added to toluene, the layered mixture was added, the reaction was heated with stirring, centrifuged, washed, and dried to obtain an intercalated layered mixture; S3 coupling reaction: phytic acid, nano-silica, and sodium dihydrogen phosphate were added to water, the intercalated layered mixture was added, hydrothermal reaction was performed, centrifuged, washed, and dried to obtain a phytic acid / nano-silica @ intercalated layered mixture; S4. Deposition of graphene quantum dots: Adding a phytic acid / nanosilica@intercalated layered mixture to water, adding citric acid, heating the mixture, centrifuging, washing, and drying to obtain a graphene quantum dot / phytic acid / nanosilica@intercalated layered mixture; S5. Preparation of a flame retardant and antistatic modifier: A graphene quantum dot / phytic acid / nano-silica intercalated layered mixture was added to a Tris-HCl solution, followed by tannic acid. The mixture was heated and stirred for reaction, followed by centrifugation, washing, and drying to obtain a flame retardant and antistatic modifier.

3. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 2, characterized in that: The mass ratio of UiO-66-NH2 and MXene nanosheets in step S1 is 10:12-15, and the MXene nanosheets are Ti3C2T x Multilayer nanosheets.

4. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 2, characterized in that: The mass ratio of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene, base and layered mixture in step S2 is 3-5:4-6:10-12, the temperature of the heating and stirring reaction is 90-100° C., the time is 3-5 hours, and the base is selected from at least one of triethylamine, NaOH and KOH.

5. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 2, characterized in that: In step S3, the mass ratio of phytic acid, nano-silica, sodium dihydrogen phosphate, and intercalated layered mixture is 2-3:1-2:0.05-0.1:7-10, and the temperature of the hydrothermal reaction is 140-160° C., and the time is 8-10 hours.

6. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 2, characterized in that: In step S4, the mass ratio of the phytic acid / nano-silica@intercalated layered mixture to citric acid is 10:3-4, and the heating reaction temperature is 190-210° C. for 20-24 hours.

7. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 2, characterized in that: The pH value of the Tris-HCl solution in step S5 is 8.5-9.5, the mass ratio of the graphene quantum dots / phytic acid / nanosilica@intercalated layered mixture and tannic acid is 10:2-3, the temperature of the heating and stirring reaction is 40-50° C., and the time is 2-4 hours.

8. The halogen-free flame-retardant and antistatic PC / ABS alloy according to claim 1, characterized in that: The auxiliary agent includes antioxidant 1010 and pentaerythritol stearate in a mass ratio of 3-5:2-4. The compatibilizer is maleic anhydride grafted linear low-density polyethylene. The anti-dripping agent is polytetrafluoroethylene.

9. A method for preparing a halogen-free flame-retardant and antistatic PC / ABS alloy according to any one of claims 1 to 8, characterized in that: The following steps are involved: The polycarbonate resin and acrylonitrile-butadiene-styrene plastic are heated and melted, and a flame retardant and antistatic modifier, an anti-dripping agent, an auxiliary agent and a compatibilizer are added, stirred and mixed evenly, extruded into granules, dried, and injection molded to obtain a halogen-free flame retardant and antistatic PC / ABS alloy.

10. The preparation method according to claim 9, characterized in that The heating and melting temperature is 230-240°C.

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