Acrylonitrile-styrene-butadiene copolymer material and preparation method thereof

Abstract

The invention discloses an acrylonitrile-styrene-butadiene copolymer material, which is prepared from 50 to 70 parts of acrylonitrile-styrene-butadiene copolymer (ABS), 1 to 5 parts of phosphorus flame retardant, 1 to 5 parts of nitrogen flame retardant and 10 to 20 parts of modified polysilsesquioxane flame retardant, the modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, a compound B and a catalyst in an alkaline environment, the silsesquioxane A comprises at least one epoxy group D, and the compound B contains a phosphorus element P and a nitrogen element N and at least comprises a halogen end group X. The modified polysilsesquioxane flame retardant forms a carbon layer, a ceramic barrier layer, a protective film or a heat insulation coke layer and other protective layers in the combustion process, the anti-dripping effect is greatly improved, meanwhile, heat and oxygen transfer is isolated, the flame retardant property of the material is remarkably improved, and the service life of the material is prolonged. The acrylonitrile-styrene-butadiene copolymer material provided by the invention has excellent flame retardance and physical and mechanical properties, is safe and environment-friendly, and greatly improves the anti-dripping effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of materials, in particular to a kind of acrylonitrile-styrene-diene copolymer material and preparation method thereof. BACKGROUND

[0002] Silsesquioxane is a kind of compound with machine-inorganic hybrid structure, which is composed of silicon framework and its embedded oxygen atom, and its structure includes the silicon-oxygen chain composed of long bond distance, large bond angle and high bond energy Si-O bond, which is very soft, and its viscous flow activation energy is very low, in addition, the mutual compensation of dppp bond between Si-O bond and the mutual compensation between Si-O dipole, make Si-O bond form helical structure, this special composition and molecular structure make it have many excellent properties such as high and low temperature resistance, weather resistance, electrical insulation, hydrophobicity, non-toxicity and non-corrosion.

[0003] Acrylonitrile-styrene-diene copolymer (ABS resin) is a kind of thermoplastic polymer material with high strength, good toughness and easy to process. ABS resin is a terpolymer composed of acrylonitrile, butadiene and styrene. This material combines the advantages of the three monomers, has high surface hardness, toughness, good low temperature impact resistance, good creep resistance, good dimensional stability, small molding shrinkage and other excellent properties, but its oxygen index is only 18.33-20 (<21), which belongs to flammable material, which has become a great obstacle to the further popularization and development of ABS resin. ABS resin is easy to drip when burning, and needs to add anti-dripping agent, but the commonly used anti-dripping agent on the market is still fluorine-containing anti-dripping agent, and inorganic anti-dripping agent is mostly montmorillonite, kaolin, etc. Large amount of addition is needed to achieve effective results, but the mechanical properties of ABS will be greatly affected when a large amount of inorganic powder is added. Therefore, it is necessary to develop a new type of acrylonitrile-styrene-diene copolymer material, which has halogen-free high flame retardance, anti-dripping effect, high physical and mechanical properties and anti-cracking performance. SUMMARY

[0004] In view of the shortcomings of the prior art, the present application provides an acrylonitrile-styrene-diene copolymer material and a preparation method thereof, which aims to solve the problems of poor flame retardance, poor physical and mechanical properties and dripping during combustion of the current ABS material.

[0005] To achieve the above objectives, this invention proposes an acrylonitrile-styrene-butadiene copolymer material. The raw materials of the acrylonitrile-styrene-butadiene copolymer material, by weight, include 50-70 parts of acrylonitrile-styrene-butadiene copolymer, 1-5 parts of phosphorus-based flame retardant, 1-5 parts of nitrogen-based flame retardant, and 10-20 parts of modified polysilsesquioxane flame retardant. The modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B, and a catalyst under an alkaline environment. Silsesquioxane A includes at least one epoxy group D, and compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen end group X.

[0006] Optionally, the structure of silsesquioxane A includes at least one of fully cage-like silsesquioxanes, and its structural formula includes at least one... , Where 6≥n≥1, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

[0007] Optionally, the compound B includes at least one cyclic structure E with a carbon-hydrogen ratio of not less than 1, and the halogen end group X is not directly connected to the cyclic structure E.

[0008] Optionally, the cyclic structure E with a carbon-to-hydrogen ratio of not less than 1 includes at least one of a benzene ring group and an imidazole group.

[0009] Optionally, the modified polysilsesquioxane flame retardant is synthesized by a nucleophilic substitution reaction of silsesquioxane A and compound B under the action of a catalyst after ring-opening, characterized by the following reaction route: .

[0010] Optionally, the method for synthesizing the modified polysilsesquioxane flame retardant includes the following steps: (1) First, dissolve silsesquioxane A in an organic solvent solution, then add a catalyst. Under the action of the catalyst, stir evenly and add a small amount of water. Continue stirring for 4-8 hours, then place the whole thing in an ice-water bath and stir. (2) Dissolve compound B in an organic solution, and slowly add the organic solution of compound B to step (1) through a constant pressure dropping funnel, while slowly adding an alkaline agent. Under alkaline conditions, the epoxy group D in silsesquioxane A undergoes a nucleophilic ring-opening substitution reaction with the halogen end group X in compound B to obtain the modified polysilsesquioxane flame retardant preproduct. (3) The reaction preproduct in step (2) is rotary evaporated to remove the organic solvent. Then it is washed with saturated sodium chloride solution, filtered and dried to obtain the modified polysilsesquioxane flame retardant.

[0011] Optionally, the molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:1.

[0012] Optionally, the catalyst includes at least one of an acidic catalyst, a metal catalyst, and a basic catalyst; the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones; and the basic agent is at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium phosphate, and sodium silicate.

[0013] Optionally, the raw materials of the acrylonitrile-styrene-butadiene copolymer material, by weight, include 50-60 parts of acrylonitrile-styrene-butadiene copolymer ABS, 2-5 parts of phosphorus-based flame retardant, 2-5 parts of nitrogen-based flame retardant, and 15-20 parts of modified polysilsesquioxane flame retardant.

[0014] Optionally, the acrylonitrile-styrene-butadiene copolymer includes at least one of general-purpose ABS, impact-resistant ABS, high-impact ABS, cold-resistant ABS, heat-resistant ABS, flame-retardant ABS, reinforced ABS, and electroplating ABS; the phosphorus-based flame retardant includes at least one of diethylaluminum hypophosphite, aluminum hypophosphite, phosphate ester, phosphite ester, and phosphonate ester; and the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0015] Optionally, the raw materials for the acrylonitrile-styrene-butadiene copolymer material further include at least one of a lubricant and an antioxidant; wherein, by weight, the lubricant comprises 0.5-1 parts and the antioxidant comprises 0.5-1 parts.

[0016] This invention provides a method for preparing an acrylonitrile-styrene-butadiene copolymer material, comprising 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.

[0017] Optionally, the raw materials may also include at least one of lubricant, antioxidant, light stabilizer and matting agent.

[0018] In this invention, the acrylonitrile-styrene-butadiene copolymer material possesses excellent elasticity, chemical resistance, and abrasion resistance. ABS resin and modified polysilsesquioxane flame retardant are the main components of the acrylonitrile-styrene-butadiene copolymer material. The modified polysilsesquioxane flame retardant's skeleton contains numerous Si-O bonds that decompose upon heating to form a dense ceramic barrier layer. Simultaneously, the modified polysilsesquioxane flame retardant works synergistically with both P-based and N-based flame retardants. The P element in the modified polysilsesquioxane flame retardant, together with the P-based flame retardant, provides an acid source, while the N element in the modified polysilsesquioxane flame retardant, together with the N-based flame retardant, provides non-combustible gas, resulting in stronger flame retardancy. Furthermore, the abundant hydroxyl groups in the modified polysilsesquioxane flame retardant can absorb a large amount of heat, thereby inhibiting combustion. The modified polysilsesquioxane flame retardant proposed in this invention is a viscous liquid. When added to acrylonitrile-styrene-butadiene copolymer materials, it has little impact on the performance of acrylonitrile-styrene-butadiene copolymer materials. Moreover, a high addition amount is not required to obtain acrylonitrile-styrene-butadiene copolymer materials with excellent flame retardancy. The prepared acrylonitrile-styrene-butadiene copolymer materials have good processing performance, elasticity, and flame retardancy, and significantly improve the crack resistance and anti-dripping effect of acrylonitrile-styrene-butadiene copolymer materials, while being safe and environmentally friendly. Attached Figure Description

[0019] Figure 1 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 1 of the present invention; Figure 2 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 2 of the present invention; Figure 3 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 3 of the present invention; Figure 4 This is another molecular structure diagram of the modified polysilsesquioxane flame retardant 3 of the present invention; Figure 5 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 4 of the present invention; Figure 6 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 5 of the present invention; Figure 7 This is another molecular structure diagram of the modified polysilsesquioxane flame retardant 5 of the present invention; Figure 8 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 6 of the present invention; Figure 9 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 7 of the present invention; Figure 10 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 8 of the present invention; Figure 11 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 9 of the present invention; Figure 12 This is another molecular structure diagram of the modified polysilsesquioxane flame retardant 9 of the present invention; Figure 13 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 10 of the present invention; Figure 14 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 11 of the present invention; Figure 15 This is a molecular structure diagram of the glycidyl etheroxypropyl-isooctyl polysilsesquioxane in this invention. Figure 16 This is a molecular structure diagram of bis(4-nitrophenyl)phosphochloride in this invention. Detailed Implementation

[0020] 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.

[0021] Unless otherwise specified, all technical and scientific terms used herein have their usual meaning within the field to which the subject matter is claimed.

[0022] To facilitate understanding of this embodiment, the symbols, instruments, and terms are explained below: Acrylonitrile-styrene-butadiene copolymer (ABS) is a widely used thermoplastic engineering plastic with high strength, good toughness, dimensional stability, and excellent cost performance. ABS is widely used in automotive parts, electronics, household consumer goods, and building materials, and is one of the most important general-purpose engineering plastics today.

[0023] Silsesquioxanes are a class of compounds with an organic-inorganic hybrid structure, consisting of a silicon framework and intercalated oxygen atoms. Their structure comprises Si-O bonded silicon-oxygen chains with long bond distances, large bond angles, and high bond energies. They are very flexible and have very low viscous flow activation energies. In addition, the mutual compensation of dppp bonds between Si-O bonds and the mutual compensation between Si-O dipoles causes the Si-O bonds to form a helical structure. This special composition and molecular structure endow them with many excellent properties such as resistance to high and low temperatures, weather resistance, electrical insulation, hydrophobicity, non-toxicity, and non-corrosiveness.

[0024] 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, possessing 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. Most inorganic anti-dripping agents are montmorillonite, kaolin, etc., requiring large amounts to be effective. However, large amounts of inorganic powder significantly affect the mechanical properties of ABS. Therefore, it is essential to develop a new acrylonitrile-styrene-butadiene copolymer material with halogen-free high flame retardancy, anti-dripping effect, high physical and mechanical properties, and crack resistance.

[0025] To address the aforementioned problems, in a first aspect, this invention provides an acrylonitrile-styrene-butadiene copolymer material. The raw materials for this acrylonitrile-styrene-butadiene copolymer material, by weight, include 50-70 parts of acrylonitrile-styrene-butadiene copolymer, 1-5 parts of a phosphorus-based flame retardant, 1-5 parts of a nitrogen-based flame retardant, and 10-20 parts of a modified polysilsesquioxane flame retardant. The modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B, and a catalyst under an alkaline environment. Silsesquioxane A includes at least one epoxy group D, and compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen end group X.

[0026] Understandably, in acrylonitrile-styrene-butadiene copolymer materials, ABS resin is in any number of parts between 50 and 70, such as 50, 55, 60, 65, or 70; PP is in any number of parts between 15 and 50, such as 15, 25, 35, 45, or 50; phosphorus-based flame retardant is in any number of parts between 1 and 5, such as 1, 2, 3, 4, or 5; nitrogen-based flame retardant is in any number of parts between 1 and 5, such as 1, 2, 3, 4, or 5; and modified polysilsesquioxane flame retardant is in any number of parts between 10 and 20, such as 10, 15, 18, or 20.

[0027] Understandably, modified polysilsesquioxane flame retardants are prepared from raw materials including silsesquioxane A, compound B, and a catalyst under an alkaline environment. Silsesquioxane A includes at least one epoxy group D, and compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen end group X. Under the catalysis of the catalyst, epoxy group D, due to ring strain, is easily subjected to nucleophilic attack and ring-opening. Under trace amounts of water and acidic or alkaline conditions, the epoxy group undergoes a ring-opening reaction, generating a diol structure with primary and secondary alcohols. The more reactive primary alcohol on the silsesquioxane acts as a nucleophile to attack the P atom with the halogen end group X, removing the HX molecule and generating the modified polysilsesquioxane flame retardant. Therefore, the modified polysilsesquioxane flame retardant contains a large number of Si-O bonds from silsesquioxane A and phosphorus (P) and nitrogen (N) from compound B, and also contains hydroxyl groups obtained after the ring-opening of the epoxy group.

[0028] Modified polysilsesquioxane flame retardants contain a large number of Si-O bonds, which decompose upon heating to form a dense ceramic barrier layer. This layer isolates the release of combustible gases and the entry of external heat into the interior. Simultaneously, the dense ceramic barrier layer significantly improves the material's anti-dripping effect and flame retardant performance. During combustion, the phosphorus element in the modified polysilsesquioxane flame retardant decomposes to produce highly dehydrating substances such as phosphoric acid and polyphosphoric acid, promoting carbonization on the material surface to form a heat-insulating layer (condensation mechanism). It also releases phosphorus-containing free radicals, capturing the H• and OH• free radicals necessary for combustion in the gas phase, interrupting the combustion chain reaction. This dual effect results in very high flame retardant efficiency. The nitrogen element itself decomposes upon combustion to provide a large amount of non-combustible gas, which, in conjunction with the phosphorus element, causes the forming viscous char layer to foam, forming a porous, dense, and robust expanded char layer.

[0029] Meanwhile, the modified polysilsesquioxane flame retardant contains a large number of hydroxyl groups. During the initial and subsequent combustion phases, these hydroxyl groups absorb a significant amount of heat, substantially reducing the surface temperature of the polymer material and slowing down its thermal decomposition rate, thus inhibiting combustion. The water vapor produced by the combustion of hydroxyl groups effectively dilutes the concentration of combustible gases and oxygen near the material surface, weakening or extinguishing the combustion reaction due to lack of fuel and oxygen.

[0030] Modified polysilsesquioxane flame retardants contain abundant silicon, oxygen, phosphorus, and nitrogen elements. During polymer combustion, they rapidly form a char layer. The SiO2 generated after combustion permeates 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. Simultaneously, the combustion of nitrogen produces a large amount of non-combustible gas, which causes the incompletely carbonized ABS portion to foam in the molten state, resulting in numerous pores in the burning polymer. Meanwhile, organic matter continues to react, dehydrate, and carbonize, forming inorganic matter and residual carbon. Upon completion of the reaction, the system gels and solidifies, ultimately forming a porous foamed char layer.

[0031] Acrylonitrile-styrene-butadiene copolymers possess excellent elasticity, chemical resistance, and abrasion resistance. ABS resin and modified polysilsesquioxane flame retardants serve as the main components of these copolymers. The modified polysilsesquioxane flame retardant's skeleton contains numerous Si-O bonds that decompose upon heating to form a dense ceramic barrier layer. Furthermore, the modified polysilsesquioxane flame retardant works synergistically with both phosphorus and nitrogen-based flame retardants. The phosphorus element in the modified polysilsesquioxane flame retardant, together with the phosphorus-based flame retardants, provides an acid source, while the nitrogen element, together with the nitrogen-based flame retardants, provides non-combustible gas, resulting in enhanced flame retardancy. Additionally, the abundant hydroxyl groups in the modified polysilsesquioxane flame retardant can absorb a significant amount of heat, thereby inhibiting combustion. The modified polysilsesquioxane flame retardant proposed in this invention is a viscous liquid. When added to acrylonitrile-styrene-butadiene copolymer materials, it has little impact on the performance of acrylonitrile-styrene-butadiene copolymer materials. Moreover, a high addition amount is not required to obtain acrylonitrile-styrene-butadiene copolymer materials with excellent flame retardancy. The prepared acrylonitrile-styrene-butadiene copolymer materials have good processing performance, elasticity, and flame retardancy, and significantly improve the crack resistance and anti-dripping effect of acrylonitrile-styrene-butadiene copolymer materials, while being safe and environmentally friendly.

[0032] Furthermore, the structure of silsesquioxane A includes at least one of fully cage-like silsesquioxanes, and its structural formula includes at least one... , Where 6≥n≥1, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

[0033] Silsesquioxane A includes at least one of fully caged silsesquioxanes. Fully caged silsesquioxanes are hollow and have a closed structure, with all three dimensions within the nanoscale range. They possess a hexahedral inorganic framework core with a nanostructure, exhibiting unique thermodynamic properties. As the main component of the molecular skeleton of hybrid materials, fully caged silsesquioxanes, due to their large volume effect, effectively control the chain movement of the matrix material, significantly increasing the glass transition temperature (Tg). When the temperature of the silsesquioxane organic polymer rises to the point where the polymer begins to melt, the silsesquioxane molecular structure remains unchanged. When the organic molecules on its surface are oxidized at high temperatures, the silsesquioxane, due to its oxygen stability, can fix the oxidized organic molecules, forming a refractory layer and providing structural support. After the monomers of fully caged silsesquioxane macromolecules containing epoxy groups are cured, they have a high decomposition temperature and can form a high-temperature resistant cured layer.

[0034] In some embodiments, silsesquioxane A is preferably at least one of glycidyl etheroxypropylcyclotetrasiloxane, octa[(3-glycidyloxypropyl)dimethylsiloxy]-substituted PSS, 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane, acryloyloxypropyl-glycidyl etheroxypropyl cage-like polysilsesquioxane, glycidyl etheroxypropyl-isooctyl polysilsesquioxane, glycidyl etheroxypropyl cage-like polysilsesquioxane, cyclohexyloxypropyl-glycidyl etheroxypropyl cage-like polysilsesquioxane, and octacyclohexyloxypropyl cage-like polysilsesquioxane.

[0035] Understandably, the structural formula of glycidyl etheroxypropylcyclotetrasiloxane is... , where n is 1, and R1, R2, R3, R4, R5, R6, R7, and R8 include 4 epoxy groups D.

[0036] Understandably, the structural formula of PSS substituted with [3-oxyglycidylpropyl)dimethylsiloxy] is... , where n is 2, and R1, R2, R3, R4, R5, R6, R7, and R8 include 7 epoxy groups D.

[0037] Understandably, the structural formula of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane is... , where n is 3, and R1, R2, R3, R4, R5, R6, R7, and R8 include 3 epoxy groups D.

[0038] Understandably, the structural formula of acryloyloxypropyl-glycidyloxypropyl cage-type polysilsesquioxane is as follows: , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include one epoxy group D.

[0039] Understandably, the structural formula of glycidyl etheroxypropyl-isooctyl polysilsesquioxane is... , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 4 epoxy groups D.

[0040] Understandably, the structural formula of glycidyl etheroxypropyl cage-like polysilsesquioxane is... , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 8 epoxy groups D.

[0041] Understandably, the structural formula of epoxycyclohexylethyl-glycidyloxypropyl cage-like polysilsesquioxane is as follows: , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 8 epoxy groups D.

[0042] Understandably, the structural formula of octacyclohexylethyl cage-like polysilsesquioxane is... , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 8 epoxy groups D.

[0043] Understandably, each specific n represents a specific silsesquioxane. When n is the same, the R1, R2, R3, R4, R5, R6, R7, and R8 groups on the specific silsesquioxane structure can include different groups, including but not limited to oxypropyl, isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl.

[0044] Furthermore, compound B includes at least one cyclic structure E with a carbon-to-hydrogen ratio of not less than 1, and the halogen end group X is not directly connected to the cyclic structure E.

[0045] Modified polysilsesquioxane flame retardants contain fully cage-like silsesquioxanes and cyclic groups with a carbon-to-hydrogen ratio of not less than 1, as well as phosphorus and nitrogen elements. The fully cage-like silsesquioxanes 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 cyclic structure with a carbon-to-hydrogen ratio of not less than 1 has a high carbon-to-hydrogen ratio and a large amount of carbon. During combustion, this large amount of carbon forms a heat-insulating coke layer. This coke layer isolates air, prevents heat transfer, and reduces the release of combustible gases. This structure, through the formation of a carbon layer and ceramic barrier during combustion... Barrier layers, protective films, or heat-insulating coke layers significantly 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. On the other hand, when halogen end groups are directly connected to the cyclic structure E, the high bond energy makes it difficult to break the bonds and nucleophilic substitution is difficult. Direct nucleophilic substitution requires the formation of a high-energy carbanion intermediate, which makes the reaction extremely difficult. Halogens will stably connect to the cyclic structure E, resulting in the presence of halogens in the modified polysilsesquioxane flame retardant, which affects the environmental performance of acrylonitrile-styrene-butadiene copolymer materials.

[0046] In some embodiments, compound B comprises a cyclic structure with a carbon-hydrogen ratio of not less than 1. It is understood that cyclic structures with a carbon-hydrogen ratio (C / H) greater than 1 are very common. The structure has relatively few hydrogen atoms, indicating that the structure includes unsaturated hydrocarbons (containing double or triple bonds) or is a fused-ring aromatic hydrocarbon, or a carbon allotrope composed entirely of carbon.

[0047] In some embodiments, compound B comprises two cyclic structures with a carbon-to-hydrogen ratio of not less than 1. It is understood that compound B may contain two benzene ring groups. The stability of compound B can be achieved by setting symmetrical benzene ring groups. At the same time, the two benzene ring groups increase the carbon content in the generated modified polysilsesquioxane flame retardant, thereby increasing the content of the heat-insulating coke layer formed by carbon during combustion, isolating heat and oxygen, and further improving the flame retardancy and anti-dripping performance of the material.

[0048] Furthermore, the cyclic structure E with a carbon-to-hydrogen ratio of not less than 1 includes at least one of a benzene ring group and an imidazole group.

[0049] Understandably, compound B is preferably at least one of bis(4-nitrophenyl)phosphochloride, bis(4-nitrobenzyl)chlorophosphate, di[2-(p-nitrophenyl)ethyl]chlorophosphate, 2-(4-nitrophenyl)ethylhydro(5-chloropentyl)phosphonate, Bis(3-chloropropyl) p-nitrophenyl phosphate, DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE, and N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphochloride.

[0050] Understandably, the structural formula of bis(4-nitrophenyl)phosphochloride is... .

[0051] Understandably, the structural formula of bis(4-nitrobenzyl)chlorophosphate is... .

[0052] Understandably, the structural formula of di[2-(p-nitrophenyl)ethyl]chlorophosphate is... .

[0053] Understandable, 3-nitro-N-(2,2,2-trichloro-1- The structural formula of Diethoxy–phosphorylethyl)benzamide is: .

[0054] Understandably, the structural formula of Bis(3-chloropropyl)p-nitrophenyl phosphate is... .

[0055] Understandably, the structural formula of DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE is... .

[0056] Understandably, the structural formula of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryldichloro is... .

[0057] Compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen terminal group X and at least one cyclic structure E with a carbon-to-hydrogen ratio of not less than 1. The halogen terminal group X includes -Cl, -Br, and -F. The halogen terminal group undergoes a nucleophilic substitution reaction with an epoxy group. It is understood that when compound B has only one halogen terminal group, one epoxy group is attached to compound B; when compound B has two halogen terminal groups, two epoxy groups are attached to compound B. That is, when silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane and compound B is preferably Bis(3-chloropropyl) p-nitrophenyl phosphate, Bis(3-chloropropyl) p-nitrophenyl The two chlorine-terminal groups in phosphate react with the two epoxy groups in glycidyl etheroxypropylcyclotetrasiloxane via nucleophilic substitution to form a new cyclic structure. Similarly, when compound B has only one cyclic structure E with a carbon-hydrogen ratio of not less than 1, cyclic structure E can be a benzene ring or an imidazole ring, possessing a high carbon-hydrogen ratio. This allows it to form a protective layer during combustion, improving flame retardancy and anti-dripping effects. When compound B has two benzene ring structures, the carbon-hydrogen ratio of cyclic structure E in compound B increases, making the flame retardancy and anti-dripping effects more pronounced.

[0058] Furthermore, a method for synthesizing a modified polysilsesquioxane flame retardant involves a nucleophilic substitution reaction between silsesquioxane A and compound B under the action of a catalyst after ring-opening. The reaction route is as follows: .

[0059] After hydrolysis and ring opening, silsesquioxane A forms a structure with two alcoholic hydroxyl groups, generating a diol structure containing a primary alcohol and a secondary alcohol. The more reactive primary alcohol on the silsesquioxane acts as a nucleophile to attack the P atom with a halogenated end group X, removing the HX molecule and generating a modified polysilsesquioxane flame retardant.

[0060] The synthesis method of modified polysilsesquioxane flame retardants includes the following steps: (1) First, dissolve silsesquioxane A in an organic solvent solution, then add a catalyst. Under the action of the catalyst, stir evenly and add a small amount of water. Continue stirring for 4-8 hours, then place the whole thing in an ice-water bath and stir. (2) Dissolve compound B in an organic solution, and slowly add the organic solution of compound B to step (1) through a constant pressure dropping funnel, while slowly adding an alkaline agent. Under alkaline conditions, the primary alcohol after ring opening in silsesquioxane A undergoes a nucleophilic ring-opening substitution reaction with the halogen end group X in compound B to obtain the modified polysilsesquioxane flame retardant preproduct. (3) The reaction preproduct in step (2) is rotary evaporated to remove the organic solvent. Then it is washed with saturated sodium chloride solution, filtered and dried to obtain the modified polysilsesquioxane flame retardant.

[0061] In some embodiments, silsesquioxane A is first dissolved in an organic solvent solution, then a catalyst is added. Under the action of the catalyst, the mixture is stirred evenly and a trace amount of water is added. After stirring continuously for 6 hours, the whole mixture is placed in an ice-water bath and stirred.

[0062] Furthermore, the molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:1.

[0063] The spatial structure of silsesquioxane A is relatively large. Sufficiently small steric hindrance is required during the reaction to obtain the modified polysilsesquioxane flame retardant. During the reaction, each epoxy group D is attached to one halogen group X, meaning the molar ratio of epoxy group D to halogen end group X is 1:1. This ensures sufficient space for silsesquioxane A and achieves structural stability in the modified polysilsesquioxane flame retardant. The primary alcohol groups formed after ring opening of each epoxy group undergo nucleophilic substitution reactions with halogens, thus yielding the modified polysilsesquioxane flame retardant. The overall reaction requires only a single substance, is simple to operate, and is easy to implement.

[0064] like Figure 1 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 1, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably di(4-nitrophenyl)phosphoryl chloride.

[0065] like Figure 2 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 2, silsesquioxane A is preferably octa[(3-glycidylpropyl)dimethylsiloxy]-substituted PSS and di[2-(p-nitrophenyl)ethyl]chlorophosphate.

[0066] like Figure 3 and Figure 4As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 3, silsesquioxane A is preferably 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane, and compound B is preferably DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOY L]PHOSPHONATE; Understandably, this compound B contains three F-terminal groups, in 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane with DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOS During the PHONATE reaction, the three epoxy groups in 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane of one molecule can react with the three epoxy groups in DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPH The three F-terminal groups in ONATE react one-to-one to form a modified polysilsesquioxane flame retardant 3 with a three-ring structure; similarly, the three epoxy groups in one molecule of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane can react with three different molecules of DIETHYL[2-(2,4-DINITROPHENYL)-3- In (TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE, one F-terminal group corresponds to the reaction link, thereby forming a modified polysilsesquioxane flame retardant 3, which is a polymeric network. Both of the above structures can exist in the modified polysilsesquioxane flame retardant 3. Similarly, 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3].The three epoxy groups of [15,11] heptasiloxane can react with the two F-terminal groups in the same DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL) BENZOHYDRAZONOYL]PHOSPHONATE molecule and another different DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)] PHOSPHONATE molecule. In the [BENZOHYDRAZONOYL]PHOSPHONATE molecule, one F-terminal group reacts to form both a cyclic structure and a polymeric network structure. This structure is also present in modified polysilsesquioxane flame retardant 3, where one molecule of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane can connect 1-3 DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL) BENZOHYDRAZONOYL]PHOSPHONATE molecules. The specific molecular structure of modified polysilsesquioxane flame retardant 3 is not specifically limited here.

[0067] like Figure 5 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 4, silsesquioxane A is preferably acryloyloxypropyl-glycidyloxypropyl cage-type polysilsesquioxane, and compound B is preferably bis(4-nitrobenzyl)chlorophosphate.

[0068] like Figure 6 and Figure 7As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 5, silsesquioxane A is preferably glycidyl etheroxypropyl-isooctyl polysilsesquioxane, and compound B is preferably Bis(3-chloropropyl) p-nitrophenyl phosphate. It is understood that this compound B contains two Cl-terminal groups. During the reaction of glycidyl etheroxypropyl-isooctyl polysilsesquioxane with Bis(3-chloropropyl) p-nitrophenyl phosphate, one glycidyl etheroxypropyl-isooctyl polysilsesquioxane molecule contains four epoxy groups. One molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane corresponds to two molecules of Bis(3-chloropropyl) p-nitrophenyl phosphate. The four epoxy groups in one molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane can react with two molecules of Bis(3-chloropropyl) p-nitrophenyl phosphate. The Cl-terminal groups of phosphate are reacted one-to-one to form a modified polysilsesquioxane flame retardant 5 with two cyclic groups. Similarly, one molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane can react with one Cl-terminal group of four different Bis(3-chloropropyl) p-nitrophenyl phosphate molecules, forming a polymeric network of modified polysilsesquioxane flame retardant 5. Both of these structures exist in modified polysilsesquioxane flame retardant 5. Likewise, during the reaction, one glycidyl etheroxypropyl-isooctyl polysilsesquioxane molecule can react with two Cl-terminal groups of the same Bis(3-chloropropyl) p-nitrophenyl phosphate molecule and another different Bis(3-chloropropyl) p-nitrophenyl One Cl terminal group in the phosphate molecule reacts and connects to form both a cyclic structure and a polymeric network structure. This structure also exists in the modified polysilsesquioxane flame retardant 5, that is, one molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane can connect 2-4 Bis(3-chloropropyl) p-nitrophenyl phosphate molecules. The specific molecular structure of the modified polysilsesquioxane flame retardant 3 is not specifically limited here.

[0069] like Figure 8As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 6, silsesquioxane A is preferably epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane, and compound B is preferably N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride. The epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane contains eight epoxy groups, and the N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride contains two Cl-terminal groups. It is understood that the N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride contains two Cl-terminal groups. The two Cl terminal groups in phosphoryl dichloride can react and connect with two groups in the same epoxycyclohexyl ethyl-glycidyl oxypropyl cage polysilsesquioxane molecule, or react and connect with epoxy groups in two different epoxycyclohexyl ethyl-glycidyl oxypropyl cage polysilsesquioxane molecules. This can simultaneously form a cyclic structure and a polymeric network structure. That is, one molecule of epoxycyclohexyl ethyl-glycidyl oxypropyl cage polysilsesquioxane can connect 4-8 N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride molecules. The specific molecular structure of the modified polysilsesquioxane flame retardant 6 is not specifically limited here.

[0070] like Figure 9 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 7, silsesquioxane A is preferably octacyclooxycyclohexylethyl cage-like polysilsesquioxane, and compound B is preferably di(4-nitrophenyl)phosphoryl chloride.

[0071] like Figure 10 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 8, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably dibenzylphosphoyl chloride.

[0072] like Figure 11 and Figure 12 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 9, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably cyclophosphamide.

[0073] like Figure 13 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 10, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably Ethyl 3-(3-chloropropyl)-5-nitrophenylacetate.

[0074] like Figure 14As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 11, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably bis(2-chlorophenyl)phosphoryl chloride.

[0075] Furthermore, the catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts; the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones; and the basic agent is at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium phosphate, and sodium silicate.

[0076] Catalysts can precisely control the selectivity and reaction pathway of a reaction, while lowering the activation energy, increasing the reaction rate, and controlling the three-dimensional configuration of the product molecules. Basic agents keep the reaction in an alkaline environment, absorbing the acidic substances generated by the reaction of primary alcohol groups with halogen end groups X, thereby ensuring that the nucleophilic substitution reaction can continue to occur.

[0077] In some embodiments, the catalyst is preferably sodium hydroxide.

[0078] In some embodiments, the organic solvent is preferably ethanol.

[0079] In some embodiments, the alkaline agent is preferably triethylamine.

[0080] Furthermore, the raw materials for the acrylonitrile-styrene-butadiene copolymer material, by weight, include 50-60 parts of acrylonitrile-styrene-butadiene copolymer ABS, 2-5 parts of phosphorus-based flame retardant, 2-5 parts of nitrogen-based flame retardant, and 15-20 parts of modified polysilsesquioxane flame retardant.

[0081] Reducing the amount of ABS resin in acrylonitrile-styrene-butadiene copolymer materials can further improve the mechanical and flame-retardant properties of acrylonitrile-styrene-butadiene copolymer materials.

[0082] Furthermore, the acrylonitrile-styrene-butadiene copolymer includes at least one of general-purpose ABS, impact-resistant ABS, high-impact ABS, cold-resistant ABS, heat-resistant ABS, flame-retardant ABS, reinforced ABS, and electroplating ABS; the phosphorus-based flame retardant includes at least one of diethylaluminum hypophosphite, aluminum hypophosphite, phosphate ester, phosphite ester, and phosphonate ester; and the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0083] In some embodiments, the ABS resin is preferably general-purpose ABS.

[0084] In some embodiments, the P-based flame retardant is preferably diethyl aluminum hypophosphite.

[0085] In some embodiments, the N-based flame retardant is preferably melamine urate.

[0086] Furthermore, 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 raw materials contain 0.5-1 parts of lubricant and 0.5-1 parts of antioxidant.

[0087] Lubricants can improve the flowability of acrylonitrile-styrene-butadiene copolymer resin, reduce the coefficient of friction, make the surface of the product smoother, improve processing efficiency, and also improve the transparency and gloss of plastics. Antioxidants can effectively reduce the oxidation rate of materials during processing and use by capturing free radicals, decomposing peroxides and complexing metal ions, thereby delaying or preventing oxidation or auto-oxidation processes, protecting plastic products from oxidation and extending their service life.

[0088] In some embodiments, the lubricant is at least one of silicone lubricant, PE wax, PP wax, fatty acid and fatty acid salt, and the lubricant is preferably PE wax.

[0089] In some embodiments, the antioxidant is at least one of asymmetric hindered phenolic antioxidants, aromatic amine antioxidants, thioether antioxidants, and phosphite antioxidants, and the antioxidant is preferably antioxidant 1010.

[0090] To address the above problems, this invention also proposes a method for preparing an acrylonitrile-styrene-butadiene copolymer material, comprising the following steps: S1: Substitution reaction yields modified polysilsesquioxane flame retardant; S2: Mix the raw materials evenly and granulate them by twin-screw extrusion to obtain granules; dry the granules to obtain acrylonitrile-styrene-butadiene copolymer material.

[0091] In some embodiments, extrusion granulation is achieved using a twin-screw extruder.

[0092] The processing temperatures of each zone of the extruder are as follows: Zone 1 90-100℃, Zone 2 160-180℃, Zone 3 190-200℃, Zone 4 190-220℃, Zone 5 190-220℃, Zone 6 190-220℃, Zone 7 190-220℃, Zone 8 190-220℃, Zone 9 180-200℃, Zone 10 180-200℃, Zone 11 200-210℃, and the die head 200-210℃. The main machine speed is 400-600 r / min, and the feeding speed is 30-60 r / min.

[0093] In some embodiments, the temperature at which the acrylonitrile-styrene-butadiene copolymer material is obtained by extrusion granulation is 170°C-190°C.

[0094] In some embodiments, the drying time is preferably 8-12 hours.

[0095] Furthermore, the raw materials also include at least one of lubricants and antioxidants.

[0096] The following specific embodiments and data explain the content of the present invention.

[0097] Information on the raw materials involved in the specific implementation method is shown in Table 1: Table 1 Information on raw materials for the examples and comparative examples Information on the raw materials involved in the specific implementation method is shown in Table 1:

[0098]

[0099] Example 1: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath for stirring. 4 mol of bis(4-nitrophenyl)phosphoryl chloride was dissolved in ethanol solution. The organic solution of bis(4-nitrophenyl)phosphoryl chloride was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 1. 50 parts ABS, 1 part P-series flame retardant, 2 parts N-series flame retardant, 10 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0100] Example 2: The preparation method is the same as in Example 1, except that: 70 parts ABS, 2 parts P-series flame retardant, 3 parts N-series flame retardant, 15 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0101] Example 3: The preparation method is the same as in Example 1, except that: 55 parts ABS, 5 parts P-series flame retardant, 4 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0102] Example 4: The preparation method is the same as in Example 1, except that: 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 18 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0103] Example 5: 1 mol of octa[(3-glycidyl oxydimethylsiloxy)-substituted PSS] was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The mixture was then placed in an ice-water bath and stirred. 8 mol of di[2-(p-nitrophenyl)ethyl]chlorophosphate was dissolved in ethanol solution. The organic solution of di[2-(p-nitrophenyl)ethyl]chlorophosphate was slowly added dropwise through a constant-pressure dropping funnel to the ethanol solution of octa[(3-glycidyl oxydimethylsiloxy)-substituted PSS, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 2. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0104] Example 6: 1 mol of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring thoroughly with the catalyst, a small amount of water was added. The mixture was stirred continuously for 4-8 hours, and then the entire mixture was placed in an ice-water bath and stirred. 1 mol... DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE was dissolved in an ethanol solution. DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE was then slowly added dropwise through a constant-pressure dropping funnel to an ethanol solution of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane. An organic solution of PHOSPHONATE (4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL)PHOSPHONATE was prepared by slowly adding sodium hydroxide solution to create an alkaline environment, resulting in a pre-product of modified polysilsesquioxane flame retardant. The pre-product was then subjected to rotary evaporation to remove the organic solvent, followed by washing with saturated sodium chloride solution. After filtration and drying, modified polysilsesquioxane flame retardant 3 was obtained. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0105] Example 7: 1 mol of acryloyloxypropyl-glycidyl etheroxypropyl cage-type polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The entire mixture was then placed in an ice-water bath for further stirring. 1 mol of bis(4-nitrobenzyl)chlorophosphate was dissolved in ethanol solution. The organic solution of bis(4-nitrobenzyl)chlorophosphate was slowly added dropwise to the ethanol solution of acryloyloxypropyl-glycidyl etheroxypropyl cage-type polysilsesquioxane through a constant pressure dropping funnel. Simultaneously, sodium hydroxide solution was slowly added dropwise to maintain an alkaline environment, yielding a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 4. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0106] Example 8: 1 mol of glycidyl etheroxypropyl-isooctyl polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The entire mixture was then placed in an ice-water bath for stirring. 4 mol of Bis(3-chloropropyl) p-nitrophenyl phosphate was dissolved in ethanol solution. The organic solution of Bis(3-chloropropyl) p-nitrophenyl phosphate was slowly added dropwise to the ethanol solution of glycidyl etheroxypropyl-isooctyl polysilsesquioxane through a constant pressure dropping funnel, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 5. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0107] Example 9: 1 mol of epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring thoroughly under the action of the catalyst, a trace amount of water was added. The mixture was stirred continuously for 4-8 hours, and then the entire mixture was placed in an ice-water bath for stirring. 4 mol of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride was dissolved in ethanol solution and added to the epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane through a constant pressure dropping funnel. An organic solution of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride was slowly added dropwise to an ethanol solution of a cage-like polysilsesquioxane, while sodium hydroxide solution was slowly added dropwise to maintain an alkaline environment, thus obtaining a pre-product of a modified polysilsesquioxane flame retardant. The obtained pre-product of the modified polysilsesquioxane flame retardant was subjected to rotary evaporation to remove the organic solvent, followed by washing with a saturated sodium chloride solution, and then filtered and dried to obtain modified polysilsesquioxane flame retardant 6.

[0108] 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0109] Example 10: 1 mol of octacyclohexylethyl cage-like polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The mixture was then placed in an ice-water bath for further stirring. 8 mol of bis(4-nitrophenyl)phosphoryl chloride was dissolved in ethanol solution. The organic solution of bis(4-nitrophenyl)phosphoryl chloride was slowly added dropwise through a constant-pressure dropping funnel to the ethanol solution of octacyclohexylethyl cage-like polysilsesquioxane, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 7. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0110] Comparative Example 1: The preparation method is the same as in Example 1, except that: 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 30 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0111] Comparative Example 2: The preparation method is the same as in Example 1, except that: 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 3 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0112] Comparative Example 3: The preparation method is the same as in Example 1, except that: 60 parts ABS, 10 parts P-series flame retardant, 10 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0113] Comparative Example 4: The preparation method is the same as in Example 1, except that: 60 parts ABS, 0.3 parts P-series flame retardant, 0.3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0114] Comparative Example 5: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath for stirring. 4 mol of dibenzyl phosphoric acid chloride was dissolved in ethanol solution. The organic solution of dibenzyl phosphoric acid chloride was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 8. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0115] Comparative Example 6: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath and stirred. 2 mol of cyclophosphamide was dissolved in ethanol solution. The organic solution of cyclophosphamide was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 9. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0116] Comparative Example 7: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The mixture was then placed in an ice-water bath and stirred. 4 mol of Ethyl 3-(3-chloropropyl)-5-nitrophenylacetate was dissolved in ethanol solution. The organic solution of Ethyl 3-(3-chloropropyl)-5-nitrophenylacetate was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane using a constant pressure dropping funnel, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 10. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0117] Comparative Example 8: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath for stirring. 4 mol of bis(2-chlorophenyl)phosphoryl chloride was dissolved in ethanol solution. The organic solution of bis(2-chlorophenyl)phosphoryl chloride was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 11. 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0118] Comparative Example 9: 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts glycidyl etheroxypropyl-isooctyl polysilsesquioxane, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0119] Comparative Example 10: 60 parts ABS, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 20 parts di(4-nitrophenyl)phosphoyl chloride, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0120] Comparative Example 11: 60 parts ABS, 26 parts diethyl aluminum hypophosphite, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0121] Comparative Example 12: 60 parts ABS, 26 parts MCA flame retardant, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0122] Comparative Example 13: 60 parts of ABS, 26 parts of glycidyl etheroxypropyl-isooctyl polysilsesquioxane, 0.5 parts of lubricant, and 1 part of antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0123] Comparative Example 14: 60 parts ABS, 26 parts di(4-nitrophenyl)phosphoyl chloride, 0.5 parts lubricant, and 1 part antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a preform of acrylonitrile-styrene-butadiene copolymer material. After drying at 80°C, a high flame-retardant and crack-resistant acrylonitrile-styrene-butadiene copolymer material was obtained.

[0124] The acrylonitrile-styrene-butadiene copolymer materials obtained in the above examples and comparative examples were injection molded or pressed into sheets, and their tensile strength, flame retardancy rating, oxygen index, whether they dripped during combustion, halogen acid gas content, and notched beam impact strength were tested according to the following standards: (1) Flame retardancy rating test The test was conducted according to UL94 standard, with a sample thickness of 3 mm and a test temperature of 23±2°C. Three samples were tested using the UL94 vertical burning test apparatus from Jiangsu Zhengrui Taibang Electronics Co., Ltd., while observing for any dripping.

[0125] (2) Oxygen index According to GB / T2406.2-2009, 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.

[0126] (3) Tensile strength The test was conducted according to Clause 9 of GB1040—2008, at a temperature of 23±2°C. 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 was taken.

[0127] (4) Impact strength of cantilever beam notch The test was conducted according to Type A of GB / T1843-2008, with a test temperature of 23±2°C. 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.

[0128] (5) Halogen acid gas content The test shall be conducted in accordance with Part 7 of GB / T 17650-1-2021 standard, and the content of halogen acid gas shall be ≤5mg / g in accordance with the requirements for halogen-free materials in IEC62821-1.

[0129] (6) Does it drip when testing flame retardancy rating? To determine whether dripping occurs during flame retardancy rating testing, the test was conducted according to UL94 standards. The sample thickness was 3mm, and the test temperature was 23±2℃. The test was performed using the UL94 vertical burning test apparatus from Jiangsu Zhengrui Taibang Electronics Co., Ltd.

[0130] Table 2 summarizes the components and key preparation variables of Examples 1-10 and Comparative Examples 1-14.

[0131] The test results are detailed in Table 3.

[0132] Table 2 shows the components of Examples 1-10 and Comparative Examples 1-14 of the present invention.

[0133]

[0134]

[0135] According to the specifications in UL94, GB / T2406.2-2009, GB / T 1040-2008, GB / T1843-2008, and GB / T 17650, the acrylonitrile-styrene-butadiene copolymer materials in Examples 1-10 and Comparative Examples 1-14 were tested for tensile strength, flame retardancy rating, oxygen index, dripping during combustion, halogen acid gas content, and notched beam impact strength. The test results are recorded in Table 3 below: Table 3 Performance test table of Examples 1-10 and Comparative Examples 1-14 of the present invention Tensile strength / MPa Flame retardant rating Oxygen index (%) Dripping or not Halogen free environmental requirement Out-come Izod notched impact strength (J / m) Example 1 33 V0 26 No dripping Environmental No out-come 185 Example 2 32 V0 27 No dripping Environmental No out-come 190 Example 3 25 V0 34 No dripping Environmental No out-come 210 Example 4 28 V0 30 No dripping Environmental No out-come 200 Example 5 26 V0 35 No dripping Environmental No out-come 204 Example 6 24 V0 29 No dripping Environmental No out-come 213 Example 7 27 V0 26 No dripping Environmental No out-come 196 Example 8 28 V0 31 No dripping Environmental No out-come 192 Example 9 28 V0 32 No dripping Environmental No out-come 186 Example 10 34 V0 35 No dripping Environmental No out-come 176 Comparative Example 1 18 V0 37 No dripping Environmental No out-come 240 Comparative Example 2 38 V0 22 Dripping Environmental No out-come 153 Comparative Example 3 20 V0 37 No dripping Environmental No out-come 90 Comparative Example 4 29 V0 30 No dripping Environmental No out-come 225 Comparative Example 5 26 V1 27 No dripping Environmental No out-come 216 Comparative Example 6 24 V0 26 Dripping Environmental No out-come 220 Comparative Example 7 27 V2 23 No dripping Environmental No out-come 226 Comparative Example 8 26 V0 29 No dripping Non-environmental No out-come 227 Comparative Example 9 28 V2 23 No dripping Environmental No out-come 219 Comparative Example 10 18 V2 29 Dripping Non-environmental Out-come 252 Comparative Example 11 29 V2 28 Dripping Environmental No out-come 72 Comparative Example 12 30 V2 22 Dripping Environmental No out-come 83 Comparative Example 13 26 V2 24 No dripping Environmental No out-come 208 Comparative Example 14 16 V2 27 Dripping Non-environmental Out-come 249 Based on the test results above, it can be seen that in Examples 1-4, the modified polysilsesquioxane flame retardant 1 of the present invention was added, and the flame retardant rating was V0, with an oxygen index of 26-34%. Examples 1-4 exhibited excellent flame retardancy and high flame retardant efficiency. Example 5 added modified polysilsesquioxane flame retardant 2, Example 6 added modified polysilsesquioxane flame retardant 3, Example 7 added modified polysilsesquioxane flame retardant 4, Example 8 added modified polysilsesquioxane flame retardant 5, Example 9 added modified polysilsesquioxane flame retardant 6, and Example 10 added modified polysilsesquioxane flame retardant 7. The components of modified polysilsesquioxane flame retardants 2 to 7 all contain P, N elements, a Si-O backbone, and a cyclic structure with a carbon-hydrogen ratio of not less than 1. The acrylonitrile-styrene-butadiene copolymer materials obtained in Examples 5 to 10 all exhibited high tensile strength and elongation at break. The acrylonitrile-styrene-butadiene copolymer materials obtained in Examples 5 to 10 exhibit good physical and mechanical properties. Furthermore, these materials demonstrate excellent flame retardant properties, indicating that changes in the substrate and the type of modified polysilsesquioxane flame retardant do not affect the performance of the prepared acrylonitrile-styrene-butadiene copolymer materials. The modified polysilsesquioxane flame retardant provided by this invention can stably improve the flame retardancy of the prepared materials. The acrylonitrile-styrene-butadiene copolymer materials obtained in Examples 5 to 10 did not exhibit dripping during flame retardancy rating tests, and did not crack during thermal shock tests at 110°C, 130°C, and 150°C. This indicates that the acrylonitrile-styrene-butadiene copolymer materials prepared with the added modified polysilsesquioxane flame retardant exhibit excellent adaptability and reliability under rapidly changing temperature conditions, providing assurance for use in harsh environments.

[0136] Comparative Example 1 increased the amount of the modified polysilsesquioxane flame retardant of the present invention, while Comparative Example 2 decreased the amount of the modified polysilsesquioxane flame retardant of the present invention. In both comparative examples, the amount of modified polysilsesquioxane flame retardant was outside the range proposed in the present invention. Experimental data shows that the acrylonitrile-styrene-butadiene copolymer material prepared in Comparative Example 1 had a tensile strength of less than 20 MPa. This indicates that when the amount of modified polysilsesquioxane flame retardant exceeded the range proposed in the present invention, it indicated an excess of modified polysilsesquioxane. The flame retardant has an excessively strong plasticizing effect on thermoplastic polyester elastomer raw materials. This excessive plasticizing effect weakens the entanglement between ABS molecules and also disrupts the effective aggregation between the hard segments of ABS molecules, reducing crystallization and thus reducing the mechanical properties of the prepared thermoplastic polyester elastomer material. In contrast, the acrylonitrile-styrene-butadiene copolymer material prepared in Comparative Example 2 has a flame retardancy rating of V2, indicating that when the amount of modified polysilsesquioxane flame retardant added is too small, the flame retardant performance of the prepared acrylonitrile-styrene-butadiene copolymer material is insufficient.

[0137] Comparative Example 3 contained 10 parts of P-based flame retardant and 10 parts of N-based flame retardant. The proportions of both P-based and N-based flame retardants exceeded the range proposed in this invention. Experimental data showed that Comparative Example 3 had a flame retardant rating of V0 and an oxygen index of 37%, indicating that Comparative Example 3 had excellent flame retardant performance. However, due to the excessive addition of P-based and N-based flame retardants, the mechanical properties of Comparative Example 3 decreased, and its notched beam impact strength was 90 J / m, which was far lower than any of the examples in Examples 1 to 10. Comparative Example 4 contained 0. The amount of P-based flame retardant (3 parts) and N-based flame retardant (0.3 parts) was lower than the range proposed in this invention. Experimental data showed that Comparative Example 4 had a flame retardant rating of V1, indicating insufficient flame retardant performance. This suggests that during combustion, the P and N elements provided by the modified polysilsesquioxane flame retardant were insufficient to support the flame retardant performance of the ABS resin. This reflects the synergistic effect of the modified polysilsesquioxane flame retardant, P-based flame retardant, and N-based flame retardant, ensuring the excellent flame retardant effect of the prepared acrylonitrile-styrene-butadiene copolymer material.

[0138] The modified polysilsesquioxane flame retardant 8 added in Comparative Example 5 contains no nitrogen (N), and the modified polysilsesquioxane flame retardant 10 added in Comparative Example 7 contains no phosphorus (P). Experimental data shows that Comparative Example 5 has a flame retardant rating of V1, and Comparative Example 7 has a flame retardant rating of V2, indicating poor flame retardancy. The modified polysilsesquioxane flame retardant 9 added in Comparative Example 6 lacks cyclic structures with a carbon-to-hydrogen ratio of not less than 1, such as benzene rings. During combustion, it cannot rapidly generate a large number of Si-C bonds, resulting in insufficient char layer and dripping during flame retardant rating testing. The modified polysilsesquioxane flame retardant 11 added in Comparative Example 8 contains no nitrogen and excess halogens, producing halogen acid gas during combustion, which is environmentally unfriendly. Comparative Example 9 added glycidyl etheroxypropyl-isooctyl polysilsesquioxane as a flame retardant. While glycidyl etheroxypropyl-isooctyl polysilsesquioxane has numerous Si-O bonds, it lacks P, N elements, and a cyclic structure with a carbon-to-hydrogen ratio of at least 1. Experimental data shows that the acrylonitrile-styrene-butadiene copolymer material prepared in Comparative Example 9 exhibits insufficient flame retardant properties. Comparative Example 10 added bis(4-nitrophenyl)phosphoryl chloride as a flame retardant. While bis(4-nitrophenyl)phosphoryl chloride contains P, N elements, halogens, and a cyclic structure with a carbon-to-hydrogen ratio of at least 1, it fails to form a char layer during combustion. Experimental data indicates that Comparative Example 10's flame retardant properties are insufficient. The performance of the modified polysilsesquioxane flame retardant was poor, and it dripped during combustion. Furthermore, due to its halogen content, it produced halogen acid gas during combustion, which is environmentally unfriendly. After a period of storage, it also showed signs of precipitation. Comparative Example 11 added only the P-based flame retardant diethylaluminum hypophosphite as a flame retardant, and Comparative Example 12 added only the N-based flame retardant MCA as a flame retardant, to replace the modified polysilsesquioxane flame retardant of this invention. Experimental data showed that the acrylonitrile-styrene-butadiene copolymer materials prepared by Comparative Examples 11 and 12 had insufficient flame retardant performance, with both having a flame retardant rating of V2. They also dripped during combustion, and in the cantilever beam notched impact test, both had a strength below 85 J / L. The presence of a value below m indicates that, under the same additive ratio, neither P-based nor N-based flame retardants alone can achieve the flame retardant effect exhibited by the modified polysilsesquioxane flame retardant of this invention. Furthermore, because P-based and N-based flame retardants achieve flame retardancy by providing an acid and gas source during combustion, they cannot generate substances such as a char layer. Therefore, they cannot achieve the anti-dripping effect during combustion. Comparative Example 13 only added glycidyl etheroxypropyl-isooctyl polysilsesquioxane as a flame retardant component, and Comparative Example 14 only added di(4-nitrophenyl)phosphoryl chloride as a flame retardant component. As can be seen from the experimental data, the flame retardant performance of Comparative Example 13 and Comparative Example 14 is insufficient, and Comparative Example 14 exhibits dripping during combustion.

[0139] Therefore, this invention verifies that modifying polysilsesquioxane flame retardants improves the flame retardancy of ABS acrylonitrile-styrene-butadiene copolymer materials, giving them excellent physical and mechanical properties and excellent anti-dripping effect during combustion. It is also safe and environmentally friendly, has extremely high industrial value, and can be widely applied and promoted.

[0140] 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: Acrylonitrile-styrene-butadiene copolymer (ABS) 50-70 parts, 1-5 parts of phosphorus-based flame retardant 1-5 parts of nitrogen-based flame retardant 10-20 parts of modified polysilsesquioxane flame retardant, The modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B, and catalyst under an alkaline environment. The silsesquioxane A includes at least one epoxy group D, and the compound B contains phosphorus P and nitrogen N, and includes at least one halogen end group X.

2. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The structure of the silsesquioxane A includes at least one of the fully cage-like silsesquioxanes, and its structural formula includes at least one ， Where 6≥n≥1, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

3. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The compound B includes at least one cyclic structure E with a carbon-hydrogen ratio of not less than 1, and the halogen end group X is not directly connected to the cyclic structure E.

4. The acrylonitrile-styrene-butadiene copolymer material as described in claim 3, characterized in that, The cyclic structure E with a carbon-to-hydrogen ratio of not less than 1 includes at least one of a benzene ring group and an imidazole group.

5. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The modified polysilsesquioxane flame retardant is synthesized by a nucleophilic substitution reaction of silsesquioxane A and compound B under the action of a catalyst after ring-opening, characterized by the following reaction route: .

6. The acrylonitrile-styrene-butadiene copolymer material as described in claim 5, characterized in that, The method for synthesizing the modified polysilsesquioxane flame retardant includes the following steps: (1) First, dissolve silsesquioxane A in an organic solvent solution, then add a catalyst. Under the action of the catalyst, stir evenly and add a small amount of water. Continue stirring for 4-8 hours, then place the whole thing in an ice-water bath and stir. (2) Dissolve compound B in an organic solution, and slowly add the organic solution of compound B to step (1) through a constant pressure dropping funnel, while slowly adding an alkaline agent. Under alkaline conditions, the epoxy group D in silsesquioxane A undergoes a nucleophilic ring-opening substitution reaction with the halogen end group X in compound B to obtain the modified polysilsesquioxane flame retardant preproduct. (3) The reaction preproduct in step (2) is rotary evaporated to remove the organic solvent. Then it is washed with saturated sodium chloride solution, filtered and dried to obtain the modified polysilsesquioxane flame retardant.

7. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:

1.

8. The acrylonitrile-styrene-butadiene copolymer material as described in claim 6, characterized in that, The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts; the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones; and the basic agent is at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium phosphate, and sodium silicate.

9. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The raw materials for the acrylonitrile-styrene-butadiene copolymer material, by weight, include: Acrylonitrile-styrene-butadiene copolymer (ABS) 50-60 parts, 2-5 parts of phosphorus-based flame retardant 2-5 parts of nitrogen-based flame retardant 15-20 parts of modified polysilsesquioxane flame retardant.

10. The acrylonitrile-styrene-butadiene copolymer material as described in claim 1, characterized in that, The acrylonitrile-styrene-butadiene copolymer includes at least one of general-purpose ABS, impact-resistant ABS, high-impact ABS, cold-resistant ABS, heat-resistant ABS, flame-retardant ABS, reinforced ABS, and electroplating ABS. The phosphorus-based flame retardant includes at least one of diethylaluminum hypophosphite, aluminum hypophosphite, phosphate ester, phosphite ester, and phosphonate ester. The nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

11. 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 0.5-1 parts and the antioxidant is 0.5-1 parts.

12. 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.

13. The method for preparing the acrylonitrile-styrene-butadiene copolymer material according to claim 12, characterized in that, The raw materials also include at least one of lubricant and antioxidant.

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