Acrylonitrile-styrene-butadiene copolymer materials and methods for making the same

Abstract

This invention discloses an acrylonitrile-styrene-butadiene copolymer material, comprising the acrylonitrile-styrene-butadiene copolymer, a phosphorus-based flame retardant, a nitrogen-based flame retardant, and a modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist. Because the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist contains boron, a cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1, and two inorganic silicon cage cores, these structures form protective layers such as a carbon layer, a ceramic barrier layer, a protective film, or a heat-insulating coke layer during combustion, significantly improving the anti-dripping effect. Simultaneously, it isolates heat and oxygen transfer, reducing the release of flammable gases. These multiple mechanisms work together to significantly improve the flame retardant performance of the material. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergistically works with the phosphorus-based flame retardant (providing an acid source) and the nitrogen-based flame retardant (providing a gas source) to synergistically retard the flame, reducing the amount of flame retardant required while improving the flame retardant and mechanical properties of the acrylonitrile-styrene-butadiene copolymer material. The acrylonitrile-styrene-butadiene copolymer material provided by this invention has good flame retardant properties and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of materials, and more specifically to an acrylonitrile-styrene-butadiene copolymer material. Background Technology

[0002] Polyhedral oligomeric silsesquioxane (POSS) is a special type of organic amorphous material. It is a polycyclic organic monomer composed of a silicon framework and its intercalated oxygen atoms. It is an inorganic-organic hybrid nanomaterial. The inorganic silicon cage core in POSS decomposes upon heating to form a dense ceramic barrier layer, which isolates the release of flammable gases and the entry of external heat into the interior, thereby delaying further decomposition of the material. POSS shows great application potential in the field of flame retardants.

[0003] Acrylonitrile-styrene-butadiene copolymer (ABS resin) is a high-strength, tough, and easily processed thermoplastic polymer. ABS resin is a terpolymer composed of acrylonitrile, butadiene, and styrene. This material combines the advantages of the three monomers, exhibiting excellent properties such as high surface hardness, toughness, good low-temperature impact resistance, good creep resistance, good dimensional stability, and low molding shrinkage. However, its oxygen index is only 18.33–20 (<21), classifying it as a flammable material, which has become a major obstacle to the further promotion and development of ABS resin. ABS resin drips easily during combustion, requiring the addition of anti-dripping agents. However, currently, the commonly used anti-dripping agents on the market are still fluorinated anti-dripping agents. Inorganic anti-dripping agents are mostly montmorillonite, kaolin, etc., requiring large amounts to be effective. However, large amounts of inorganic powders significantly affect the mechanical properties of ABS. Therefore, it is essential to develop an acrylonitrile-styrene-butadiene copolymer material that can simultaneously improve flame retardancy and mechanical properties. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention proposes an acrylonitrile-styrene-butadiene copolymer material, which aims to solve the problems of poor flame retardant and mechanical properties of current acrylonitrile-styrene-butadiene copolymer materials.

[0005] The above-mentioned objective of this invention is achieved through the following technical solution:

[0006] In a first aspect, the present invention provides an acrylonitrile-styrene-butadiene copolymer material, wherein the raw materials of the acrylonitrile-styrene-butadiene copolymer material, by weight, comprise:

[0007] 50-70 parts of acrylonitrile-styrene-butadiene copolymer

[0008] 5-10 parts of phosphorus-based flame retardant

[0009] 5-10 parts of nitrogen-based flame retardant

[0010] 2-8 parts of modified polyhedral oligomeric silsesquioxanes and their derivatives as flame retardant synergists.

[0011] The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is as follows:

[0012]

[0013] Wherein, R is a non-reactive group, such as isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl, and R1 is n-propyl or phenylene;

[0014] R2 is a cyclic structure with a carbon-to-hydrogen ratio greater than 1, including at least one of benzofuran group and polycyclic aromatic group.

[0015] In some embodiments of the present invention, the benzofuran group includes at least one of the benzofuran group and the dibenzofuran group;

[0016] And / or, the polycyclic aromatic group includes at least one of a naphthalene ring group, anthracene ring group, phenanthrene ring group, acenaphthene ring group, fluorene ring group and perylene ring group.

[0017] In some embodiments of the present invention, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is prepared by dehydration reaction of compound 1 and compound 2 under the action of a catalyst, and the reaction route is as follows:

[0018]

[0019] In some embodiments of the present invention, the molar ratio of compound 1 to compound 2 is 2:1.

[0020] In some embodiments of the present invention, the preparation method of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist includes the following steps:

[0021] Compound 1 was dissolved in an organic solvent, and an aqueous solution of compound 2 was added under the action of a catalyst. After catalytic reaction, the mixture was washed and dried to obtain the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist.

[0022] The organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

[0023] The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts.

[0024] In some embodiments of the present invention, the phosphorus-based flame retardant includes at least one of phosphate esters and phosphites. ,

[0025] In some embodiments of the present invention, the phosphate ester flame retardant includes at least one of tri(β-chloroethyl) phosphate, tributyl phosphate, triphenyl phosphate, and dimethyl methyl phosphate; the phosphite flame retardant includes at least one of diisopropanol ether diphenyl phosphite, triisoquinone phosphite, triphenyl phosphite, dimethyl phosphite, and diethyl phosphite.

[0026] In some embodiments of the present invention, the raw materials of the acrylonitrile-styrene-butadiene copolymer material further include at least one of a lubricant and an antioxidant; wherein, by weight, the lubricant is 0.2-1 parts and the antioxidant is 0.5-2 parts;

[0027] And / or, the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0028] In a second aspect, the present invention provides a method for preparing the above-mentioned acrylonitrile-styrene-butadiene copolymer material, comprising the following steps: mixing the raw materials uniformly, extruding and granulating them through an extruder to obtain granules, namely the acrylonitrile-styrene-butadiene copolymer material.

[0029] In some embodiments of the present invention, the raw materials further include at least one of lubricant and antioxidant;

[0030] And / or, the extruder is a twin-screw extruder, and the processing temperatures of each temperature zone of the extruder are: Zone 1 140-160℃, Zone 2 170-180℃, Zone 3 190-200℃, Zone 4 190-200℃, Zone 5 190-200℃, Zone 6 190-200℃, Zone 7 190-200℃, Zone 8 170-190℃, and the die head 200-210℃, with a screw speed of 150-170 r / min.

[0031] The acrylonitrile-styrene-butadiene copolymer material of the present invention includes acrylonitrile-styrene-butadiene copolymer, phosphorus-based flame retardant, nitrogen-based flame retardant, and modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists. Because the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists contain boron, a cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1, and two inorganic silicon cage cores, the boron forms boric acid during combustion, which dehydrates and carbonizes the material surface, forming a carbon layer. The two inorganic silicon cage cores decompose upon heating to form a dense ceramic barrier layer, isolating the release of combustible gases and the entry of external heat into the interior. The cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio, and the benzofuran group and polycyclic aromatic groups contain a large amount of carbon. During combustion, the large amount of carbon forms a glassy protective film or a heat-insulating coke layer. These protective films or coke layers can isolate air, prevent heat transfer, and reduce the release of combustible gases. These structures, through the formation of protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, greatly improve the anti-dripping effect. At the same time, they isolate heat and oxygen transfer and reduce the release of combustible gases. The combined effect of these multiple mechanisms significantly improves the flame retardant performance of the material. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists work in conjunction with the phosphorus-based flame retardant providing the acid source to synergistically retard the flame, reducing the amount of flame retardant required while improving the flame retardant and mechanical properties of the acrylonitrile-styrene-butadiene copolymer material. The acrylonitrile-styrene-butadiene copolymer material provided by this invention exhibits good flame retardant and mechanical properties. Attached Figure Description

[0032] Figure 1 This is a molecular structure diagram of the modified POSS flame retardant synergist 1 of the present invention;

[0033] Figure 2 This is a molecular structure diagram of the modified POSS flame retardant synergist 2 of the present invention. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0035] Unless otherwise specified, all technical and scientific terms used herein have their usual meaning within the field to which the subject matter is claimed.

[0036] Polyhedral oligomeric silsesquioxane (POSS) is a special type of organic amorphous material. It is a polycyclic organic monomer composed of a silicon framework and its intercalated oxygen atoms. It is an inorganic-organic hybrid nanomaterial. The inorganic silicon cage core in POSS decomposes upon heating to form a dense ceramic barrier layer, which isolates the release of flammable gases and the entry of external heat into the interior, thereby delaying further decomposition of the material. POSS shows great application potential in the field of flame retardants.

[0037] Acrylonitrile-styrene-butadiene copolymer (ABS resin) is a high-strength, tough, and easily processed thermoplastic polymer. ABS resin is a terpolymer composed of acrylonitrile, butadiene, and styrene. This material combines the advantages of the three monomers, exhibiting excellent properties such as high surface hardness, toughness, good low-temperature impact resistance, good creep resistance, good dimensional stability, and low molding shrinkage. However, its oxygen index is only 18.33–20 (<21), classifying it as a flammable material, which has become a major obstacle to the further promotion and development of ABS resin. ABS resin drips easily during combustion, requiring the addition of anti-dripping agents. However, currently, the commonly used anti-dripping agents on the market are still fluorinated anti-dripping agents. Inorganic anti-dripping agents are mostly montmorillonite, kaolin, etc., requiring large amounts to be effective. However, large amounts of inorganic powders significantly affect the mechanical properties of ABS. Therefore, it is essential to develop an acrylonitrile-styrene-butadiene copolymer material that can simultaneously improve flame retardancy and mechanical properties.

[0038] To address the aforementioned problems, in a first aspect, the present invention provides an acrylonitrile-styrene-butadiene copolymer material, wherein the raw materials of the acrylonitrile-styrene-butadiene copolymer material, by weight, comprise:

[0039] 50-70 parts of acrylonitrile-styrene-butadiene copolymer

[0040] 5-10 parts of phosphorus-based flame retardant,

[0041] 5-10 parts of nitrogen-based flame retardant

[0042] 2-8 parts of modified polyhedral oligomeric silsesquioxanes and their derivatives as flame retardant synergists.

[0043] The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is as follows:

[0044]

[0045] Wherein, R is a non-reactive group, such as isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl, and R1 is n-propyl or phenylene;

[0046] R2 is a cyclic structure with a carbon-to-hydrogen ratio greater than 1, including at least one of benzofuran group and polycyclic aromatic group.

[0047] Understandably, the acrylonitrile-styrene-butadiene copolymer is in any number of parts between 50 and 70, such as 50, 55, 60, 65, and 70; the phosphorus-based flame retardant is in any number of parts between 5 and 10, such as 5, 7, 9, and 10; the nitrogen-based flame retardant is in any number of parts between 5 and 10, such as 5, 7, 9, and 10; and the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists are in any number of parts between 2 and 8, such as 2, 4, 6, and 8.

[0048] Understandably, when R1 connected to Si in the inorganic silicon cage core is a phenylene ring, the phenylene ring contains a benzene ring with a high carbon-hydrogen ratio and high carbon content. During combustion, it works together with the large amount of Si in the inorganic silicon cage core to further improve the flame retardant properties of the inorganic silicon cage core, thereby improving the flame retardant properties of the modified polyhedral oligomeric silsesquioxane flame retardant synergist.

[0049] Understandably, phosphorus-based flame retardants decompose during combustion to form a non-flammable liquid film of phosphoric acid. Simultaneously, the phosphoric acid further dehydrates to form metaphosphoric acid, which then polymerizes to form polymetaphosphoric acid. In this process, not only does the coating layer formed by the phosphoric acid provide a covering effect, but the resulting polymetaphosphoric acid, being a strong acid and a powerful dehydrating agent, dehydrates and carbonizes the polymer, altering the combustion process and forming a carbon film on its surface to isolate it from air, thus exerting a stronger flame-retardant effect. Furthermore, phosphorus-based flame retardants are also free radical scavengers. Mass spectrometry has revealed that any phosphorus-containing compound forms PO· during polymer combustion. This PO· can combine with hydrogen atoms in the flame region, inhibiting flame spread. In addition, the moisture generated during the flame retardation process of phosphorus-based flame retardants can lower the temperature of the condensed phase and dilute the concentration of combustibles in the gas phase. The boron in the modified polyhedral oligomeric silsesquioxane and its derivatives synergistic flame retardant has a 2Pz empty orbital that can accept lone pairs of electrons, and its coordination with phosphorus can produce a synergistic effect, thereby improving the flame retardant effect. Furthermore, boron forms boric acid during combustion, which dehydrates and carbonizes the material surface, forming a carbon layer. The two inorganic silicon cages decompose upon heating to form a dense ceramic barrier layer, isolating the release of combustible gases and preventing external heat from entering the interior. (The last sentence appears to be incomplete and possibly refers to a separate process: "hydrocarbons...") The cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio. The benzofuran group and polycyclic aromatic groups contain a large amount of carbon. During combustion, the large amount of carbon will form a glassy protective film or a heat-insulating coke layer. These protective films or coke layers can isolate air, prevent heat transfer, and reduce the release of flammable gases. By forming protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, these structures greatly improve the anti-dripping effect. At the same time, they isolate heat and oxygen transfer and reduce the release of flammable gases. The combined effect of multiple mechanisms significantly improves the flame retardant performance of the material. Modified polyhedral oligomeric silsesquioxanes and their derivatives, as synergistic flame retardants, contain abundant silicon and oxygen. During polymer combustion, they react with the acidic gases produced by phosphorus-based flame retardants to form phosphates, promoting the reaction between phosphorus and the polymer and rapidly forming a char layer. The SiO2 generated after combustion of the modified polyhedral oligomeric silsesquioxanes and their derivatives interpenetrates within the char layer, similar to the role of sand in cement, making the char layer more stable. The char layer makes it difficult for heat to penetrate the condensed phase, preventing oxygen from entering the combustion zone and preventing gaseous or liquid products from degradation from overflowing the material surface. The boron in the modified polyhedral oligomeric silsesquioxanes and their derivatives possesses a 2Pz empty orbital that can accept lone pairs of electrons, and its coordination with phosphorus produces a synergistic effect. The synergistic effect of boron and phosphorus further accelerates the aforementioned reaction. Simultaneously, the combustion of nitrogen-based flame retardants produces a large amount of non-combustible gas. This non-combustible gas causes foaming in the molten state of the incompletely carbonized ABS, resulting in numerous pores in the burning polymer.Meanwhile, the organic matter continues to react, dehydrate, and carbonize, forming inorganic matter and carbon residue. When the reaction is complete, the system gels and solidifies, finally forming a porous foam carbon layer.

[0050] The acrylonitrile-styrene-butadiene copolymer material of the present invention comprises acrylonitrile-styrene-butadiene copolymer, 5-10 parts of phosphorus-based flame retardant, nitrogen-based flame retardant, and modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist. Because the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists contain boron, a cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1, and two inorganic silicon cage cores, the boron forms boric acid during combustion, which dehydrates and carbonizes the material surface, forming a carbon layer. The two inorganic silicon cage cores decompose upon heating to form a dense ceramic barrier layer, isolating the release of combustible gases and the entry of external heat into the interior. The cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio, and the benzofuran group and polycyclic aromatic groups contain a large amount of carbon. During combustion, the large amount of carbon forms a glassy protective film or a heat-insulating coke layer. These protective films or coke layers can isolate air, prevent heat transfer, and reduce the release of combustible gases. These structures, through the formation of protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, greatly improve the anti-dripping effect. At the same time, they isolate heat and oxygen transfer and reduce the release of combustible gases. The combined effect of these multiple mechanisms significantly improves the flame retardant performance of the material. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists work in conjunction with the phosphorus-based flame retardant providing the acid source to synergistically retard the flame, reducing the amount of flame retardant required while improving the flame retardant and mechanical properties of the acrylonitrile-styrene-butadiene copolymer material. The acrylonitrile-styrene-butadiene copolymer material provided by this invention exhibits good flame retardant and mechanical properties.

[0051] In some embodiments, the benzofuran group includes at least one of the benzofuran group and the dibenzofuran group.

[0052] Phenyl groups have a high carbon-to-hydrogen ratio and a high carbon content, which can slow down the spread of flames during combustion. They can also self-extinguish quickly after the flames are removed, reducing the duration and intensity of combustion. Furan groups, while having a high carbon content, also contain oxygen elements that do not participate in combustion. The combination of these two groups forms benzofuran groups or dibenzofuran groups, which have both a high carbon-to-hydrogen ratio and low combustion elements. Together, they form a glassy protective film or heat-insulating coke layer during combustion. These protective films or coke layers can isolate air, prevent heat transfer, reduce the content of combustibles, and indirectly promote char formation.

[0053] In some embodiments, R2 is a benzofuran group.

[0054] In some embodiments, the polycyclic aromatic group includes at least one of a naphthalene ring group, anthracene ring group, phenanthrene ring group, acenaphthene ring group, fluorene ring group, and perylene ring group.

[0055] Naphthyl ring groups, anthracene ring groups, phenanthrene ring groups, acenaphthene ring groups, fluorene ring groups, and perylene ring groups have a high hydrocarbon ratio and contain a large amount of carbon, making them more likely to form a glassy protective film or heat-insulating coke layer during combustion.

[0056] In some embodiments, R2 is a naphthalene ring group.

[0057] In some embodiments, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is prepared by dehydration reaction of compound 1 and compound 2 under the action of a catalyst, and the reaction route is as follows:

[0058]

[0059] In some embodiments, the molar ratio of compound 1 to compound 2 in the above reaction process is 2:1.

[0060] Compound 1, a polyhedral oligomeric silsesquioxane, has a relatively large spatial structure. During the reaction, compound 2 needs to have sufficiently small steric hindrance to react with compound 1 and yield compound 3, a modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist. In the reaction, each compound 2 is connected to two compounds 1, meaning the molar ratio of compound 1 to compound 2 is 2:1. This ensures sufficient space for compound 3 and achieves structural stability. Compound 2 contains two hydroxyl groups. The two hydroxyl groups of one compound 2 react with one amino group from each of the two compounds 1 to undergo a dehydration reaction, yielding compound 3. The overall reaction requires only a single substance, is simple to operate, and is easy to implement.

[0061] In some embodiments, compound 1 is aminopropylheptaisobutyl cage-like polysilsesquioxane.

[0062] In some embodiments, compound 1 is aminophenyl heptaisobutyl cage-like polysilsesquioxane.

[0063] In some embodiments, compound 2 is benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid.

[0064] In some embodiments, compound 2 is dibenzofuran-3-boronic acid.

[0065] In some embodiments, the structural formula of compound 3 is:

[0066]

[0067] The following is counted as modified POSS flame retardant synergist 1.

[0068] In some embodiments, the structural formula of compound 3 is:

[0069]

[0070] The following is counted as modified POSS flame retardant synergist 2.

[0071] In some embodiments, the preparation method of compound 3 includes the following steps:

[0072] Compound 1 was dissolved in an organic solvent, and an aqueous solution of compound 2 was added under the action of a catalyst. After catalytic reaction, the mixture was washed and dried to obtain compound 3.

[0073] The organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

[0074] The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts.

[0075] In some embodiments, the catalyst is acetic acid.

[0076] In some implementations, the solvent is ethanol.

[0077] In some embodiments, the phosphorus-based flame retardant includes at least one of phosphate esters and phosphites.

[0078] In some embodiments, the phosphate ester flame retardant includes at least one of tri(β-chloroethyl) phosphate, tributyl phosphate, triphenyl phosphate, and dimethyl methyl phosphate; the phosphite flame retardant includes at least one of diisopropanol ether diphenyl phosphite, triisoquinone phosphite, triphenyl phosphite, dimethyl phosphite, and diethyl phosphite.

[0079] In some embodiments, the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0080] In some embodiments, the raw materials of the acrylonitrile-styrene-butadiene copolymer material further include at least one of a lubricant and an antioxidant; wherein, by weight, the lubricant is 0.2-1 parts and the antioxidant is 0.5-2 parts.

[0081] In some embodiments, the lubricant includes, but is not limited to, PTFE powder, zinc stearate, magnesium stearate, silicone, calcium stearate, or ethylene bis-stearamide. Adding a lubricant facilitates more uniform mixing of the various raw materials, improves the flowability of the polymer resin, reduces the coefficient of friction, makes the surface of the product smoother, improves processing efficiency, and also improves the transparency and gloss of the plastic. The type of lubricant is not limited herein; those skilled in the art can select one according to actual needs.

[0082] In some embodiments, antioxidants include, but are not limited to, asymmetric hindered phenolic antioxidants, aromatic amine antioxidants, thioether antioxidants, and phosphite antioxidants. Hindered phenolic antioxidants include, but are not limited to, antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), BHT (2,6-di-tert-butyl-p-cresol), and antioxidant 1076 (octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); aromatic amine antioxidants include, but are not limited to, diphenylamine, p-phenylenediamine, and dihydroquinoline and their derivatives or polymers, such as antioxidant 445 (4,4'-bis(α.α-... Dimethylbenzyl (diphenylamine); thioether antioxidants include, but are not limited to, DLTP (dilauryl thiodipropionate), DSTDP (distearate thiodipropionate), and DSTP (octadecyl thiodipropionate); phosphite antioxidants include, but are not limited to, antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite), antioxidant 618 (pentaerythritol diphosphite bis(octadecyl)), and antioxidant 626 (bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite). Adding antioxidants improves the antioxidant properties and aging resistance of polymer materials, extending their service life. The types of antioxidants are not limited here; those skilled in the art can select them according to actual needs.

[0083] In a second aspect, the present invention provides a method for preparing the above-mentioned acrylonitrile-styrene-butadiene copolymer material, comprising the following steps: mixing the raw materials uniformly, extruding and granulating them through an extruder to obtain granules, namely the acrylonitrile-styrene-butadiene copolymer material.

[0084] In some embodiments, the raw material further includes at least one of a lubricant and an antioxidant;

[0085] And / or, the extruder is a twin-screw extruder, and the processing temperatures of each temperature zone of the extruder are: Zone 1 140-160℃, Zone 2 170-180℃, Zone 3 190-200℃, Zone 4 190-200℃, Zone 5 190-200℃, Zone 6 190-200℃, Zone 7 190-200℃, Zone 8 170-190℃, and the die head 200-210℃, with a screw speed of 150-170 r / min.

[0086] The following specific embodiments and data explain the content of the present invention.

[0087] Information on the raw materials involved in the specific implementation method is shown in Table 1:

[0088] Table 1 Information on raw materials for the examples and comparative examples.

[0089]

[0090]

[0091] Preparation method of modified POSS flame retardant synergist 1

[0092] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was rotary evaporated under reduced pressure, washed with water, and dried to obtain benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 1.

[0093] Preparation method of modified POSS flame retardant synergist 2

[0094] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of dibenzofuran-3-boric acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was rotary evaporated under reduced pressure, washed with water, and dried to obtain dibenzofuran-3-boric acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 2.

[0095] Preparation method of modified POSS flame retardant synergist 3

[0096] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of methylboric acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was then rotary evaporated under reduced pressure, washed with water, and dried to obtain methylboric acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 3.

[0097] Preparation method of modified POSS flame retardant synergist 4

[0098] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of phenylboronic acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was then rotary evaporated under reduced pressure, washed with water, and dried to obtain phenylboronic acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 4.

[0099] Example 1:

[0100] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0101] 70 parts of ABS resin;

[0102] TCP 5 copies;

[0103] MCA 10 copies

[0104] 15 parts of modified POSS flame retardant synergist;

[0105] 0.5 parts PE wax;

[0106] Antioxidant 10100.5 parts;

[0107] The preparation method is as follows:

[0108] ABS resin, TCP, MCA, modified POSS flame retardant synergist 1, and PE wax antioxidant 1010 were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The extruder was granulated under the following conditions: temperatures in zones one to eight of the extruder were 150℃, 180℃, 190℃, 200℃, 200℃, 200℃, and 180℃, respectively; the die head temperature was 200℃; and the screw speed was 160 r / min. This yielded an acrylonitrile-styrene-butadiene copolymer material.

[0109] Example 2:

[0110] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0111] 50 parts of ABS resin;

[0112] TCP 8 copies;

[0113] 5 copies of MCA

[0114] 18 parts of modified POSS flame retardant synergist;

[0115] 0.5 parts PE wax;

[0116] Antioxidant 10100.5 parts;

[0117] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0118] Example 3:

[0119] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0120] 70 parts of ABS resin;

[0121] TCP 5 copies;

[0122] MCA 8 copies

[0123] 12 parts of modified POSS flame retardant synergist;

[0124] 0.5 parts PE wax;

[0125] Antioxidant 10100.5 parts;

[0126] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0127] Example 4:

[0128] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0129] 60 parts of ABS resin;

[0130] TCP 10 copies;

[0131] MCA 10 copies

[0132] 15 parts of modified POSS flame retardant synergist;

[0133] 0.5 parts PE wax;

[0134] Antioxidant 10100.5 parts;

[0135] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0136] Example 5:

[0137] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0138] 60 parts of ABS resin;

[0139] TCP 8 copies;

[0140] MCA 8 copies

[0141] 15 parts of modified POSS flame retardant synergist;

[0142] 0.5 parts PE wax;

[0143] Antioxidant 10100.5 parts;

[0144] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0145] Example 6:

[0146] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0147] 60 parts of ABS resin;

[0148] TCP 8 copies;

[0149] MCA 8 copies

[0150] 25 parts of modified POSS flame retardant synergist;

[0151] 0.5 parts PE wax;

[0152] Antioxidant 10100.5 parts;

[0153] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0154] Comparative Example 1:

[0155] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0156] 60 parts of ABS resin;

[0157] TCP 6 copies;

[0158] MCA 8 copies

[0159] 110 parts of modified POSS flame retardant synergist;

[0160] 0.5 parts PE wax;

[0161] Antioxidant 10100.5 parts;

[0162] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0163] Comparative Example 2:

[0164] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0165] 60 parts of ABS resin;

[0166] TCP 13 copies;

[0167] MCA 8 copies

[0168] 0.5 parts PE wax;

[0169] Antioxidant 10100.5 parts;

[0170] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0171] Comparative Example 3:

[0172] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0173] 60 parts of ABS resin;

[0174] MCA 16 copies

[0175] 15 parts of modified POSS flame retardant synergist;

[0176] 0.5 parts PE wax;

[0177] Antioxidant 10100.5 parts;

[0178] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0179] Comparative Example 4:

[0180] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0181] 60 parts of ABS resin;

[0182] TCP 16 copies;

[0183] 15 parts of modified POSS flame retardant synergist;

[0184] 0.5 parts PE wax;

[0185] Antioxidant 10100.5 parts;

[0186] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0187] Comparative Example 5:

[0188] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0189] 60 parts of ABS resin;

[0190] 121 parts of modified POSS flame retardant synergist;

[0191] 0.5 parts PE wax;

[0192] Antioxidant 10100.5 parts;

[0193] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0194] Comparative Example 6:

[0195] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0196] 60 parts of ABS resin;

[0197] TCP 21 copies;

[0198] 0.5 parts PE wax;

[0199] Antioxidant 10100.5 parts;

[0200] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0201] Comparative Example 7:

[0202] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0203] 60 parts of ABS resin;

[0204] 21 copies of MCA;

[0205] 0.5 parts PE wax;

[0206] Antioxidant 10100.5 parts;

[0207] Comparative Example 8:

[0208] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0209] 60 parts of ABS resin;

[0210] TCP 8 copies;

[0211] 8 copies of MCA;

[0212] 5 parts of benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid;

[0213] 0.5 parts PE wax;

[0214] Antioxidant 10100.5 parts;

[0215] Comparative Example 9:

[0216] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0217] 60 parts of ABS resin;

[0218] TCP 8 copies;

[0219] 8 copies of MCA;

[0220] 5 parts of aminopropyl heptaisobutyl cage-like polysilsesquioxane;

[0221] 0.5 parts PE wax;

[0222] Antioxidant 10100.5 parts;

[0223] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0224] Comparative Example 10:

[0225] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0226] 60 parts of ABS resin;

[0227] TCP 8 copies;

[0228] 8 copies of MCA;

[0229] 1.6 parts of benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid;

[0230] 3.4 parts of aminopropyl heptaisobutyl cage-like polysilsesquioxane;

[0231] 0.5 parts PE wax;

[0232] Antioxidant 10100.5 parts;

[0233] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0234] Comparative Example 11:

[0235] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0236] 60 parts of ABS resin;

[0237] TCP 8 copies;

[0238] 8 copies of MCA;

[0239] 35 parts of modified POSS flame retardant synergist;

[0240] 0.5 parts PE wax;

[0241] Antioxidant 10100.5 parts;

[0242] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0243] Comparative Example 12:

[0244] 60 parts of ABS resin;

[0245] TCP 8 copies;

[0246] 8 copies of MCA;

[0247] 45 parts of modified POSS flame retardant synergist;

[0248] 0.5 parts PE wax;

[0249] Antioxidant 10100.5 parts;

[0250] The preparation method is basically the same as in Example 1, except that the composition and quantity of each raw material component are different. Please refer to Table 1 and Table 2.

[0251] The acrylonitrile-styrene-butadiene copolymer materials obtained in the above examples and comparative examples were injection molded into sheets or molded into sheets, and their flame retardancy rating, oxygen index, tensile strength, and notched beam impact strength were tested according to the following standards:

[0252] (1) Flame retardancy rating test

[0253] The test was conducted according to UL94 standard, with a sample thickness of 3 mm and a test temperature of 23±2℃. Three samples were tested using the UL94 vertical burning test apparatus from Jiangsu Zhengrui Taibang Electronics Co., Ltd., while observing for any dripping.

[0254] (2) Oxygen Index

[0255] According to GB / T 2406.2-2009, the sample size was prepared according to Type IV sample size. The test was conducted according to Method A - Top Surface Ignition Method. The oxygen index of three samples was tested using an oxygen index tester manufactured by Nanjing Jiangning District Fangshang Analytical Instrument Equipment Factory, and the results were averaged.

[0256] (3) Tensile strength

[0257] The test was conducted according to Clause 9 of GB 1040—2008, with a test temperature of 23±2℃. The tensile test used a standard dumbbell-shaped specimen with a tensile speed of 250 mm / min. The tensile strength of three specimens was tested using a micro-controlled electronic universal tensile testing machine from Dongguan High-Speed ​​Railway Testing Co., Ltd., and the average value of the results was taken.

[0258] (4) Impact strength of the cantilever beam notch

[0259] The test was conducted according to Type A of GB / T 1843-2008, with a test temperature of 23±2℃. The cantilever beam notched impact strength of three specimens was tested using a cantilever beam pendulum impact tester from Guangdong Aisrui Instrument Technology Co., Ltd., and the average value of the results was taken.

[0260] The test results are detailed in Table 3.

[0261] Table 2. Formulations of embodiments and comparative examples of the present invention.

[0262]

[0263]

[0264] Table 3 Performance test table of embodiments and comparative examples of the present invention

[0265]

[0266]

[0267] As can be seen from Table 3, the ABS injection molded sheets of Examples 1-6 have good flame retardant and mechanical properties. The flame retardant rating of all samples reached V0 level. They did not drip when tested at V0 level. The oxygen index of all samples was >30%, the tensile strength of all samples was >29MPa, and the notched beam impact strength of all samples was >170J / m. This shows that the ABS material of the present invention has good flame retardant and mechanical properties. Examples 5 and Comparative Example 1 show that when the modified POSS flame retardant 1 part is too high, the flame retardant grade is V1, the flame retardant performance is substandard, the oxygen index decreases, the mechanical properties decrease, and both tensile strength and cantilever notched impact strength are reduced. Examples 5 and Comparative Example 2 show that when modified POSS flame retardant 1 is not added, the flame retardant grade is V2, there are drippings, the flame retardant performance is substandard, the oxygen index decreases, and the cantilever notched impact strength is reduced. Examples 5 and Comparative Example 3 show that when the phosphorus-based flame retardant tricresyl phosphate TCP is not added, the flame retardant grade is V2, the flame retardant performance is substandard, the oxygen index decreases, the mechanical properties decrease, and both tensile strength and cantilever notched impact strength are reduced. Examples 5 and Comparative Example 4 show that when the nitrogen-based flame retardant melamine urate (MCA) is not added, the flame retardant grade is V2, there are drippings, the flame retardant performance is substandard, the oxygen index decreases, and the tensile strength is reduced. The following examples illustrate the effects of modified POSS flame retardant 1: Example 5 and Comparative Example 5 show that when only modified POSS flame retardant 1 is used as the flame retardant, the flame retardant rating is V2, the flame retardant performance is substandard, the oxygen index is reduced, and the cantilever notched impact strength is reduced. Example 5 and Comparative Example 6 show that when only the phosphorus-based flame retardant tricresyl phosphate TCP is used, the flame retardant rating is V2, there is dripping, the flame retardant performance is substandard, the oxygen index is reduced, and the tensile strength is reduced. Example 5 and Comparative Example 7 show that when only the nitrogen-based flame retardant melamine urate (MCA) is used, the flame retardant rating is V2, there is dripping, the flame retardant performance is substandard, the oxygen index is low, and the cantilever notched impact strength is reduced. These results demonstrate that modified polyhedral oligomeric silsesquioxanes and their derivatives have a synergistic flame retardant effect with phosphorus-based and nitrogen-based flame retardants, improving the flame retardant and mechanical properties of ABS materials while reducing the amount of various flame retardants used.Examples 5 and Comparative Example 8 show that modified POSS flame retardant 1, compared with benzo[B]naphtho[2,3-D]furan-2-hydroxyboric acid flame retardant, exhibits improved anti-dripping performance, oxygen index, and cantilever notched impact strength. Examples 5 and Comparative Example 9 show that modified POSS flame retardant 1, compared with aminopropyl heptaisobutyl cage-like polysilsesquioxane flame retardant, exhibits improved flame retardancy rating, anti-dripping performance, oxygen index, tensile strength, and cantilever notched impact strength. Examples 5 and Comparative Example 10 show that modified POSS flame retardant 1, compared with a mixture of aminopropyl heptaisobutyl cage-like polysilsesquioxane and benzo[B]naphtho[2,3-D]furan-2-hydroxyboric acid flame retardant, shows improved anti-dripping performance. The flame retardant rating, anti-dripping properties, oxygen index, tensile strength, and notched beam impact strength were all improved. Examples 3 and 11 show that modified POSS flame retardant 1, compared to modified POSS flame retardant 3 (methylboronic acid modified aminopropyl heptaisobutyl cage-like polysilsesquioxane flame retardant), exhibited improved flame retardant rating, anti-dripping properties, oxygen index, tensile strength, and notched beam impact strength. Examples 5 and 12 show that modified POSS flame retardant 1, compared to modified POSS flame retardant 4 (phenylboronic acid modified aminopropyl heptaisobutyl cage-like polysilsesquioxane flame retardant), demonstrated better anti-dripping performance and oxygen index. This indicates that the polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists of the present invention exhibit excellent flame retardant performance.

[0268] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. An acrylonitrile-styrene-butadiene copolymer material, characterized in that, The raw materials for the acrylonitrile-styrene-butadiene copolymer material, by weight, include: 50-70 parts of acrylonitrile-styrene-butadiene copolymer 5-10 parts of phosphorus-based flame retardant 5-10 parts of nitrogen-based flame retardant 2-8 parts of modified polyhedral oligomeric silsesquioxanes and their derivatives as flame retardant synergists. The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is as follows: Wherein, R is isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl or phenyl, and R1 is propylene or phenylene; R2 is a cyclic structure with a carbon-to-hydrogen ratio greater than 1, comprising at least one of a benzofuran group and a polycyclic aromatic group, wherein the benzofuran group comprises at least one of a benzofuran group and a dibenzofuran group; and the polycyclic aromatic group comprises at least one of a naphthyl ring group, anthracene ring group, phenanthrene ring group, acenaphthene ring group, fluorene ring group, and perylene ring group.

2. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist were prepared by dehydration reaction of compound 1 and compound 2 under the action of a catalyst, and the reaction route is as follows: 。 3. The acrylonitrile-styrene-butadiene copolymer material as described in claim 2, characterized in that, The molar ratio of compound 1 to compound 2 is 2:

1.

4. The acrylonitrile-styrene-butadiene copolymer material as described in claim 2, characterized in that, The preparation method of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist includes the following steps: Compound 1 was dissolved in an organic solvent, and an aqueous solution of compound 2 was added under the action of a catalyst. After catalytic reaction, the mixture was washed and dried to obtain the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist. The organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones. The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts.

5. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The phosphorus-based flame retardant includes at least one of phosphate esters and phosphites.

6. The acrylonitrile-styrene-butadiene copolymer material as described in claim 5, characterized in that, The phosphate ester flame retardant includes at least one of tri(β-chloroethyl) phosphate, tributyl phosphate, triphenyl phosphate, and dimethyl methyl phosphate; the phosphite flame retardant includes at least one of diisopropanol ether diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, dimethyl phosphite, and diethyl phosphite.

7. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The raw materials for the acrylonitrile-styrene-butadiene copolymer material also include at least one of a lubricant and an antioxidant; wherein, by weight, the lubricant is 0.2-1 parts and the antioxidant is 0.5-2 parts. And / or, the nitrogen-based flame retardant includes at least one of melamine urate, melamine inorganic acid salt, dicyandiamide, and melamine.

8. A method for preparing the acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The process includes the following steps: mixing the raw materials evenly, extruding and granulating them through an extruder to obtain granules, namely the acrylonitrile-styrene-butadiene copolymer material.

9. The method for preparing the acrylonitrile-styrene-butadiene copolymer material as described in claim 8, characterized in that, The raw materials also include at least one of lubricant and antioxidant; And / or, the extruder is a twin-screw extruder, and the processing temperatures of each temperature zone of the extruder are: Zone 1 140-160℃, Zone 2 170-180℃, Zone 3 190-200℃, Zone 4 190-200℃, Zone 5 190-200℃, Zone 6 190-200℃, Zone 7 190-200℃, Zone 8 170-190℃, and the die head 200-210℃, with a screw speed of 150-170 r / min.

Images