High heat-resistant mineral reinforced halogen-free flame-retardant PC / ABS alloy and preparation method thereof

Abstract

The application belongs to the technical field of polymer material processing, and discloses a high-heat-resistance mineral-reinforced halogen-free flame-retardant PC / ABS alloy and a preparation method thereof.The high-heat-resistance mineral-reinforced halogen-free flame-retardant PC / ABS alloy contains, in terms of weight fraction, PC resin 50-85 parts, ABS resin or ABS obtained by blending AS and high glue powder 5-20 parts, toughening agent 2-8 parts, phosphorus-containing triphenylene flame retardant grafted reinforced mineral filler 5-30 parts, anti-dripping agent 0.2-1 part, antioxidant 0.1-0.5 part, and lubricant 0.1-1 part.The flame-retardant material grafts the phosphorus-containing triphenylene flame retardant on the surface of the reinforced mineral filler through a silane coupling agent, improves the heat resistance temperature of the phosphorus-containing triphenylene flame retardant, and makes the flame retardant stable in the processing process, then adds the reinforced mineral filler grafted by the phosphorus-containing triphenylene flame retardant into the PC / ABS alloy, and the phosphorus-containing triphenylene and the reinforced mineral filler synergistically act to enhance the flame-retardant effect, reduce the addition amount of the phosphorus-based flame retardant, reduce the heat deformation decline amplitude, and improve the rigidity of the material.

Description

Technical Field

[0001] This invention relates to the field of polymer material processing technology, specifically to a high heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy and its preparation method. Background Technology

[0002] PC / ABS alloy is a high-performance engineering plastic obtained by blending polycarbonate (PC) with acrylonitrile / butadiene / styrene copolymer (ABS). PC, the raw material, contains flexible carbonate groups and rigid benzene rings, giving it many advantages such as good mechanical properties, high heat distortion temperature, transparency, and dimensional stability. However, its disadvantages include stress sensitivity, susceptibility to residual internal stress leading to cracking, and poor flowability, affecting injection molding. ABS, the raw material, combines the processing flowability and gloss provided by the styrene component, the toughness provided by the butadiene component, and the heat resistance, chemical resistance, and rigidity provided by the acrylonitrile component. The reasonable ratio of these three components results in balanced mechanical properties and good processing flowability. The PC / ABS alloy integrates the excellent properties of both PC and ABS. On the one hand, this alloy can improve the heat resistance and mechanical properties of ABS; on the other hand, it can improve the processing flowability of PC, reduce notch sensitivity, and improve resistance to stress cracking.

[0003] Commonly used halogenated flame retardants such as decabromodiphenyl ether (DBD) have side effects during material catalytic cracking and ignition, producing corrosive gases and fumes that pollute the environment and cause secondary pollution. With technological advancements and increasingly stringent environmental protection requirements for materials, particularly the enactment of the EU RoHS and WEEE directives, halogenated flame-retardant PC / ABS alloys are facing growing limitations. Commonly used phosphorus-based flame retardants often result in products with lower heat resistance temperatures, making them more prone to deformation at high temperatures and limiting their applications. Therefore, developing a high-temperature-resistant, mineral-reinforced, halogen-free flame-retardant PC / ABS alloy has broad applications in automotive dashboards, pillars, grilles, hair dryers, and microwave oven interior and exterior components, enabling differentiated competition at the same price point and aligning with current market prospects.

[0004] Chinese patent CN 108623844 A discloses a DOPO-LDH composite flame retardant synthesized from DOPO, a silane coupling agent, and magnesium-aluminum type hydrotalcite. The grafting rate of this flame retardant is 0.5-5%, aiming to reduce the high flame retardant content in EPDM rubber materials. However, since the main components of magnesium-aluminum type hydrotalcite are magnesium hydroxide and aluminum hydroxide, the alkaline components will cause degradation of PC raw materials, thus it cannot be applied to PC alloy systems. Chinese patent CN 110218444 A discloses a material composed of nylon 6, DOPO, and MWCNTs for flame retardancy and antistatic properties of nylon 6. Although this material has conductivity and a V-2 flame retardancy rating, MWCNTs are expensive, lack grafting sites, and require treatment with various strong acids such as sulfuric acid and nitric acid, resulting in high finished product prices and hindering industrial production. Chinese patent CN 110218444A discloses an ultra-high heat-resistant halogen-free flame-retardant PC / ABS composite material. This material contains aromatic PC resin, ABS resin, grafted modified heat-resistant agent, flame retardant, etc. Although the material has a high heat distortion temperature, the addition of heat-resistant agent significantly increases the amount of flame retardant used, which is not an economical and practical approach in terms of cost. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of commonly used phosphorus-based flame retardants, which require large amounts and weaken the inter-chain forces of polymers, leading to a significant reduction in the thermal deformation of the finished product. This invention provides a high-temperature resistant mineral-reinforced halogen-free flame-retardant PC / ABS and its preparation method. In this invention, a phosphaphenanthrene flame retardant is grafted onto the surface of the reinforcing mineral filler using a silane coupling agent. This increases the heat resistance temperature of the phosphaphenanthrene flame retardant, ensuring its stability during processing. The grafted phosphaphenanthrene flame retardant reinforcing mineral filler is then added to the PC / ABS alloy. The phosphaphenanthrene and the reinforcing mineral filler work synergistically to enhance the flame retardant effect, reduce the amount of phosphorus-based flame retardant required, decrease the reduction in thermal deformation, and simultaneously improve the rigidity of the material.

[0006] To achieve the objectives of this invention, the high heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy of this invention comprises, by weight, 50-85 parts of PC resin, 5-20 parts of ABS resin or ABS obtained by blending AS with high-polymer powder, 2-8 parts of toughening agent, 5-30 parts of reinforcing mineral filler grafted with phosphorus-phenanthrene flame retardant, 0.2-1 part of anti-dripping agent, 0.1-0.5 parts of antioxidant, and 0.1-1 part of lubricant.

[0007] Furthermore, in some embodiments of the present invention, the high heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy, by weight, comprises 50-85 parts of PC resin, 5-20 parts of ABS resin or ABS obtained by blending AS with high-polymer powder, 3-5 parts of toughening agent, 10-30 parts of reinforcing mineral filler grafted with phosphorus-phenanthroline flame retardant, 0.2-1 parts of anti-dripping agent, 0.1-0.3 parts of antioxidant, and 0.1-0.5 parts of lubricant.

[0008] Furthermore, in some embodiments of the present invention, the preparation method of the reinforced mineral filler after grafting with the phosphaphenanthrene flame retardant includes: weighing the reinforced mineral filler, the phosphaphenanthrene flame retardant and the silane coupling agent, stirring and mixing them evenly, placing them in an environment of 150-170℃ for 2-6 hours, rinsing and filtering with ethanol, drying, and then breaking them into powder to obtain the reinforced mineral filler after grafting with the phosphaphenanthrene flame retardant.

[0009] Furthermore, in some embodiments of the present invention, the reinforced mineral filler after grafting with the phosphorus phenanthrene flame retardant contains, by weight, 60-100 parts of reinforced mineral filler, 10-20 parts of phosphorus phenanthrene flame retardant, and 10-20 parts of silane coupling agent.

[0010] Furthermore, in some embodiments of the present invention, the reinforcing mineral filler is one or more of silica, talc, kaolin, and mica.

[0011] Furthermore, in some embodiments of the present invention, the phosphoranone flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as DOPO (DOP).

[0012] Furthermore, in some embodiments of the present invention, the silane coupling agent is one or more selected from KH-550 (γ-aminopropyltriethoxysilane), KH-560 (γ-glycidyl etheroxypropyltrimethoxysilane), KH-570 (γ-methacryloyloxypropyltrimethoxysilane), KH-792 (γ-aminoethylaminopropyltrimethoxysilane), and KH-602 (N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane).

[0013] Furthermore, in some embodiments of the present invention, the drying is performed at 70-90°C.

[0014] Furthermore, in some embodiments of the present invention, the toughening agent is one or a combination of two of MBS, ACR, and EMA.

[0015] Furthermore, in some embodiments of the present invention, the anti-dripping agent is pure PTFE powder or PTFE powder coated with one or more of SAN and MMA.

[0016] Furthermore, in some embodiments of the present invention, the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant, or an antioxidant of a combination system of hindered phenolic antioxidant and phosphite antioxidant; preferably, the mass ratio of hindered phenolic antioxidant to phosphite antioxidant in the antioxidant is 1:1-3.

[0017] Furthermore, in some embodiments of the present invention, the lubricant is one or more of polyethylene wax, calcium stearate, and pentaerythritol stearate.

[0018] On the other hand, the present invention also provides a method for preparing the aforementioned high heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy, the method comprising the following steps:

[0019] (1) Weigh out the required parts by weight of PC resin, ABS resin, toughening agent, grafted reinforced mineral filler with phosphorus phenanthrene flame retardant, anti-dripping agent, antioxidant and lubricant, and mix them well.

[0020] (2) The material mixed in step (1) is placed in a co-rotating twin-screw extruder, and after melting, plasticizing, extrusion, cooling and pelletizing, a high heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0021] Furthermore, in some embodiments of the present invention, the screw diameter of the co-rotating twin-screw extruder is 35-75mm, the length-to-diameter ratio of the screw is 32-52:1, and the melting and plasticizing temperature is set as follows: first stage 220℃-240℃, second stage 240℃-270℃, third stage 240℃-270℃, fourth stage 240℃-270℃, fifth stage 240℃-270℃, sixth stage 230℃-260℃, seventh stage 230℃-260℃, eighth stage 230℃-260℃, ninth stage 230℃-260℃, tenth stage 240℃-270℃, melt temperature 240℃-280℃, and die head temperature 240-280℃.

[0022] Compared with the prior art, the advantages of the present invention are as follows:

[0023] (1) The phosphanium flame retardant of the present invention has a low thermal decomposition temperature and decomposes at 190°C, making it impossible to process at the PC / ABS alloy temperature. However, the phosphanium flame retardant grafted onto the surface of the reinforcing mineral filler has a significantly higher thermal decomposition temperature, which keeps it stable during processing.

[0024] (2) Commonly used phosphorus flame retardants are added in large quantities, which weakens the interaction between polymer chains and leads to a significant reduction in the heat distortion temperature of the finished product. However, the grafted modified phosphorus flame retardant of this invention has a synergistic flame retardant effect with the reinforcing mineral filler. The amount of flame retardant added is less, the reduction in heat distortion temperature is smaller, and the product cost is lower due to the smaller amount of flame retardant added.

[0025] (3) The addition of reinforcing mineral filler in this invention improves the rigidity of the material and also increases the heat distortion temperature of the material.

[0026] (4) In the prior art, maintaining high heat deformation is mainly achieved by adding heat-resistant agents. The application of DOPO grafted reinforcing minerals in PC alloys is an innovation of this invention. Products obtained in this way can be applied to automotive dashboards, trim pillars, grilles, hair dryers, microwave oven interior and exterior parts, etc., expanding the application range of phosphorus-based flame-retardant PC / ABS alloys, enabling differentiated competition of "what others have, I have better", obtaining higher product profits, and conforming to the current market prospects. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. Additional aspects and advantages of this invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. It should be understood that the following description is merely illustrative and not intended to limit the invention.

[0028] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0029] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1 to 2”, “1 to 2 and 4 to 5”, “1 to 3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0030] The indefinite articles “a” and “an” preceding an element or component of this invention do not impose any limitation on the quantity (i.e., number of times) of the element or component. Therefore, “an” or “a” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural form, unless the quantity clearly refers only to the singular form.

[0031] Furthermore, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., described below refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms are not necessarily directed at the same embodiment or example. Moreover, the technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0032] An embodiment of the present invention provides a high heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy, which is composed of the following components by mass percentage:

[0033] 50-85 parts of PC resin,

[0034] 5-20 parts of ABS obtained by blending ABS resin or AS with high-polymer powder.

[0035] Toughening agent MBS 2-8 parts,

[0036] 5-30 parts of reinforced mineral filler grafted with phosphaphenanthrene flame retardant.

[0037] Anti-dripping agent PTFE 0.2-1 part,

[0038] Antioxidant 1076 + Antioxidant 168, 0.2-0.5 parts.

[0039] Lubricant PETS 0.2-1 part.

[0040] Unless otherwise specified, in the embodiments of the present invention:

[0041] The reinforced mineral filler grafted with phosphaphenanthrene flame retardant was prepared by the following steps: Weigh the reinforced mineral filler, phosphaphenanthrene flame retardant and silane coupling agent, stir and mix for 10 min, place in an oven at 160℃ for 4 h, wash and filter with ethanol, dry in an oven at 80℃, take it out and break it into powder with a high-speed mixer to obtain the reinforced mineral filler grafted with phosphaphenanthrene flame retardant.

[0042] The reinforced mineral filler grafted with phosphorus phenanthrene flame retardant contains, by weight, 60-100 parts of reinforced mineral filler, 10-20 parts of phosphorus phenanthrene flame retardant, and 10-20 parts of silane coupling agent KH-560.

[0043] Example 1

[0044] Weigh 60 parts of talc powder, 10 parts of phosphorus phenanthrene flame retardant and 10 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant graft treatment.

[0045] Weigh out 85 parts of PC resin, 5 parts of ABS resin, 3 parts of toughening agent MBS, 10 parts of the reinforced mineral filler grafted with the obtained phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0046] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0047] Example 2

[0048] Weigh out 60 parts of talc powder, 20 parts of phosphorus phenanthrene flame retardant and 20 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant grafting treatment.

[0049] Weigh out 85 parts of PC resin, 5 parts of ABS resin, 3 parts of toughening agent MBS, 10 parts of reinforced mineral filler grafted with phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0050] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0051] Example 3

[0052] Weigh out 60 parts of talc powder, 20 parts of phosphorus phenanthrene flame retardant and 20 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant grafting treatment.

[0053] Weigh out 65 parts of PC resin, 10 parts of ABS resin, 5 parts of toughening agent MBS, 20 parts of reinforced mineral filler grafted with phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0054] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0055] Example 4

[0056] Weigh out 60 parts of talc powder, 20 parts of phosphorus phenanthrene flame retardant and 20 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant grafting treatment.

[0057] Weigh out 50 parts of PC resin, 20 parts of ABS resin, 5 parts of toughening agent MBS, 30 parts of reinforced mineral filler grafted with phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0058] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0059] Example 5

[0060] Weigh out 60 parts of silica, 20 parts of phosphorus phenanthrene flame retardant and 20 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant graft treatment.

[0061] Weigh out 65 parts of PC resin, 10 parts of ABS resin, 5 parts of toughening agent MBS, 20 parts of reinforced mineral filler grafted with phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0062] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0063] Example 6

[0064] Weigh out 60 parts of talc powder, 20 parts of phosphorus phenanthrene flame retardant and 20 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant grafting treatment.

[0065] Weigh out 65 parts of PC resin, 5 parts of AS resin, 5 parts of ABS high-rubber powder, 5 parts of toughening agent MBS, 20 parts of reinforced mineral filler grafted with phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0066] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0067] Example 7

[0068] Weigh out 60 parts of talc powder, 20 parts of phosphorus phenanthrene flame retardant and 20 parts of silane coupling agent KH-560, stir and mix for 10 minutes, place in an oven at 160℃ for 4 hours, wash and filter with ethanol, dry in an oven at 80℃, take out and break into powder with a high-speed mixer to obtain the reinforced mineral filler after phosphorus phenanthrene flame retardant grafting treatment.

[0069] Weigh out 65 parts of PC resin, 10 parts of ABS resin, 5 parts of toughening agent MBS, 20 parts of reinforced mineral filler grafted with phosphorus phenanthrene flame retardant, 0.3 parts of anti-dripping agent PTFE, 0.1 parts of antioxidant 1076, 0.1 parts of antioxidant 168 and 0.2 parts of lubricant PETS, and mix them together.

[0070] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 75 mm and a length-to-diameter ratio of 52:1. The melting and plasticizing temperatures are set as follows: first stage 240℃, second stage 270℃, third stage 270℃, fourth stage 270℃, fifth stage 270℃, sixth stage 260℃, seventh stage 260℃, eighth stage 260℃, ninth stage 260℃, and tenth stage 270℃; melt temperature 270℃; and die head temperature 270℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0071] Comparative Example 1

[0072] Weigh out 65 parts PC resin, 10 parts ABS resin, 5 parts toughening agent MBS, 12 parts talc, 4 parts phosphorus phenanthrene flame retardant, 0.3 parts anti-dripping agent PTFE, 0.1 parts antioxidant 1076, 0.1 parts antioxidant 168 and 0.2 parts lubricant PETS, and mix them together.

[0073] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0074] Comparative Example 2

[0075] Weigh out 65 parts PC resin, 10 parts ABS resin, 5 parts toughening agent MBS, 12 parts talc, 12 parts phosphorus phenanthrene flame retardant, 0.3 parts anti-dripping agent PTFE, 0.1 parts antioxidant 1076, 0.1 parts antioxidant 168 and 0.2 parts lubricant PETS, and mix them together.

[0076] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0077] Comparative Example 3

[0078] Weigh out 65 parts PC resin, 10 parts ABS resin, 5 parts toughening agent MBS, 12 parts phosphorus phenanthrene flame retardant, 0.3 parts anti-dripping agent PTFE, 0.1 parts antioxidant 1076, 0.1 parts antioxidant 168 and 0.2 parts lubricant PETS, and mix them together.

[0079] The mixed materials are placed in a co-rotating twin-screw extruder with a screw diameter of 40 mm and a length-to-diameter ratio of 40:1. The melting and plasticizing temperatures are set as follows: first stage 220℃, second stage 240℃, third stage 240℃, fourth stage 240℃, fifth stage 240℃, sixth stage 230℃, seventh stage 230℃, eighth stage 230℃, ninth stage 230℃, and tenth stage 240℃; melt temperature 250℃; and die head temperature 245℃. After melting, plasticizing, extrusion, cooling, and pelletizing, a high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained.

[0080] Table 1. Performance test results of PC / ABS alloys prepared in each embodiment and comparative example.

[0081]

[0082] Table 1 shows the performance test results of the PC / ABS alloys prepared in each embodiment and comparative example. A comparison of the test results of Examples 1-7 and Comparative Examples 1-3 in the table shows that the reinforcing mineral filler grafted with the phosphorus-phenanthroline flame retardant prepared in this invention plays an important role in achieving the flame retardant properties of the PC / ABS alloy and improving its flexural strength.

[0083] A comparison of the test results from Examples 1-4 and Comparative Examples 1-2 shows that the phosphaphenanthrene flame retardant grafted onto the surface of the reinforcing mineral filler has a synergistic flame retardant effect with the reinforcing mineral filler. Even with the proportion of phosphaphenanthrene in the formulation reduced to 1%-4%, flame retardant effects can be achieved in specific formulations. However, the untreated phosphaphenanthrene flame retardant requires an addition of 11.5% to achieve a V-0 flame retardant rating. This large addition of phosphaphenanthrene leads to a strong plasticizing effect from the phosphorus-based flame retardant, resulting in a significant reduction in heat distortion. Simultaneously, due to the lower decomposition temperature of the untreated phosphaphenanthrene flame retardant, the material's impact performance decreases significantly, making the material brittle.

[0084] The results of Example 5 show that grafted fillers, such as talc powder and silica powder, formed by grafting phosphaphenanthrene flame retardant onto silica-based fillers, can achieve similar effects. Example 6 demonstrates that ABS can be replaced by a compound of AS and high-resin ABS powder, with similar results. Example 7 demonstrates that changing the temperature within the processing range can also achieve the flame retardant and reinforcing effects of this invention.

[0085] Based on the above experimental data, it can be seen that the reinforced mineral filler after grafting with the phosphanium phenanthrene flame retardant of the present invention has a high thermal decomposition temperature, maintaining the stability of its composition during processing; at the same time, since the grafted phosphanium phenanthrene flame retardant and the reinforced mineral filler have a synergistic flame retardant effect, the amount of flame retardant added is less, the reduction in heat distortion temperature is smaller, and the high heat distortion of the material is maintained; the addition of the reinforced mineral filler improves the rigidity of the material and enhances its heat distortion.

[0086] Those skilled in the art will readily understand that the above description is merely an embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A high heat mineral reinforced halogen free flame retardant PC / ABS alloy characterized in that, The high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy comprises, by weight fraction, PC resin 50-85 parts, ABS resin 5-20 parts, toughening agent 2-8 parts, phosphorus hetero-fused flame retardant grafted enhanced mineral filler 5-30 parts, anti-dripping agent 0.2-1 part, antioxidant 0.1-0.5 part, and lubricant 0.1-1 part. Or the high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy comprises, by weight fraction, PC resin 50-85 parts, ABS obtained by blending AS and high-gel powder 5-20 parts, toughening agent 2-8 parts, phosphorus hetero-fused flame retardant grafted enhanced mineral filler 5-30 parts, anti-dripping agent 0.2-1 part, antioxidant 0.1-0.5 part, and lubricant 0.1-1 part. The preparation method of the phosphorus hetero-fused flame retardant grafted enhanced mineral filler comprises the following steps: stirring and uniformly mixing the enhanced mineral filler, phosphorus hetero-fused flame retardant, and silane coupling agent, placing them in an environment at 150-170 ℃ for 2-6 h, rinsing and filtering with ethanol, drying, and then dispersing into powder to obtain the phosphorus hetero-fused flame retardant grafted enhanced mineral filler. The phosphorus hetero-fused flame retardant grafted enhanced mineral filler comprises, by weight fraction, enhanced mineral filler 60-100 parts, phosphorus hetero-fused flame retardant 10-20 parts, and silane coupling agent 10-20 parts. The phosphorus hetero-fused flame retardant is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; the silane coupling agent is one or more of KH-550, KH-560, KH-570, KH-792, and KH-602; and the drying is performed at 70-90 ℃.

2. The highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy according to claim 1, characterized in that, The high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy comprises, by weight fraction, PC resin 50-85 parts, ABS resin 5-20 parts, toughening agent 3-5 parts, phosphorus hetero-fused flame retardant grafted enhanced mineral filler 10-30 parts, anti-dripping agent 0.2-1 part, antioxidant 0.1-0.3 part, and lubricant 0.1-0.5 part. Or the high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy comprises, by weight fraction, PC resin 50-85 parts, ABS obtained by blending AS and high-gel powder 5-20 parts, toughening agent 3-5 parts, phosphorus hetero-fused flame retardant grafted enhanced mineral filler 10-30 parts, anti-dripping agent 0.2-1 part, antioxidant 0.1-0.3 part, and lubricant 0.1-0.5 part.

3. The highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy as claimed in claim 1, wherein, The toughening agent is one or a combination of MBS, ACR, and EMA.

4. The highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy as claimed in claim 1, wherein, The anti-dripping agent is pure PTFE powder or PTFE powder coated with one or more of SAN and MMA.

5. The highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy as claimed in claim 1, wherein, The antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant, or a combination of a hindered phenolic antioxidant and a phosphite antioxidant.

6. The highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy as claimed in claim 1, wherein, The mass ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 1:1-3.

7. The highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy as claimed in claim 1, wherein, The lubricant is one or more of polyethylene wax, calcium stearate, and pentaerythritol stearate.

8. Process for the preparation of the highly heat resistant mineral reinforced halogen-free flame retarded PC / ABS alloy according to any one of claims 1 to 7, characterized in that, The preparation method comprises the following steps: (1) PC resin, ABS resin, toughening agent, phosphorus-containing flame retardant grafted reinforcing mineral filler, anti-dripping agent, antioxidant and lubricant are weighed according to the required weight fraction, and mixed uniformly after weighing; (2) The material mixed by step (1) is placed in a co-rotating twin-screw extruder, and high-heat-resistant mineral-reinforced halogen-free flame-retardant PC / ABS alloy is obtained through melting plasticization, extrusion, cooling and granulation.

9. The process for the preparation of highly heat resistant mineral reinforced halogen free flame retardant PC / ABS alloy as claimed in claim 8, wherein, The co-rotating twin-screw extruder has a screw diameter of 35-75 mm and a length-diameter ratio of 32-52:

1. The temperature of the melting plasticization is set as follows: first section 220-240℃, second section 240-270℃, third section 240-270℃, fourth section 240-270℃, fifth section 240-270℃, sixth section 230-260℃, seventh section 230-260℃, eighth section 230-260℃, ninth section 230-260℃, tenth section 240-270℃, melt temperature 240-280℃, and die temperature 240-280℃.

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