High-toughness chemical-resistant flame-retardant PC alloy material and preparation method thereof

Abstract

The invention relates to the technical field of alloy polymer materials with the IPC main classification number of C08L69 / 00, in particular to a high-toughness chemical-resistant flame-retardant PC alloy material and a preparation method thereof. The flame-retardant PC / ABS alloy material is prepared from the following raw materials in parts by weight: 65 to 75 parts of PC, 10 to 28 parts of ABS, 1 to 4.5 parts of a compatilizer, 3 to 7 parts of a toughening agent, 8 to 12 parts of a ternary synergistic flame retardant, 1 to 5 parts of a functional aid, 0.2 to 0.4 part of an antioxidant and 0 to 3 parts of other aids, the functional additive is a fluorine-silicon compound containing fluorine atoms and silicon atoms in a molecular structure; the flexibilizer is composed of MBS with a core-shell structure and an organic silicon elastomer, and the organic silicon elastomer is an amino modified organic silicon material. Through targeted optimization design of the compatilizer, the flame-retardant system, the flexibilizer, the functional additive and other components in the PC alloy formula system, the PC alloy material realizes comprehensive performance improvement in the aspects of toughness, strength, flame retardance, chemical resistance and the like.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of alloy polymer materials, and belongs to the technical field of high-toughness and chemical-resistance-resistant flame-retardant PC alloy materials and a preparation method thereof. BACKGROUND

[0002] Polycarbonate (PC) alloy materials have become an important choice for replacing metals and ceramics due to their excellent mechanical properties, heat resistance and transparency. However, the traditional PC alloy materials face multiple bottlenecks in practical applications: firstly, the chemical corrosion resistance is insufficient, and stress cracking is easily caused when contacting carbon tetrachloride, glacial acetic acid and other strong polar solvents, resulting in failure of key components such as electronic device housings and new energy automobile battery housings; secondly, the toughening and flame-retardant properties are difficult to be coordinated, and the introduction of conventional toughening agents (such as MBS) will weaken the flame-retardant efficiency, and a high addition amount of flame retardant will lead to a decrease in material toughness and deterioration of processing performance; thirdly, the upgrading of environmental protection requirements forces the development of halogen-free flame-retardant technology, but the existing halogen-free systems (such as phosphorus and nitrogen systems) have problems such as low flame-retardant efficiency and poor thermal stability, and it is difficult to meet the high-level requirements such as UL 94V0@1.5mm and 5VA@3.0mm. Moreover, the conventional PC alloy materials (such as PC / ABS and PC / ASA) not only have insufficient chemical corrosion resistance, but also have poor compatibility between PC and non-polar resins (such as ABS), resulting in weak interfacial bonding of the blended materials and difficult improvement of mechanical properties. In the prior art, the selection of base resin ratio and compatibilizer lacks systematic research, resulting in large material performance fluctuation and substandard chemical resistance. SUMMARY

[0003] In view of the above technical problems, in the application, the performance is optimized by innovative compounding toughening technology (MBS / silicon system synergy), fluorine-silicon chemical resistance modification and halogen-free phosphorus-nitrogen-silicon ternary flame-retardant system design, and the contradiction between traditional materials “toughening-flame-retardant-chemical resistance” is broken through. The application is verified in the scene applications such as new energy automobile battery housings and consumer electronic housings, and promotes the import substitution and industrialization upgrading of domestic high-end engineering plastics in the fields with strict requirements on environmental protection, safety and reliability.

[0004] Specifically, the first aspect of the application provides a tough and chemical-resistance-resistant flame-retardant PC alloy material, and the preparation raw materials are as follows in terms of weight parts:

[0005] PC 65-75 parts by weight;

[0006] ABS 10-28 parts by weight;

[0007] compatibilizer 1-4.5 parts by weight;

[0008] toughening agent 3-7 parts by weight;

[0009] Ternary synergistic flame retardant 8-12 parts by weight;

[0010] Functional aid 1-5 parts by weight;

[0011] Antioxidant 0.2-0.4 parts by weight;

[0012] Other aids 0-3 parts by weight;

[0013] The functional aid is a fluorine-silicon complex containing fluorine atoms and silicon atoms in the molecular structure; the toughening agent is composed of core-shell structure MBS and organic silicone elastomer, and the organic silicone elastomer is an amino-modified silicone material.

[0014] As a preferred technical solution of the present application, the fluorine-silicon complex is nano-silicon dioxide grafted perfluoropolyether material.

[0015] As a preferred technical solution of the present application, the preparation raw material of the nano-silicon dioxide grafted perfluoropolyether material includes nano-silicon dioxide and perfluoropolyether compound, and the average functionality of the molecules of the perfluoropolyether compound is 1.5-3.5; further preferably, the active functional groups of the perfluoropolyether compound can be the same or different.

[0016] As a preferred technical solution of the present application, the number average molecular weight of the perfluoropolyether compound is not less than 2000.

[0017] As a preferred technical solution of the present application, the perfluoropolyether compound includes HFPO carboxylic acid and HFPO amido alcohol.

[0018] As a preferred technical solution of the present application, the mass ratio of the HFPO carboxylic acid and the HFPO amido alcohol is (2-3):1.

[0019] As a preferred technical solution of the present application, the compatilizer is maleic anhydride grafted ABS; preferably, the maleic anhydride grafting rate in the maleic anhydride grafted ABS is not less than 1.5%.

[0020] As a preferred technical solution of the present application, the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate and silicone powder; preferably, the weight ratio of the ammonium polyphosphate, melamine cyanurate and silicone powder is (1-2):1:(0.5-1.5).

[0021] As a preferred technical solution of the present application, the weight ratio of the core-shell structure MBS and the organic silicone elastomer is (1-2):1.

[0022] The second aspect of the present application provides a preparation method of the high-toughness and chemical-resistant flame-retardant PC alloy material as described above, which includes the following steps:

[0023] The raw materials for preparing the PC alloy material are measured according to the formula, and each component is added to a high-speed mixer for stirring and mixing. Then, the mixture is added to a twin-screw extruder for melt extrusion, granulation, and drying to obtain the PC alloy material.

[0024] The high-toughness, chemical-resistant, and flame-retardant PC alloy material provided by this invention has the following advantages compared with existing related products:

[0025] This invention achieves comprehensive performance improvements in PC alloy materials in terms of toughness, strength, flame retardancy, and chemical resistance through targeted optimization of components such as compatibilizers, flame retardants, toughening agents, and functional additives in the PC alloy formulation system. During solvent immersion, the fluorine-silicon synergistic layer of the PC alloy material blocks the penetration of carbon tetrachloride (non-polar) and glacial acetic acid (polar) through a dual mechanism of physical shielding and chemical inertness. Within 48 hours, the surface shows no corrosion or cracking, and the tensile strength retention rate is ≥90%. Furthermore, through targeted optimization and matching of the flame retardant system in the formulation system, a flame retardant rating of 5VA@3.0mm is achieved with a heat distortion temperature ≥85℃, while maintaining a total flame retardant addition of ≤15%. Optimization of the maleic anhydride grafting rate in maleic anhydride-grafted BAS allows for mutual fusion of the matrix resin materials, enhancing the interphase bonding. Simultaneously, the anhydride groups undergo esterification with the terminal hydroxyl groups of PC, forming chemical bonds that bridge the gap, reducing interfacial tension, and significantly improving the weather resistance and other properties of the alloy material. Detailed Implementation

[0026] In this application, when a content, dosage, 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, it 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 that range is disclosed individually. For example, when the range “2-8” is disclosed, the described range should be interpreted as including ranges “2-8”, “2-7”, “2-6”, “2-5 and 6, 7”, “2-3 and 4-8”, etc.

[0027] The raw materials for preparing the high-toughness, chemical-resistant, and flame-retardant PC alloy material provided in this invention include (by weight) 65-75 parts PC, 10-28 parts ABS, 1-4.5 parts compatibilizer, 3-7 parts toughening agent, 8-12 parts ternary synergistic flame retardant, 1-5 parts functional additives, 0.2-0.4 parts antioxidant, and 0-3 parts other additives. The PC mentioned in this invention is polycarbonate, and various types of polycarbonate materials well known to those skilled in the art can be used, including but not limited to bisphenol A type polycarbonate, bisphenol F type polycarbonate, etc. Commercially available products include but are not limited to Wanhua Chemical's CLARNATE series (weight average molecular weight of approximately 20,000-25,000), Japan's Idemitsu FN series, Mitsubishi Chemical's E series, LG's LI series, etc.

[0028] In order to give the PC alloy material excellent toughness, heat resistance and other advantages, an appropriate amount of ABS material is added to the raw materials in this invention. The ABS material is the acrylonitrile / butadiene / styrene copolymer material well known to those skilled in the art. Based on 65 to 75 parts by weight of the PC material, the weight of the ABS is 10 to 28 parts by weight. For example, the weight can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28 parts by weight, etc. The present invention does not impose any special limitation on the specific type and source of the ABS. Commercially available products known to those skilled in the art can be used, including but not limited to BASF GP-22 (18 g / 10 min (220 ℃, 10 kg)), Chi Mei Industrial PA-747F (15 g / 10 min (220 ℃ / 10 kg)), Shengxi Ao Zhangjiagang 8434 (28 g / 10 min (230 ℃ / 3.8 kg)), Northern Huajin Chemical ABS275 (10 g / 10 min (220 ℃ / 10 kg)), Jilin Petrochemical HF-681 (39.4 g / 10 min (220 ℃ / 10 kg)), Jilin Petrochemical 0215A (5.5 g / 10 min (220 ℃ / 10 kg)), etc.

[0029] Because PC materials have poor compatibility with non-polar resins (such as ABS), the interfacial bonding of the blended materials is weak, making it difficult to synergistically improve mechanical properties. Therefore, in this invention, an appropriate amount of compatibilizer component is added to the raw materials for preparing the PC alloy material. The compatibilizer component is mainly used to improve the compatibility between PC and ABS components. Based on 65-75 parts by weight of the PC material, the weight of the compatibilizer is 1-4.5 parts by weight. Examples of possible weights include 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.7 parts by weight, 3 parts by weight, 3.3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.3 parts by weight, and 4.5 parts by weight.

[0030] The compatibilizer molecular structure described in this invention simultaneously includes a polar molecular structure that interacts with polar molecular chain segments and a nonpolar molecular structure that interacts with nonpolar molecular chain segments. In some embodiments, the compatibilizer is a polyolefin polymer grafted with a polar molecular structure or the resulting functional polymer structure. More preferably, the compatibilizer is maleic anhydride-grafted ABS. Preferably, the maleic anhydride grafting rate in the maleic anhydride-grafted ABS is not less than 1.5%. Preferably, the maleic anhydride grafting rate in the maleic anhydride-grafted ABS is 1.8~2.5%. For example, the maleic anhydride grafting rate in the maleic anhydride-grafted ABS can be 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, etc. In this invention, the term "grafting rate" refers to the percentage of maleic anhydride grafted onto the ABS molecular chain in a maleic anhydride-grafted ABS polymer relative to the total mass of the grafted product. This percentage can be determined by testing in a manner well-known to those skilled in the art, such as by calculation using alkaline hydrolysis-acid back titration. This invention does not impose any specific limitations on the source of the maleic anhydride-grafted ABS; commercially available products well-known to those skilled in the art can be used, including but not limited to Ningbo Nengzhiguang New Materials RA-218 (grafting rate 2.0–2.5%), Anhui Xingbeida New Materials ST-4200 (grafting rate 2.0–2.3%), Shenyang Ketong Plastics KT-850 (grafting rate 2.0–2.3%), and Shenyang Siwei Polymer SW-800G (grafting rate 2.0–2.5%). It can also be prepared using methods well-known to those skilled in the art, such as peroxide initiation and co-directional twin-screw melt grafting. In this invention, by adjusting the ratio of PC and ABS and adding an appropriate amount of compatibilizer, the phase structure of the alloy material is controlled to form islands or bicontinuous phases, thereby improving the uniformity of the blend system. Furthermore, by optimizing the maleic anhydride grafting rate in maleic anhydride-grafted BAS, the matrix resin materials are fused together, enhancing the interphase bonding. Simultaneously, the anhydride groups undergo esterification with the terminal hydroxyl groups of PC, forming chemical bonds that bridge the gap and reduce interfacial tension, thus contributing to improved weather resistance and other properties of the alloy material.

[0031] The raw materials for preparing the high-toughness, chemical-resistant, and flame-retardant PC alloy material of the present invention include an appropriate amount of toughening agent to improve the toughness of the alloy material. Based on 65-75 parts by weight of the PC material, the toughening agent weighs 3-7 parts by weight. Examples of possible weights include 3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4.0 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, 5.0 parts by weight, 5.3 parts by weight, 5.5 parts by weight, 5.8 parts by weight, 6.0 parts by weight, 6.2 parts by weight, 6.5 parts by weight, 6.7 parts by weight, 6.8 parts by weight, and 7.0 parts by weight. The toughening agent in this invention is composed of a core-shell structure MBS and an organosilicon elastomer, wherein the organosilicon elastomer is an amino-modified organosilicon. The core-shell structure MBS is a methyl methacrylate-butadiene-styrene terpolymer, a "hard core-soft shell" polymer.

[0032] In some preferred embodiments, the particle size of the core-shell MBS is not higher than 200 nm; more preferably, the particle size is not lower than 100 nm; preferably, the particle size of the core-shell MBS is 140 nm to 170 nm, and examples include 140 nm, 142 nm, 145 nm, 148 nm, 150 nm, 152 nm, 155 nm, 158 nm, 160 nm, 163 nm, 165 nm, 167 nm, 170 nm, etc. More preferably, the melt flow index of the core-shell structure MBS at 200 °C / 5 kg is 10~20 g / 10 min. Examples of melt flow indexes include 10 g / 10 min, 11 g / 10 min, 12 g / 10 min, 13 g / 10 min, 14 g / 10 min, 15 g / 10 min, 16 g / 10 min, 17 g / 10 min, 18 g / 10 min, 19 g / 10 min, and 20 g / 10 min. The specific source of the core-shell MBS in this invention is not specifically limited. Products that are commercially available to those skilled in the art can be used, including but not limited to Shandong Yuanbang YB-MS (particle size 150nm), Shandong Ruifeng RF-MBS 66 (particle size 160nm), Kane Ace M-701 (particle size 140nm), Kane Ace M-702 (particle size 140nm), Mitsubishi S-2030 (particle size 170nm), and Anhui Xingbeida MBS-S60 (particle size 145nm).

[0033] The organosilicon elastomer described in this invention is an amino-modified organosilicon material, which may have a core-shell structure. Furthermore, amino modification can be performed on either the core or shell molecular structure. This invention does not impose specific limitations on the preparation method or source of the amino-modified organosilicon material. It can be prepared using methods well-known to those skilled in the art, such as emulsion polymerization, or commercially available through means familiar to them. For example, it may use, but is not limited to, Mitsubishi Rayon S-2001 amino-modified organosilicon core-shell toughening agent (particle size 150 nm) or Mitsubishi Rayon S-2030 amino-modified organosilicon core-shell toughening agent (particle size 170 nm).

[0034] In some embodiments of the present invention, the amount of core-shell structure MBS in the toughening agent is not less than the amount of organosilicon elastomer; more preferably, the weight ratio of the core-shell structure MBS to the organosilicon elastomer is (1-2):1; examples include weight ratios of 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc.

[0035] In order to make the high-toughness, chemical-resistant, and flame-retardant PC alloy material of the present invention have certain flame retardancy, an appropriate amount of flame retardant is added to its preparation raw materials. The flame retardant mentioned in the present invention is a halogen-free flame retardant system. Further, the flame retardant is a ternary synergistic flame retardant. The ternary synergistic flame retardant refers to a flame retardant containing at least three types of flame retardants in the art, including but not limited to phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, metal flame retardants, and organic flame retardants. Based on 65-75 parts by weight of the PC material, the ternary synergistic flame retardant has a weight of 8-12 parts by weight. Examples of its weight include 8 parts by weight, 8.2 parts by weight, 8.5 parts by weight, 8.8 parts by weight, 9.0 parts by weight, 9.2 parts by weight, 9.5 parts by weight, 9.8 parts by weight, 10 parts by weight, 10.2 parts by weight, 10.5 parts by weight, 10.8 parts by weight, 11 parts by weight, 11.3 parts by weight, 11.5 parts by weight, 11.7 parts by weight, 11.9 parts by weight, and 12 parts by weight.

[0036] In some preferred embodiments, the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder; preferably, the weight ratio of the ammonium polyphosphate, melamine cyanurate, and silicone powder is (1-2):1:(0.5-1.5). Examples of such weight ratios include 1:1:0.5, 1:1:1, 1:1:1.5, 1.5:1:0.5, 1.5:1:1, 1.5:1:1.5, 2:1:0.5, 2:1:1, 2:1:1.5, etc.

[0037] This invention uses ammonium polyphosphate as the acid source, melamine cyanurate (MCA) as the gas source, and organosilicon flame retardant (such as silicone powder) as the charring agent. Ammonium polyphosphate decomposes upon heating to generate polyphosphoric acid, catalyzing the dehydration of PC to form char. Melamine cyanurate decomposes to release ammonia and water, diluting the concentration of flammable gases. Silicone powder migrates to the material surface at high temperatures, forming a Si-O-Si network covering the char layer and enhancing the barrier effect. Zinc borate is introduced as a synergist, reacting with ammonium polyphosphate to form a borophosphate glass, improving the thermal stability of the char layer. The total amount of flame retardant added is ≤15%, achieving a flame retardant rating of 5VA@3.0mm, while maintaining a heat distortion temperature ≥85℃.

[0038] The high-toughness, chemical-resistant, and flame-retardant PC alloy material of the present invention contains an appropriate amount of functional additives. These functional additives enhance the interaction between components in the PC alloy material formulation system, thereby improving the overall performance of the alloy material. The functional additives are fluorine-silicon composites containing fluorine and silicon atoms in their molecular structure. Based on 65-75 parts by weight of the PC material, the weight of the functional additive is 1-5 parts by weight. Examples of such weights include 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.3 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.7 parts by weight, and 5 parts by weight.

[0039] Furthermore, the fluorine-silicon composite is a nano-silica grafted perfluoropolyether material; the nano-silica grafted perfluoropolyether material described in this invention is a component prepared by grafting nano-silica and perfluoropolyether compounds through a grafting reaction (including but not limited to solution free radical polymerization, interfacial polymerization, etc.; for example, using a silane coupling agent such as KH-570 (γ-methacryloyloxypropyltrimethoxysilane) (or KH-550) in a solvent to obtain a SiO2-KH570 intermediate with double bonds on the surface, and then reacting it with the perfluoropolyether compound through free radical polymerization under the action of an initiator (e.g., benzoyl peroxide), and then obtaining the nano-silica grafted perfluoropolyether material by cooling, centrifugation, washing and drying). It can be prepared by methods well known to those skilled in the art, or commercially available products can be used. More preferably, the raw materials for preparing the nano-silica-grafted perfluoropolyether material include nano-silica and a perfluoropolyether compound, wherein the average functionality of the perfluoropolyether compound molecules is 1.5 to 3.5; the silica can be nano-silica with an average particle size of 50 to 250 nm; wherein, the term "average functionality" refers to the average number of active functional groups that can participate in the reaction in each molecular structure, wherein the active functional groups include various functional groups known to those skilled in the art, including but not limited to unsaturated double bonds, amino groups, hydroxyl groups, carboxyl groups, thiol groups, epoxy groups, etc.; the average functionality of the perfluoropolyether compound molecules in this invention can be listed as 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, etc. More preferably, the active functional groups of the perfluoropolyether compound can be the same or different; that is, each molecule can contain more than one identical functional group, or it can contain two or more different types of functional groups. More preferably, the number average molecular weight of the perfluoropolyether compound is not less than 2000, and more preferably, its number average molecular weight is 2400~8100.

[0040] In some embodiments, the perfluoropolyether compound includes HFPO carboxylic acid and HFPO amide alcohol, wherein the HFPO carboxylic acid refers to a perfluoropolyether whose molecular structure is capped by a terminal carboxyl group, and may include, but is not limited to, WeissBonya CA-20 (number average molecular weight 2000-3000), CA-30 (number average molecular weight 3000-4000), CA-70 (number average molecular weight 7000-8100), etc.; wherein the HFPO amide alcohol refers to a perfluoropolyether whose molecular structure contains an amide bond and a terminal hydroxyl group, and may include, but is not limited to, WeissBonya AEA-20 (number average molecular weight 2000-3000), AEA-30 (number average molecular weight 3000-4000), AEA-70 (number average molecular weight 7000-8100), etc.

[0041] Preferably, the mass ratio of HFPO carboxylic acid to HFPO amide alcohol is (2-3):1; other examples include 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3.0:1, etc.

[0042] In some preferred embodiments of the present invention, the perfluoropolyether compound further includes HFPO diol, wherein the HFPO diol refers to a perfluoropolyether compound containing two hydroxyl groups in each molecular structure. It may include, but is not limited to, WeissBonya DIA-20 (number average molecular weight 2000-3000), DIA-30 (number average molecular weight 3000-4000), and DIA-70 (number average molecular weight 7000-8100) HFPO diols.

[0043] Preferably, the molar amount of the HFPO diol accounts for half of the amount of the HFPO amide alcohol.

[0044] One preparation method of the nano-silica grafted perfluoropolyether material includes the following steps: 100 parts by weight of nano-SiO2 (80nm) is added to an ethanol-water (95:5) mixed solvent and dispersed at high speed at room temperature for 30 min, followed by the dropwise addition of 45 parts by weight of KH-550 silane coupling agent. The mixture is heated to 78℃ and refluxed for 3 h. After cooling, centrifugation and washing, the mixture is dried at 80℃ to obtain SiO2-KH550 for later use. The SiO2-KH550 is redispersed in anhydrous acetone (15wt% solid content), and 7 parts by weight of triethylamine is added. The mixture is stirred at 50℃ and the reaction is carried out at a uniform rate. An acetone solution (50wt%) containing a perfluoropolyether compound (50 parts by weight) is added dropwise over 1 h. The mixture is kept at this temperature for 3 h. After cooling, the solvent is removed by centrifugation, and the mixture is washed twice with ethanol. The mixture is then vacuum dried at 80℃ for 8 h to obtain a white powder nano-silica grafted perfluoropolyether material (functional additive sample S).

[0045] In the process of developing this invention, the applicant discovered that adding an appropriate amount of nano-silica grafted with perfluoropolyether material can not only improve the toughness of PC alloy materials, enabling them to internally transfer and dissipate the impact energy they bear, thus exhibiting high impact resistance, but also, through the long-chain fluorocarbon structure in the functional additive molecular chain, reduce solvent adsorption through hydrophobic and oleophobic effects. The residual carboxyl groups at the ends of the carboxyl groups interact with the active groups such as the terminal hydroxyl groups of PC through intermolecular hydrogen bonding and esterification reactions, forming a dense protective layer on the surface. After nano-SiO2 is grafted with perfluoropolyether using a silane coupling agent (KH-550), it forms hydrogen bonds and van der Waals forces with the PC matrix, enhancing interfacial bonding and filling microscopic defects. During solvent immersion, the fluoro-silicon synergistic layer blocks the penetration of carbon tetrachloride (non-polar) and glacial acetic acid (polar) through a dual mechanism of physical shielding and chemical inertness. Within 48 hours, the surface shows no corrosion or cracking, and the tensile strength retention rate is ≥90%. Moreover, the applicant found that the aforementioned excellent properties such as toughness and chemical resistance are also largely related to the maleic anhydride grafting rate of the compatibilizer used. When the maleic anhydride grafting rate is too high or too low, it will cause a decrease in the impact resistance and chemical resistance of the sample. Even if the above-mentioned nano-silica grafted perfluoropolyether material is used, it will be affected to a certain extent.

[0046] The high-toughness, chemical-resistant, and flame-retardant PC alloy material of this invention contains an appropriate amount of antioxidant, which is mainly used to improve the oxidation resistance of the PC alloy material, enabling it to have anti-aging properties and a longer service life under harsh conditions. This invention does not impose special limitations on the specific type or source of the antioxidant; various antioxidants known to those skilled in the art for use in PC alloy materials can be selected, including but not limited to one or more combinations of hindered phenolic antioxidants, phosphite antioxidants, thioester antioxidants, benzofuran antioxidants, and hydroxylamine antioxidants.

[0047] The high-toughness, chemical-resistant, and flame-retardant PC alloy material of the present invention contains appropriate amounts of other additives. These other additives are those known to those skilled in the art, besides the aforementioned flame retardants, toughening agents, functional additives, antioxidants, and compatibilizers, that can be used to improve PC alloy materials. These include, but are not limited to, anti-dripping agents, UV stabilizers, synergists, lubricants, and stabilizers. Among these, the synergists include, but are not limited to, zinc borate.

[0048] This invention also provides a method for preparing the aforementioned high-toughness, chemical-resistant, and flame-retardant PC alloy material. The method includes the following steps: measuring the raw materials for the PC alloy material according to the specified ratio, adding each component to a high-speed mixer and mixing, then adding the mixture to a twin-screw extruder for melt extrusion, granulation, and drying to obtain the PC alloy material. This invention does not impose specific limitations on the temperature, speed, and other parameters of the twin-screw extruder during the preparation of the PC alloy material; these parameters can be adjusted according to actual conditions.

[0049] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0050] Example 1

[0051] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0052] 70 parts by weight of PC;

[0053] 20 parts by weight of ABS;

[0054] Compatibilizer 3.8 parts by weight;

[0055] 5.5 parts by weight of toughening agent;

[0056] 10 parts by weight of ternary synergistic flame retardant;

[0057] Functional additives, 4.5 parts by weight;

[0058] Antioxidant 0.3 parts by weight;

[0059] Other additives: 1.5 parts by weight;

[0060] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals, and the ABS is PA-747F from Chi Mei Industrial Co., Ltd.; the compatibilizer is maleic anhydride-grafted ABS KT-850 from Shenyang Ketong Plastics (grafting rate 2.3%); the toughening agent is composed of core-shell structured MBS and silicone elastomer in a mass ratio of 1.5:1, the core-shell structured MBS is KaneAce M-701 (particle size 140nm) from Japan, and the silicone elastomer is Mitsubishi Rayon S-2001 amino-modified silicone core-shell elastomer (particle size 150nm); the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1; the antioxidant is RIANOX. 245; the other additives are synergists zinc borate (ZnB); the functional additive is a fluorine-silicon composite, which is a nano-silica grafted perfluoropolyether material. Its raw materials are silica with an average particle size of 80nm and perfluoropolyether compounds (which are composed of HFPO carboxylic acid WeissBonya CA-70 (number average molecular weight 7000-8100), HFPO amide alcohol WeissBonya AEA-30 (number average molecular weight 3000-4000), and HFPO diol WeissBonya DIA-30 (number average molecular weight 3000-4000)) with a mass ratio of 2.5:1:0.5. It is prepared by the same steps as the functional additive sample S described above.

[0061] Example 2

[0062] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0063] 70 parts by weight of PC;

[0064] 20 parts by weight of ABS;

[0065] Compatibilizer 3.8 parts by weight;

[0066] 5.5 parts by weight of toughening agent;

[0067] 10 parts by weight of ternary synergistic flame retardant;

[0068] Functional additives, 4.5 parts by weight;

[0069] Antioxidant 0.3 parts by weight;

[0070] Other additives: 1.5 parts by weight;

[0071] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals, and the ABS is PA-747F from Chi Mei Industrial Co., Ltd.; the compatibilizer is maleic anhydride-grafted ABS KT-850 from Shenyang Ketong Plastics (grafting rate 2.3%); the toughening agent is composed of core-shell structured MBS and silicone elastomer in a mass ratio of 1.5:1, the core-shell structured MBS is KaneAce M-701 (particle size 140nm) from Japan, and the silicone elastomer is Mitsubishi Rayon S-2001 amino-modified silicone core-shell elastomer (particle size 150nm); the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1; the antioxidant is RIANOX. 245; the other additives are zinc borate (ZnB) synergists; the functional additive is a fluorine-silicon composite material grafted with nano-silica and perfluoropolyether, which is prepared from silica with an average particle size of 80 nm and perfluoropolyether compound (which is composed of HFPO carboxylic acid WeissBonya CA-70 (number average molecular weight 7000-8100) and HFPO amide alcohol WeissBonya AEA-30 (number average molecular weight 3000-4000)) in a mass ratio of 2.5:1, and is prepared by the same steps as functional additive sample S as described above.

[0072] Example 3

[0073] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0074] 70 parts by weight of PC;

[0075] 20 parts by weight of ABS;

[0076] Compatibilizer 3.8 parts by weight;

[0077] 5.5 parts by weight of toughening agent;

[0078] 10 parts by weight of ternary synergistic flame retardant;

[0079] Functional additives, 4.5 parts by weight;

[0080] Antioxidant 0.3 parts by weight;

[0081] Other additives: 1.5 parts by weight;

[0082] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals, and the ABS is PA-747F from Chi Mei Industrial Co., Ltd.; the compatibilizer is maleic anhydride-grafted ABS KT-850 from Shenyang Ketong Plastics (grafting rate 2.3%); the toughening agent is composed of core-shell structured MBS and silicone elastomer in a mass ratio of 1.5:1, the core-shell structured MBS is KaneAce M-701 (particle size 140nm) from Japan, and the silicone elastomer is Mitsubishi Rayon S-2001 amino-modified silicone core-shell elastomer (particle size 150nm); the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1; the antioxidant is RIANOX. 245; the other additives are zinc borate (ZnB) synergists; the functional additive is a fluorine-silicon composite material grafted with nano-silica and perfluoropolyether, which is prepared from silica with an average particle size of 80 nm and perfluoropolyether compound (which is composed of HFPO carboxylic acid WeissBonya CA-70 (number average molecular weight 7000-8100) and HFPO diol WeissBonya DIA-30 (number average molecular weight 3000-4000)) in a mass ratio of 2.5:0.5, and is prepared by the same steps as functional additive sample S as described above.

[0083] Example 4

[0084] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0085] 70 parts by weight of PC;

[0086] 20 parts by weight of ABS;

[0087] Compatibilizer 3.8 parts by weight;

[0088] 5.5 parts by weight of toughening agent;

[0089] 10 parts by weight of ternary synergistic flame retardant;

[0090] Functional additives, 4.5 parts by weight;

[0091] Antioxidant 0.3 parts by weight;

[0092] Other additives: 1.5 parts by weight;

[0093] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals, and the ABS is PA-747F from Chi Mei Industrial Co., Ltd.; the compatibilizer is maleic anhydride-grafted ABS KT-850 from Shenyang Ketong Plastics (grafting rate 2.3%); the toughening agent is composed of core-shell structured MBS and silicone elastomer in a mass ratio of 1.5:1, the core-shell structured MBS is KaneAce M-701 (particle size 140nm) from Japan, and the silicone elastomer is Mitsubishi Rayon S-2001 amino-modified silicone core-shell elastomer (particle size 150nm); the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1; the antioxidant is RIANOX. 245; the other additives are synergists zinc borate (ZnB); the functional additive is a fluorine-silicon composite material, which is a nano-silica grafted perfluoropolyether material. Its raw materials are silica with an average particle size of 80nm and perfluoropolyether compound (HFPO carboxylic acid WeissBonya CA-70 (number average molecular weight 7000-8100)) in a mass ratio of 2.5:1:0.5. It is prepared by the same steps as the functional additive sample S described above.

[0094] Example 5

[0095] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0096] 70 parts by weight of PC;

[0097] 20 parts by weight of ABS;

[0098] Compatibilizer 3.8 parts by weight;

[0099] 5.5 parts by weight of toughening agent;

[0100] 10 parts by weight of ternary synergistic flame retardant;

[0101] Functional additives, 4.5 parts by weight;

[0102] Antioxidant 0.3 parts by weight;

[0103] Other additives: 1.5 parts by weight;

[0104] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals Company, and the ABS is PA-747F from Chi Mei Industrial Co., Ltd.; the compatibilizer is maleic anhydride-grafted ABS KT-850 from Shenyang Ketong Plastics (grafting rate 2.3%); the toughening agent is composed of core-shell structured MBS and silicone elastomer in a mass ratio of 1.5:1, the core-shell structured MBS is KaneAce M-701 from Japan (particle size 140nm), and the silicone elastomer is Mitsubishi Rayon S-2001 amino-modified silicone core-shell elastomer (particle size 150nm); the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1; the antioxidant is RIANOX 245; the other additives are zinc borate (ZnB) synergist; and the functional additives are polytetrafluoroethylene micro powder.

[0105] Example 6

[0106] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0107] 70 parts by weight of PC;

[0108] 20 parts by weight of ABS;

[0109] Compatibilizer 3.8 parts by weight;

[0110] 5.5 parts by weight of toughening agent;

[0111] 10 parts by weight of ternary synergistic flame retardant;

[0112] Functional additives, 4.5 parts by weight;

[0113] Antioxidant 0.3 parts by weight;

[0114] Other additives: 1.5 parts by weight;

[0115] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals, and the ABS is PA-747F from Chi Mei Industrial Co., Ltd.; the compatibilizer is maleic anhydride-grafted ABS Shenyang Siwei High Polymer SW-800G (grafting rate 2.8%); the toughening agent is composed of core-shell structured MBS and organosilicon elastomer in a mass ratio of 1.5:1, the core-shell structured MBS is KaneAce M-701 (particle size 140nm) from Japan, and the organosilicon elastomer is Mitsubishi Rayon S-2001 amino-modified organosilicon core-shell elastomer (particle size 150nm); the ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1; the antioxidant is RIANOX. 245; the other additives are synergists zinc borate (ZnB); the functional additive is a fluorine-silicon composite, which is a nano-silica grafted perfluoropolyether material. Its raw materials are silica with an average particle size of 80nm and perfluoropolyether compounds (which are composed of HFPO carboxylic acid WeissBonya CA-70 (number average molecular weight 7000-8100), HFPO amide alcohol WeissBonya AEA-30 (number average molecular weight 3000-4000), and HFPO diol WeissBonya DIA-30 (number average molecular weight 3000-4000)) with a mass ratio of 2.5:1:0.5. It is prepared by the same steps as the functional additive sample S described above.

[0116] Example 7

[0117] This embodiment provides a high-toughness, chemical-resistant, and flame-retardant PC alloy material, the preparation of which originally includes the following components:

[0118] 70 parts by weight of PC;

[0119] 20 parts by weight of ABS;

[0120] Compatibilizer 3.8 parts by weight;

[0121] 5.5 parts by weight of toughening agent;

[0122] 10 parts by weight of ternary synergistic flame retardant;

[0123] Functional additives, 4.5 parts by weight;

[0124] Antioxidant 0.3 parts by weight;

[0125] Other additives: 1.5 parts by weight;

[0126] The PC is FB2560 polycarbonate material from Saudi Basic Chemicals, and the ABS is PA-747F from Chi Mei Corporation. The compatibilizer is maleic anhydride-grafted ABS from Koton Plastics KT-3 (grafting rate 1.4%). The toughening agent consists of core-shell structured MBS and silicone elastomer in a mass ratio of 1.5:1. The core-shell structured MBS is Kane Ace M-701 (particle size 140nm) from Japan, and the silicone elastomer is Mitsubishi Rayon S-2001 amino-modified silicone core-shell elastomer (particle size 150nm). The ternary synergistic flame retardant consists of ammonium polyphosphate, melamine cyanurate, and silicone powder in a weight ratio of 1.5:1:1. The antioxidant is RIANOX. 245; the other additives are zinc borate (ZnB) synergists; the functional additive is a fluorine-silicon composite material grafted with nano-silica and perfluoropolyether, which is prepared from silica with an average particle size of 80 nm and perfluoropolyether compounds (which are composed of HFPO carboxylic acid WeissBonya CA-70 (number average molecular weight 7000-8100), HFPO amide alcohol WeissBonya AEA-30 (number average molecular weight 3000-4000), and HFPO diol WeissBonya DIA-30 (number average molecular weight 3000-4000)) in a mass ratio of 2.5:1:0.5, and is prepared by the same steps as the functional additive sample S described above.

[0127] The applicant prepared the PC alloy material in the above embodiments according to the same preparation process. The raw materials for the preparation of the PC alloy material were measured according to the proportion. The components were added to a high-speed mixer and mixed. Then, the mixture was added to a twin-screw extruder for melt extrusion, granulation, and drying to obtain 7 test samples, which were recorded as Sample 1 to Sample 7 (corresponding to Examples 1 to 7 in sequence). The obtained samples were tested. The test methods and test results are as follows (10 test samples were used for each sample test, and the average value was taken (rounded to the nearest integer).

[0128] Bending strength: Tested according to ISO 178 standard, bending speed is 2 mm / min.

[0129] Notched impact strength: Tested according to ISO 180 / 1A standard, with a sample thickness of 4.0 mm.

[0130] The test results are shown in Table 1 below.

[0131] Table 1 Mechanical Performance Tests

[0132] Flexural strength / MPa Notched impact strength / (kJ / m²) Sample 1 87 55 Sample 2 84 50 Sample 3 82 48 Sample 4 80 46 Sample 5 81 45 Sample 6 86 52 Sample 7 77 45

[0133] Flame retardancy rating: Flame retardancy performance tests were conducted on 1.5mm and 3.0mm thick samples according to UL94-2019 and IEC 60950-1 standards.

[0134] See Table 2 below for specific test results.

[0135] Table 2 Flame retardant performance test

[0136] UL94 IEC Sample 1 V0 @ 1.5 mm 5VA @ 3.0 mm Sample 2 V0 @ 1.5 mm 5VA @ 3.0 mm Sample 3 V0 @ 1.5 mm 5VA @ 3.0 mm Sample 4 V1 @ 1.5 mm 5VA @ 3.0 mm Sample 5 V1 @ 1.5 mm 5VA @ 3.0 mm Sample 6 V0 @ 1.5 mm 5VA @ 3.0 mm Sample 7 V0 @ 1.5 mm 5VA @ 3.0 mm

[0137] Tensile properties: Tensile strength tests were performed on the above 7 tensile test samples (3 mm) according to ISO 527 standard, with a tensile speed of 50 mm / min (without solvent immersion).

[0138] Chemical resistance: The seven tensile test samples (3 mm) were immersed in glacial acetic acid / carbon tetrachloride at 70°C for 48 hours according to the ISO 175 test standard. After immersion, the samples were removed, the immersion solvent was dried, and tensile strength was tested according to the ISO 527 standard (tensile speed 50 mm / min). The test results were compared with the results of the un-immersion test, and the tensile strength retention rate (%) was calculated as ((un-immersion strength / immersion strength) * 100%, rounded to the nearest integer). In addition, the appearance of silver streaks or whitening on the sample surface after the tensile strength test was observed and classified into four levels: Level 1 represents no silver streaks or discoloration on the surface of all test samples; Level 2 represents slight loss of gloss and whitening on more than 5 test samples; Level 3 represents a small amount of silver streaks on at least 6 test samples; Level 4 represents obvious swelling and cracking on more than 6 test samples. The test results are shown in Table 3.

[0139] Table 3 Chemical Resistance Test

[0140]

[0141] In addition, the applicant applied a mixture of NaCl (5g / L) and urea (1g / L) to the test sample of the above embodiment (thickness of 4.0mm). After 72 hours, it was found that most samples did not show obvious color difference or loss of luster. In particular, the test results of sample 1 were basically consistent with those before and after the test.

[0142] The foregoing description is merely an exemplary embodiment of this disclosure and should not be construed as limiting the scope of this disclosure. Any equivalent changes and modifications made in accordance with the teachings of this disclosure shall still fall within the scope of this disclosure. Those skilled in the art will readily conceive of other embodiments of this disclosure upon considering the specification and practicing the disclosure herein. This invention is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not described herein. The specification and embodiments are to be considered exemplary only, and the scope and spirit of this disclosure are defined by the claims.

Claims

1. A high toughness, chemical resistant, flame retardant PC alloy material, characterized in that, The preparation raw material, in terms of weight parts, comprises: PC 65~75 weight parts; ABS 10~28 weight parts; Compatibility agent 1~4.5 weight parts; Toughening agent 3~7 weight parts; Ternary synergistic flame retardant 8~12 weight parts; Functional auxiliary agent 1~5 weight parts; Antioxidant 0.2~0.4 weight parts; Other auxiliary agent 0~3 weight parts; The functional auxiliary agent is a fluorine-silicon compound containing fluorine atoms and silicon atoms in the molecular structure; the toughening agent is composed of a core-shell structure MBS and an organic silicon elastomer, and the organic silicon elastomer is an amino-modified organic silicon material.

2. The high toughness, flame retardant PC alloy material of claim 1, wherein, The fluorine-silicon compound is a nano-silicon dioxide grafted perfluoropolyether material.

3. The high toughness, flame retardant PC alloy material of claim 2, wherein, The preparation raw material of the nano-silicon dioxide grafted perfluoropolyether material comprises nano-silicon dioxide and a perfluoropolyether compound, and the average functionality of the molecules of the perfluoropolyether compound is 1.5~3.

5.

4. The high toughness, flame retardant PC alloy material of claim 3, wherein, The number average molecular weight of the perfluoropolyether compound is not less than 2000.

5. The high toughness, resistant, flame-retardant PC alloy material according to claim 3 or 4, characterized in that, The perfluoropolyether compound comprises HFPO carboxylic acid and HFPO amido alcohol.

6. The high toughness, flame retardant PC alloy material of claim 5, wherein, The mass ratio of the HFPO carboxylic acid and the HFPO amido alcohol is (2-3):

1.

7. The high toughness, resistant, flame-retardant PC alloy material according to any one of claims 1-6, characterized in that, The compatibility agent is maleic anhydride grafted ABS; preferably, the maleic anhydride grafting rate of the maleic anhydride grafted ABS is not less than 1.5%.

8. The high toughness, resistant, flame-retardant PC alloy material according to any one of claims 1-6, characterized in that, The ternary synergistic flame retardant is composed of ammonium polyphosphate, melamine cyanurate, and silicone powder; preferably, the weight ratio of the ammonium polyphosphate, the melamine cyanurate, and the silicone powder is (1-2):1:(0.5-1.5).

9. The high toughness, resistant, flame-retardant PC alloy material according to any one of claims 1-6, characterized in that, The weight ratio of the core-shell structure MBS and the organic silicon elastomer is (1-2):

1.

10. The process for the preparation of high toughness, resistant, flame-retardant PC alloy materials according to any one of claims 1-9, characterized by the fact that, It comprises the following steps: According to the proportioning amount, the preparation raw material of the PC alloy material is taken, each component is added to a high-speed mixer for stirring and mixing, then it is added to a twin-screw extruder for melt extrusion, granulation, and drying, and the PC alloy material is obtained.

Images