A preparation method of a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material and a phosphorus-silicon flame retardant

Abstract

The present invention relates to a preparation method of a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material and a phosphorus-silicon flame retardant, comprising the following steps: adding phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinyl double-end capping agent into a mixed system of methanol and water according to a ratio, stirring evenly, adding an acidic catalyst, adjusting the pH value, neutralizing, washing after the reaction is completed, and performing low-boiling-point removal at -0.098 MPa and 85 °C to obtain an intermediate; adding a DOPO flame retardant with an equimolar ratio of vinyl to that in the vinyl double-end capping agent and DMF with a mass ratio equal to that of the intermediate to the intermediate, heating to 60 °C to 75 °C and reacting for 4 to 12 h, filtering, washing and drying to obtain the phosphorus-silicon flame retardant. By this method, the present invention can synthesize a novel flame retardant containing both phosphorus and silicon elements, and adding it into the PC / ABS alloy to prepare a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material.

Description

Technical Field

[0001] The present invention relates to the technical field of alloy flame retardant materials, and particularly relates to a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material and a preparation method of a phosphorus-silicon flame retardant. Background Art

[0002] In modern industry, polycarbonate / acrylonitrile-butadiene-styrene (PC / ABS) alloys have become ideal materials in fields such as electronics and electrical appliances, the automotive industry, and household appliance casings due to their excellent comprehensive properties, such as good mechanical strength, heat resistance, dimensional stability, and impact toughness. However, with the increasing complexity of application scenarios, especially in the field of electronics and electrical appliances, higher requirements for flame retardancy, safety, and environmental protection have been put forward for materials. Traditional PC / ABS alloy flame retardant materials mostly use halogen-based flame retardants, such as bromides and chlorides. These materials may release toxic and harmful hydrogen halide gases and carcinogenic substances such as dioxins during combustion, seriously threatening human health and causing irreversible damage to the environment. Therefore, the development of a halogen-free, low-smoke, and high-modulus flame retardant material has become an important research direction in current materials science.

[0003] Halogen-free flame retardant materials have received increasing attention due to their environmental advantages. Traditional halogen-based flame retardants produce a large amount of thick smoke and harmful gases during combustion, while halogen-free flame retardants can significantly reduce the generation of smoke and harmful substances while achieving an efficient flame retardant effect, and are particularly suitable for fields with strict environmental requirements. The core of halogen-free flame retardant technology is the use of environmentally friendly flame retardants to replace halogens, such as phosphorus-based, nitrogen-based, and silicon-based flame retardants. They do not produce toxic gases during combustion and provide protection through multiple flame retardant mechanisms, such as the formation of a condensed-phase carbonized layer and the capture of active free radicals in the gas phase, thereby inhibiting the propagation and development of flames.

[0004] Among many halogen-free flame retardant systems, the phosphorus-silicon synergistic flame retardant system exhibits unique advantages. Phosphorus-based flame retardants can promote the formation of a dense carbonized layer on the material surface at high temperatures, effectively isolating heat and oxygen and preventing further combustion. Silicon-based flame retardants generate a silicon dioxide (SiO) protective layer at high temperatures, enhancing the heat resistance and fire resistance of the material. The synergistic effect of phosphorus-silicon flame retardants can not only effectively improve the flame retardant performance of PC / ABS alloys, but also reduce the generation of smoke and improve the safety during the combustion process. In addition, the phosphorus-silicon flame retardant system has little impact on the mechanical properties of PC / ABS materials, and can maintain or enhance the high-modulus characteristics of the materials, adapting to application scenarios with high requirements for strength and rigidity.

[0005] In the development process of halogen-free flame-retardant PC / ABS alloy materials, in addition to flame retardancy and environmental protection, the mechanical properties of the materials, especially the modulus, also need to be considered. High-modulus PC / ABS alloy materials have better rigidity and load-bearing capacity in applications, and are particularly suitable for occasions with high requirements for strength, rigidity and durability, such as automotive interior and exterior trim parts, and the housings of electronic and electrical equipment. Therefore, the research on low-smoke, high-modulus halogen-free flame-retardant PC / ABS alloy materials has important technical and market value.

[0006] Current research mainly focuses on improving the flame retardancy and mechanical properties of PC / ABS alloys by introducing different types of phosphorus-based and silicon-based flame retardants. Phosphorus-based flame retardants can form a stable glassy or ceramic-like carbonized layer through dehydration condensation during combustion, effectively isolating the heat source and oxygen and preventing flame propagation; the silica layer generated by silicon-based flame retardants during combustion can further improve the thermal stability of the material and reduce the flame spread rate. By reasonably designing the phosphorus-silicon ratio, excellent flame retardant effects can be achieved with a lower addition amount of flame retardants, while maintaining the high modulus and low-smoke characteristics of the material.

[0007] In the specific preparation process, the uniform dispersion of phosphorus-silicon-based flame retardants and their compatibility with the PC / ABS matrix material are key technical problems. The dispersion uniformity and compatibility of flame retardants directly affect the final performance of flame-retardant materials. To ensure the effective dispersion of flame retardants in PC / ABS alloys, surface modification techniques or specific dispersants are usually required to enhance the interfacial bonding between the flame retardants and the matrix resin. In addition, process parameters such as processing temperature, pressure, and mixing speed also need to be precisely optimized to ensure the thermal stability, mechanical properties, and flame retardant properties of the materials during processing.

[0008] In addition, the low-smoke characteristic is also one of the key performance indicators in the development of modern flame-retardant materials. The smoke generated by flame-retardant materials during combustion not only affects the visibility at the fire scene but also poses serious health risks. By adjusting the chemical structure of phosphorus-silicon-based flame retardants and their dispersion state in the material, the smoke density during combustion can be significantly reduced, thereby enhancing the safety of the material.

[0009] Chinese Patent CN102604315A discloses a low-smoke-density PC / ABS alloy for automotive interior parts and its preparation method. By compounding and using four kinds of flame retardants and smoke suppressants such as zinc borate, molybdenum trioxide, ammonium octamolybdate, and zinc molybdate, the flame retardant effect is effectively improved in the PC / ABS alloy, and more effectively, the smoke density can be reduced and the smoke can be efficiently suppressed. However, molybdenum compounds such as molybdenum trioxide, ammonium octamolybdate, and zinc molybdate are also used in this patent. Chinese Patent CN112111142A discloses a low-smoke-density, flame-retardant PC / ABS alloy material and its preparation method. Using polydimethylsiloxane, zinc borate, and 10 - 12 parts of a phosphate ester flame retardant will sacrifice a part of the mechanical strength of the alloy while reducing the smoke density. Chinese Patent CN106995602A discloses a high-modulus, high-flow, halogen-free flame-retardant PC / ABS alloy material and its preparation method. Using carbon fiber as a reinforcing material, polyaryl phosphate and ultrafine phosphate as flame retardants, silicon-based triazine as a charring synergist and adding an MBS toughening agent, where the PX200 flame retardant exceeds 10 parts, which affects the modulus of the alloy itself to a certain extent. Summary of the Invention

[0010] In order to overcome the shortcomings and deficiencies existing in the prior art, the purpose of the present invention is to provide a preparation method of a phosphorus-silicon-containing flame retardant. Through this method, a new type of flame retardant containing both phosphorus and silicon elements can be synthesized, and adding it to the PC / ABS alloy can prepare a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material.

[0011] Another purpose of the present invention is to provide a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material. By adding a phosphorus-silicon-containing flame retardant, the flame retardancy of the PC / ABS material is improved, the dosage of traditional phosphate flame retardants is reduced, and the influence on the tensile strength, flexural modulus, and heat distortion temperature of the alloy is reduced; in addition, the phosphorus-silicon-containing flame retardant itself is highly compatible with PC / ABS and is easy to form a ceramic barrier layer with zinc borate, triphenylboric acid, and octamolybdenum during combustion, having the functions of smoke suppression, flame retardancy, and preventing the molten body from dripping. The prepared flame retardant material can be widely used in the production of automotive instrument display housings, household appliances, communication electronic and electrical components, and rail transit interior parts.

[0012] The purpose of the present invention is achieved through the following technical solutions: A preparation method of a phosphorus-silicon-containing flame retardant, comprising the following steps:

[0013] S1. Add phenyltrimethoxysiloxane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane into the mixed system of methanol and water according to a ratio. After stirring evenly, add an acidic catalyst, adjust the pH value to 4 - 6, control the temperature at 0 °C to 45 °C, and react for 8 - 12 h. Then neutralize, wash, and remove the low boilers at -0.098 MPa and 85 °C to obtain an intermediate for standby.

[0014] S2. Add a DOPO flame retardant with an equimolar ratio of vinyl to that in vinylbistrimethylsiloxysilane and DMF with a mass ratio equal to that of the intermediate to the intermediate obtained in step S1. Heat to 60 °C - 75 °C and react for 4 - 12 h. Then filter, wash, and dry to obtain a phosphorus-containing silicone flame retardant.

[0015] The phosphorus-containing silicone flame retardant in the present invention is prepared by the above method. By using the above method, a novel flame retardant containing both phosphorus and silicon elements can be synthesized. Adding it to the PC / ABS alloy can prepare a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material.

[0016] In addition, in the present invention, under acidic conditions, two of phenyltrimethoxysiloxane, diphenyldimethoxysilane, methylphenyldimethoxysilane, and dimethyldimethoxysilane, and vinylbistrimethylsiloxysilane or tetramethyltetravinylcyclotetrasiloxane are subjected to equilibrium polycondensation in an alcohol aqueous solution according to the above ratio, and then reacted with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and a solvent under heating conditions for several hours, and a non-polar solvent is added to obtain a phosphorus-containing silicone flame retardant.

[0017] Preferably, phenyltrimethoxysiloxane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane are mixed in a molar ratio of 0.1 - 3:0.5 - 4:0.1 - 0.5; the methanol and water form a mixed system according to a mass ratio of 1:0.8 - 1.2.

[0018] Preferably, the mass ratio of the mixture of phenyltrimethoxysiloxane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane to the amount of the mixed system of methanol and water is 1:0.8 - 1.2.

[0019] Preferably, phenyltrimethoxysiloxane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane are mixed in a molar ratio of 0.1 - 1:0.5 - 4:0.1 - 0.4, and its solid content is 35% - 60%.

[0020] Preferably, the acidic catalyst is at least one of benzenesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid, and strong acid hydrogen salts.

[0021] The present invention also provides a halogen-free flame-retardant material for low-smoke and high-modulus PC / ABS alloy, comprising the following raw materials in parts by weight: 30-60 parts of PC resin, 5-30 parts of ABS resin, 1-3 parts of silicone synergistic flame-retardant additive, 1-3 parts of silicone toughening agent, 3-5 parts of phosphorus-silicon-containing flame retardant, 0.1-2 parts of sulfonate flame retardant, 1-5 parts of zinc borate, 1-3 parts of triphenylboric acid, 0.1-0.5 parts of octamolybdenum, 0.5-3 parts of phosphate ester flame retardant, 0.1-0.5 parts of anti-dripping agent, 0.3-1 part of antioxidant, 0.2-0.5 part of ultraviolet absorber, and 0.5-1 part of lubricant.

[0022] The present invention improves the flame retardancy of PC / ABS material by adding phosphorus-silicon-containing flame retardant to the flame-retardant material, reduces the dosage of traditional phosphate ester flame retardant, and reduces the influence on the tensile strength, flexural modulus and heat distortion temperature of the alloy; in addition, the phosphorus-silicon-containing flame retardant is highly compatible with PC / ABS itself, and is easy to combine with zinc borate, triphenylboric acid and octamolybdenum during the combustion process to form a ceramic barrier layer, which has the functions of smoke suppression, flame retardancy and preventing the molten body from dripping, and the prepared flame-retardant material can be widely used in the production of automotive instrument display housings, household appliances, communication electronic and electrical components and rail transit interior parts.

[0023] Preferably, the melt index of the PC resin is 8-12 g / 10 min.

[0024] Preferably, the silicone synergistic flame-retardant additive is phenylsilsesquioxane, preferably SIFR-907 or SIFR-908 provided by Quansheng Polycarbon Technology Co., Ltd.

[0025] Preferably, the sulfonate flame retardant is selected from Quansheng KKS-A2, 870M, 5100, 6100 or KSS, HES, HES-2 of Arichem.

[0026] Preferably, the silicone toughening agent is selected from at least one of USI3310, USI3305 and USI3306 of Quansheng.

[0027] Preferably, the anti-dripping agent is selected from at least one of KT-107, KT201 and KT-P205 of Quansheng.

[0028] Preferably, the phosphate ester flame retardant is at least one of FCR210, SPB-100, HM1100, PX200 and PX220.

[0029] Preferably, the antioxidant is composed of a main antioxidant and a co-antioxidant. The main antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076 and antioxidant MD-697; the co-antioxidant is selected from at least one of antioxidant 168 and antioxidant 412S.

[0030] The low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material is prepared by the following method:

[0031] A1. Dry the PC resin at 120-130 °C until the water content is less than 0.025%, and set aside;

[0032] A2. Dry the ABS resin at 85-90 °C until the water content is less than 0.025%. Weigh various raw materials according to parts by weight, and then mix all the raw materials evenly, and set aside;

[0033] A3. Add the mixed raw materials into a twin-screw extruder, and after extrusion granulation, obtain a flame retardant PC / ABS material; among them, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 250-300 RPM.

[0034] The beneficial effects of the present invention are as follows: Through this method, the present invention can synthesize a new type of flame retardant containing both phosphorus and silicon elements, and adding it to the PC / ABS alloy can prepare a low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material.

[0035] A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material of the present invention improves the flame retardancy of the PC / ABS material by adding a phosphorus-silicon-containing flame retardant, reduces the dosage of traditional phosphate flame retardants, and reduces the impact on the tensile strength, flexural modulus and heat distortion temperature of the alloy; in addition, the phosphorus-silicon-containing flame retardant itself is highly compatible with PC / ABS, and is easy to form a ceramic barrier layer with zinc borate, triphenylboric acid and octamolybdenum during the combustion process, having the functions of smoke suppression, flame retardancy and preventing the molten body from dripping, and the prepared flame retardant material can be widely used in the production of automotive instrument display housings, household appliances, communication electronic and electrical components and rail transit interior trim parts. Specific embodiments

[0036] For the convenience of understanding by those skilled in the art, the present invention will be further described below in conjunction with embodiments. The content mentioned in the embodiments does not limit the present invention.

[0037] Example 1

[0038] A preparation method of a phosphorus-silicon-containing flame retardant, comprising the following steps:

[0039] S1. Add phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinyl bishydroxy to a mixed system of methanol and water in proportion, stir evenly, add an acidic catalyst, adjust the pH value to 4, control the temperature at 0 °C and react for 12 h, neutralize, wash, and remove the low-boiling substances at -0.098 MPa and 85 °C to obtain an intermediate, and set aside;

[0040] S2. Add DOPO flame retardant in an equal molar ratio to the vinyl in the vinyl double head and DMF in an equal mass ratio to the intermediate to the intermediate obtained in step S1, heat to 60° C. to react for 12 hours, filter, wash and dry to obtain a phosphorus-containing silicon flame retardant.

[0041] The phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinyl double head are mixed in a molar ratio of 0.1:0.5:0.1, and the solid content thereof is 35% to 60%.

[0042] The methanol and water form a mixed system in a mass ratio of 1:0.8.

[0043] The mass ratio of the mixture of phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinyl double-capped silane to the mixed system of methanol and water is 1:0.8.

[0044] The acid catalyst is benzenesulfonic acid.

[0045] A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material comprises the following raw materials in parts by weight: 30 parts of PC resin, 5 parts of ABS resin, 1 part of organic silicon synergistic flame retardant additive, 1 part of organic silicon toughening agent, 3 parts of phosphorus-containing silicon flame retardant, 0.1 part of sulfonate flame retardant, 1 part of zinc borate, 1 part of triphenyl boric acid, 0.1 part of octamolybdenum, 0.5 part of phosphate flame retardant, 0.1 part of anti-dripping agent, 0.3 part of antioxidant, 0.2 part of ultraviolet absorber and 0.5 part of lubricant.

[0046] The PC resin has a melt index of 8 g / 10 min.

[0047] The organosilicon synergistic flame retardant additive is phenyl silsesquioxane, preferably SIFR-907 provided by QuanSheng Polycarbonate Technology Co., Ltd.

[0048] The sulfonate flame retardant is selected from Quansheng KKS-A2.

[0049] The organosilicon toughening agent is selected from USI3310 produced by Quansheng.

[0050] The anti-dripping agent is selected from KT-107 of Quansheng.

[0051] The phosphate flame retardant is FCR210.

[0052] The antioxidant is composed of a primary antioxidant and an auxiliary antioxidant in a mass ratio of 1:1. The primary antioxidant is selected from antioxidant 1010; the auxiliary antioxidant is selected from antioxidant 168.

[0053] The low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material is prepared by the following method:

[0054] A1. Dry the PC resin at 120 °C until the water content is less than 0.025%, and set aside.

[0055] A2. Dry the ABS resin at 85 °C until the water content is less than 0.025%. Weigh various raw materials according to parts by weight, and then mix all the raw materials evenly and set aside.

[0056] A3. Add the mixed raw materials into a twin-screw extruder. After extrusion granulation, a flame-retardant PC / ABS material is obtained. Among them, the processing temperature of each zone of the twin-screw extruder is 220 - 240 °C, and the screw rotation speed is 300 RPM.

[0057] Example 2

[0058] A preparation method of a phosphorus-silicon flame retardant, comprising the following steps:

[0059] S1. Add phenyltrimethoxysilane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane into a mixed system of methanol and water according to a ratio. After stirring evenly, add an acidic catalyst, adjust the pH value to 5.5, control the temperature at 20 °C and react for 10 h. Neutralize, wash, and after degassing at -0.098 MPa and 85 °C, obtain an intermediate and set aside.

[0060] S2. Add a DOPO flame retardant with an equimolar ratio of vinyl to that in vinylbistrimethylsiloxysilane and DMF with an equal mass ratio to the intermediate obtained in step S1. Heat to 65 °C and react for 8 h. Filter, wash, and dry to obtain a phosphorus-silicon flame retardant.

[0061] The phenyltrimethoxysilane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane are mixed in a molar ratio of 2:2:3, and its solid content is 35% - 60%.

[0062] The methanol and water form a mixed system according to a mass ratio of 1:1.0.

[0063] The mass ratio of the mixture of phenyltrimethoxysilane, methylphenyldimethoxysilane, and vinylbistrimethylsiloxysilane to the mixed system of methanol and water is 1:1.0.

[0064] The acidic catalyst is composed of sulfuric acid, hydrochloric acid, and trifluoromethanesulfonic acid according to a mass ratio of 1:1.0:1.0.

[0065] A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material, comprising the following raw materials in parts by weight: 45 parts of PC resin, 20 parts of ABS resin, 2 parts of silicone synergistic flame-retardant additive, 2 parts of silicone toughening agent, 4 parts of phosphorus-silicon flame retardant, 1 part of sulfonate flame retardant, 3 parts of zinc borate, 2 parts of triphenylboric acid, 0.3 part of octamolybdenum, 1.5 parts of phosphate ester flame retardant, 0.3 part of anti-dripping agent, 0.8 part of antioxidant, 0.4 part of ultraviolet absorber, and 0.8 part of lubricant.

[0066] The melt index of the PC resin is 10 g / 10 min.

[0067] The silicone synergistic flame-retardant additive is phenylsilsesquioxane, preferably SIFR-908 provided by Quansheng Polycarbon Technology Co., Ltd.

[0068] The sulfonate flame retardant is selected from Quansheng 870M.

[0069] The silicone toughening agent is selected from USI3305 of Quansheng.

[0070] The anti-dripping agent is selected from KT201 of Quansheng.

[0071] The phosphate ester flame retardant is SPB-100.

[0072] The antioxidant is composed of a primary antioxidant and a secondary antioxidant in a mass ratio of 1:1.0. The primary antioxidant is selected from antioxidant 1076; the secondary antioxidant is selected from antioxidant 168.

[0073] The low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material is prepared by the following method:

[0074] A1. Dry the PC resin at 125 °C until the water content is lower than 0.025%, and set aside;

[0075] A2. Dry the ABS resin at 88 °C until the water content is lower than 0.025%. Weigh various raw materials according to the parts by weight of other raw materials, and then mix all the raw materials evenly and set aside;

[0076] A3. Add the mixed raw materials into a twin-screw extruder, and after extrusion and pelletization, obtain the flame-retardant PC / ABS material; wherein, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 280 RPM.

[0077] Example 3

[0078] A preparation method of a phosphorus-silicon flame retardant, comprising the following steps:

[0079] S1. Add phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistrimethylsiloxysilane into the mixed system of methanol and water according to a ratio. After stirring evenly, add an acidic catalyst, adjust the pH value to 6, control the temperature at 45 °C and react for 12 h. Neutralize, wash, and then remove low boilers at -0.098 MPa and 85 °C to obtain an intermediate for standby.

[0080] S2. Add DOPO flame retardant with an equimolar ratio of vinyl to that in vinylbistrimethylsiloxysilane and DMF with a mass ratio equal to that of the intermediate to the intermediate obtained in step S1. Heat to 75 °C and react for 12 h. Filter, wash and dry to obtain a phosphorus-containing silicone flame retardant.

[0081] The phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistrimethylsiloxysilane are mixed according to a molar ratio of 3:4:0.5, and its solid content is 35% - 60%.

[0082] The methanol and water form a mixed system according to a mass ratio of 1:1.2.

[0083] The mass ratio of the mixture of phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistrimethylsiloxysilane to the mixed system of methanol and water is 1:1.2.

[0084] The acidic catalyst is dodecylbenzenesulfonic acid.

[0085] A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material comprises the following raw materials in parts by weight: 60 parts of PC resin, 30 parts of ABS resin, 3 parts of organosilicon synergistic flame retardant additive, 3 parts of organosilicon toughening agent, 5 parts of phosphorus-containing silicone flame retardant, 2 parts of sulfonate flame retardant, 5 parts of zinc borate, 3 parts of triphenylboric acid, 0.5 part of octamolybdenum, 3 parts of phosphate ester flame retardant, 0.5 part of anti-dripping agent, 1 part of antioxidant, 0.5 part of ultraviolet absorber, 1 part of lubricant.

[0086] The melt index of the PC resin is 12 g / 10 min.

[0087] The organosilicon synergistic flame retardant additive is phenylsilsesquioxane, preferably SIFR-907 provided by Quansheng Polycarbon Technology Co., Ltd.

[0088] The sulfonate flame retardant is KSS from Arichem.

[0089] The organosilicon toughening agent is selected from USI3306 of Quansheng.

[0090] The anti-dripping agent is selected from KT-P205 of Quansheng.

[0091] The phosphate ester flame retardant is PX200.

[0092] The antioxidant is composed of a primary antioxidant and a secondary antioxidant in a ratio of 1:1. The primary antioxidant is selected from antioxidant MD-697; the secondary antioxidant is selected from antioxidant 412S.

[0093] The low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material is prepared by the following method:

[0094] A1. Dry the PC resin at 130 °C until the water content is less than 0.025%, and set aside.

[0095] A2. Dry the ABS resin at 90 °C until the water content is less than 0.025%. Weigh various raw materials according to parts by weight, and then mix all the raw materials evenly and set aside.

[0096] A3. Add the mixed raw materials into a twin-screw extruder. After extrusion and pelletization, a flame-retardant PC / ABS material is obtained. Among them, the processing temperature of each zone of the twin-screw extruder is 220 - 240 °C, and the screw rotation speed is 300 RPM.

[0097] Example 4

[0098] A preparation method of a phosphorus-silicon flame retardant includes the following steps:

[0099] S1. Add 39.6 g of phenyltrimethoxysiloxane, 244.0 g of methylphenyldimethoxysilane, and 55.8 g of vinyl bishydroxy to a mixed system of 339.4 g of methanol and water. Stir evenly at room temperature for 30 min, then dropwise add hydrochloric acid solution at about 20 °C to adjust the pH value to 4.5, continuously react for 12 h, then adjust to neutral with sodium carbonate, let it stand for stratification, remove the waste liquid layer, wash 3 times until neutral, add 0.3% activated carbon, stir for 1 h, filter, and obtain an intermediate after removing low-boiling components at -0.098 MPa and 120 °C, and set aside; after taking the intermediate, calibrate the vinyl content by nuclear magnetic method, 0.1 mol / 100 g.

[0100] S2. Take 100 g of the above-added intermediate and add it in an equal amount to a mixed solution of DMF and toluene with a mass ratio of 3:7. Stir evenly, then add 22.7 g of DOPO and slowly heat to 70 °C. React for 6 h, cool down, add an equal amount of methanol for sedimentation to obtain a crude product, wash 3 times with deionized water and 3 times with isopropanol, and dry in an oven at 120 °C with a yield of 98% to obtain the phosphorus-silicon flame retardant.

[0101] The methanol and water form a mixed system according to a mass ratio of 1:1.2.

[0102] Example 5

[0103] A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material, comprising the following raw materials in parts by weight: 60 parts of PC resin, 30 parts of ABS resin, 1 part of silicone synergistic flame retardant additive, 2 parts of silicone toughening agent, 4 parts of phosphorus-silicon flame retardant, 0.3 part of sulfonate flame retardant, 2 parts of zinc borate, 1 part of triphenylboric acid, 0.4 part of octamolybdenum, 2 parts of phosphate ester flame retardant, 0.3 part of anti-dripping agent, 0.3 part of antioxidant, 0.2 part of ultraviolet absorber, and 0.5 part of lubricant.

[0104] The PC resin is preferably Shandong Lihuayi Weiyuan WY-111BR; the ABS resin is selected from GP-22 of BASF.

[0105] The silicone synergistic flame retardant additive is phenylsilsesquioxane, preferably SIFR-907 provided by Quansheng Polycarbon Technology Co., Ltd.

[0106] The sulfonate flame retardant is selected from Quansheng KKS-A2.

[0107] The silicone toughening agent is selected from USI3305 of Quansheng.

[0108] The anti-dripping agent is selected from KT-P205 of Quansheng.

[0109] The phosphate ester flame retardant is PX220.

[0110] The ultraviolet absorber is preferably ultraviolet absorber UV-329; the lubricant is preferably PETS lubricant.

[0111] The antioxidant is composed of a primary antioxidant and a secondary antioxidant in a ratio of 1:1. The primary antioxidant is selected from antioxidant 1010; the secondary antioxidant is selected from antioxidant 168.

[0112] The low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material is prepared by the following method:

[0113] A1. Dry the PC resin at 120 °C until the water content is lower than 0.02%, and set aside;

[0114] A2. Dry the ABS resin at 85 °C until the water content is lower than 0.02%. Weigh various raw materials according to the parts by weight, and then mix all the raw materials evenly and set aside;

[0115] A3. Add the mixed raw materials into a twin-screw extruder, and after extrusion granulation, obtain the flame retardant PC / ABS material; wherein, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 260 RPM.

[0116] Example 6

[0117] A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material, comprising the following raw materials in parts by weight: 60 parts of PC resin, 30 parts of ABS resin, 1 part of silicone synergistic flame-retardant additive, 2 parts of silicone toughening agent, 5 parts of phosphorus-silicon flame retardant, 0.3 part of sulfonate flame retardant, 2 parts of zinc borate, 1 part of triphenylboric acid, 0.3 part of octamolybdenum, 2 parts of phosphate ester flame retardant, 0.3 part of anti-dripping agent, 0.3 part of antioxidant, 0.2 part of ultraviolet absorber, 0.5 part of lubricant.

[0118] The PC resin is preferably Shandong Lihuayi Weiyuan WY-111BR; the ABS resin is selected from GP-22 of BASF.

[0119] The silicone synergistic flame-retardant additive is phenylsilsesquioxane, preferably SIFR-908 provided by Quansheng Polycarbon Technology Co., Ltd.

[0120] The sulfonate flame retardant is selected from Quansheng KKS-A2.

[0121] The silicone toughening agent is selected from USI3305 of Quansheng.

[0122] The anti-dripping agent is selected from KT-P205 of Quansheng.

[0123] The phosphate ester flame retardant is SPB-100.

[0124] The ultraviolet absorber is preferably ultraviolet absorber UV-329; the lubricant is preferably PETS lubricant.

[0125] The antioxidant is composed of a primary antioxidant and a secondary antioxidant in a ratio of 1:1. The primary antioxidant is selected from antioxidant 1010; the secondary antioxidant is selected from antioxidant 168.

[0126] The low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material is prepared by the following method:

[0127] A1. Dry the PC resin at 120 °C until the water content is lower than 0.02%, and set aside;

[0128] A2. Dry the ABS resin at 85 °C until the water content is lower than 0.02%. Weigh various raw materials according to the parts by weight, and then mix all the raw materials evenly, and set aside;

[0129] A3. Add the mixed raw materials into a twin-screw extruder, and after extrusion and pelletization, obtain the flame-retardant PC / ABS material; wherein, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 260 RPM.

[0130] Example 7

[0131] A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material, comprising the following raw materials in parts by weight: 60 parts of PC resin, 30 parts of ABS resin, 1 part of silicone synergistic flame retardant additive, 2 parts of silicone toughening agent, 5 parts of phosphorus-silicon flame retardant, 0.3 part of sulfonate flame retardant, 2 parts of zinc borate, 1 part of triphenylboric acid, 0.4 part of octamolybdenum, 2 parts of phosphate ester flame retardant, 0.3 part of anti-dripping agent, 0.3 part of antioxidant, 0.2 part of ultraviolet absorber, 0.5 part of lubricant.

[0132] The PC resin is preferably 2805 from Covestro; the ABS resin is selected from GP-22 from BASF.

[0133] The silicone synergistic flame retardant additive is phenylsilsesquioxane, preferably SIFR-907 provided by Quansheng Polycarbon Technology Co., Ltd.

[0134] The sulfonate flame retardant is selected from Quansheng KKS-A2.

[0135] The silicone toughening agent is selected from USI3305 of Quansheng.

[0136] The anti-dripping agent is selected from KT-P205 of Quansheng.

[0137] The phosphate ester flame retardant is PX200.

[0138] The ultraviolet absorber is preferably ultraviolet absorber UV-329; the lubricant is preferably PETS lubricant.

[0139] The antioxidant is composed of a primary antioxidant and a secondary antioxidant in a ratio of 1:1. The primary antioxidant is selected from antioxidant 1010; the secondary antioxidant is selected from antioxidant 168.

[0140] The low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material is prepared by the following method:

[0141] A1. Dry the PC resin at 120 °C until the water content is lower than 0.02%, and set aside;

[0142] A2. Dry the ABS resin at 85 °C until the water content is lower than 0.02%. Weigh various raw materials according to the parts by weight, and then mix all the raw materials evenly, and set aside;

[0143] A3. Add the mixed raw materials into a twin-screw extruder, and after extrusion granulation, obtain the flame retardant PC / ABS material; wherein, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 260 RPM.

[0144] Example 8

[0145] A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material, comprising the following raw materials in parts by weight: 60 parts of PC resin, 30 parts of ABS resin, 1 part of silicone synergistic flame retardant additive, 2 parts of silicone toughening agent, 5 parts of phosphorus-silicon flame retardant, 0.3 part of sulfonate flame retardant, 2 parts of zinc borate, 1 part of triphenylboric acid, 0.4 part of octamolybdenum, 2 parts of phosphate ester flame retardant, 0.3 part of anti-dripping agent, 0.3 part of antioxidant, 0.2 part of ultraviolet absorber, 0.5 part of lubricant.

[0146] The PC resin is preferably 2805 from Covestro; the ABS resin is selected from GP-22 from BASF.

[0147] The silicone synergistic flame retardant additive is phenylsilsesquioxane, preferably SIFR-907 provided by Quansheng Polycarbon Technology Co., Ltd.

[0148] The sulfonate flame retardant is selected from Quansheng KKS-A2.

[0149] The silicone toughening agent is selected from USI3305 of Quansheng.

[0150] The anti-dripping agent is selected from KT-P205 of Quansheng.

[0151] The phosphate ester flame retardant is SPB-100.

[0152] The ultraviolet absorber is preferably ultraviolet absorber UV-329; the lubricant is preferably PETS lubricant.

[0153] The antioxidant is composed of a primary antioxidant and a secondary antioxidant in a ratio of 1:1. The primary antioxidant is selected from antioxidant 1010; the secondary antioxidant is selected from antioxidant 168.

[0154] The low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material is prepared by the following method:

[0155] A1. Dry the PC resin at 120 °C until the water content is lower than 0.02%, and set aside;

[0156] A2. Dry the ABS resin at 85 °C until the water content is lower than 0.02%. Weigh various raw materials according to the parts by weight, and then mix all the raw materials evenly and set aside;

[0157] A3. Add the mixed raw materials into a twin-screw extruder, and after extrusion and pelletization, obtain the flame retardant PC / ABS material; wherein, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 260 RPM.

[0158] Comparative Examples 1-3

[0159] The PC resin is selected from 2805 of Covestro, the ABS resin is selected from GP-22 of BASF, and other additives are experimented according to the component ratios listed in Table 1. The process is the same as that of Example 5.

[0160] The PC / ABS alloy halogen-free flame-retardant materials obtained in Examples 5 to 8 and Comparative Examples 1 to 3 were injection-molded into standard test specimens and their properties were tested. The test results are shown in Table 2.

[0161] The molding process conditions were as follows: nozzle temperature 240 °C, zone temperatures 220 °C, 235 °C, 240 °C, holding pressure time 6 - 10 s, injection pressure 30 - 50 MPa.

[0162] The test methods for each property are as follows:

[0163] Tensile strength: Tested according to ASTM D638 standard;

[0164] Flexural strength: Tested according to ASTM D790 standard; Lzod notched impact strength: Tested according to ASTM D256 standard; Smoke density: Tested according to GB / T 8627-2007 standard; Heat distortion temperature: Tested according to ASTM D648 standard;

[0165] Flame retardancy: Tested according to UL94 V0 standard.

[0166] Table 1

[0167] Material Comparative Example 1 Comparative Example 2 Comparative Example 3 PC 60.0 60.0 60.0 ABS 30.0 30.0 30.0 SIFR-907 1.0 1.0 1.0 SIFR-908 KKS-A2 0.3 0.3 0.3 PSI-FR 0 5.0 0 Zinc borate 2.0 0 0 Triphenylboric acid 1.0 0 0 Octamolybdenum 0.4 0 0 USI-3305 2.0 2.0 2.0 KT-P205 0.3 0.3 0.3 PX200 BDP 6 5 RDP 5 PX220 2 SPB-100 Antioxidant 0.3 0.3 0.3 Ultraviolet absorber 0.2 0.2 0.2 Lubricant 0.5 0.5 0.5

[0168] Table 2 Physical Property Data

[0169]

[0170]

[0171] As can be seen from Table 2, compared with Comparative Examples 1 - 3, the PC / ABS alloy halogen-free flame-retardant materials prepared in Examples 5 to 8 have good mechanical properties and flame-retardant properties, and at the same time have the advantages of low smoke and high modulus.

[0172] The above embodiments are the preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material, characterized in that: It comprises the following raw materials in parts by weight: 30 - 60 parts of PC resin, 5 - 30 parts of ABS resin, 1 - 3 parts of silicone synergistic flame retardant additive, 1 - 3 parts of silicone toughening agent, 3 - 5 parts of phosphorus-silicon flame retardant, 0.1 - 2 parts of sulfonate flame retardant, 1 - 5 parts of zinc borate, 1 - 3 parts of triphenylboric acid, 0.1 - 0.5 parts of octamolybdenum, 0.5 - 3 parts of phosphate ester flame retardant, 0.1 - 0.5 parts of anti-dripping agent, 0.3 - 1 part of antioxidant, 0.2 - 0.5 part of ultraviolet absorber, 0.5 - 1 part of lubricant; the melt index of the PC resin is 8 - 12 g / 10 min; The phosphorus-silicon flame retardant is prepared through the following steps: S1. Add phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistetrahydroindenyl into the mixed system of methanol and water according to a proportion. After stirring evenly, add an acidic catalyst, adjust the pH value to 4 - 6, control the temperature at 0℃ - 45℃ and react for 8 - 12 h. Neutralize, wash, and after degassing at -0.098 MPa and 85℃, obtain an intermediate for standby; S2. Add DOPO flame retardant with an equimolar ratio of vinyl in vinylbistetrahydroindenyl and DMF with an equal mass ratio to the intermediate obtained in step S1. Heat to 60℃ - 75℃ and react for 4 - 12 h. Filter, wash and dry to obtain the phosphorus-silicon flame retardant.

2. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to claim 1, characterized in that: The phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistetrahydroindenyl are mixed according to a molar ratio of 0.1 - 3:0.5 - 4:0.1 - 0.5; the methanol and water form a mixed system according to a mass ratio of 1:0.8 - 1.

2.

3. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to claim 1, characterized in that: The mass ratio of the mixture of phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistetrahydroindenyl to the mixed system of methanol and water is 1:0.8 - 1.

2.

4. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to claim 1, characterized in that: The phenyltrimethoxysiloxane, methylphenyldimethoxysilane and vinylbistetrahydroindenyl are mixed according to a molar ratio of 0.1 - 1:0.5 - 4:0.1 - 0.

4.

5. A low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material according to claim 1, characterized in that: The acidic catalyst is at least one of benzenesulfonic acid, p-toluenesulfonic acid, sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid, methanesulfonic acid, dodecylbenzenesulfonic acid, phosphoric acid, bisulfate.

6. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to claim 1, characterized in that: The silicone synergistic flame retardant additive is phenylsilsesquioxane.

7. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to claim 1, characterized in that: The phosphate ester flame retardant is at least one of FCR210, SPB-100, HM1100, PX200, PX220.

8. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to claim 1, characterized in that: The antioxidant consists of a main antioxidant and a co-antioxidant. The main antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076 and antioxidant MD-697; the co-antioxidant is selected from at least one of antioxidant 168 and antioxidant 412S.

9. A low-smoke, high-modulus PC / ABS alloy halogen-free flame-retardant material according to any one of claims 1-8, characterized in that: The low-smoke, high-modulus PC / ABS alloy halogen-free flame retardant material is prepared through the following method: A1. Dry the PC resin at 120 - 130℃ until the water content is lower than 0.025% for standby; A2. Dry the ABS resin at 85 - 90℃ until the water content is lower than 0.025%. Weigh various raw materials according to parts by weight for other raw materials, and then mix all the raw materials evenly for standby; A3. Add the mixed raw materials into a twin-screw extruder. After extrusion and pelletization, a flame-retardant PC / ABS material is obtained. Among them, the processing temperature of each zone of the twin-screw extruder is 220-240 °C, and the screw rotation speed is 250-300 RPM.

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