Abs modified tpu alloy material and preparation method thereof

Abstract

The application discloses an ABS modified TPU alloy material, which comprises 40-50 parts of thermoplastic polyurethane elastomer (TPU), 20-30 parts of ABS resin and 10-30 parts of modified polysilsesquioxane flame retardant, wherein the modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B and a catalyst in an alkaline environment, the silsesquioxane A comprises at least one epoxy group D, the compound B contains phosphorus element P and nitrogen element N, and at least one halogen end group X is included. The ABS modified TPU alloy material provided by the application has excellent flame retardant performance and dielectric performance, and has good processing performance and mechanical properties; meanwhile, the anti-cracking performance and anti-dripping effect of the ABS modified TPU alloy material are greatly improved, and the ABS modified TPU alloy material is safe and environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of materials, specifically to an ABS-modified TPU alloy material and its preparation method. Background Technology

[0002] 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 spacing, large bond angles, and high bond energies. They are very flexible and have a very low viscous flow activation energy. 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.

[0003] ABS-modified TPU alloys, combining the rigidity of ABS with the toughness of TPU, have seen continuous development in the field of materials science, particularly in additive manufacturing technologies such as 3D printing. By blending rigid ABS with elastic TPU, the impact resistance and damping performance of the material can be significantly improved. Due to its combination of toughness and processability, it has application potential in automotive parts, sporting goods, and durable consumer products. However, because ABS-modified TPU alloys have poor flame retardancy and the addition of TPU sacrifices some of the original tensile strength and stiffness of ABS, it is essential to develop a new type of ABS-modified TPU alloy material that possesses halogen-free high flame retardancy, anti-dripping effect, high physical and mechanical properties, and crack resistance. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention proposes an ABS modified TPU alloy material and its preparation method, aiming to solve the problems of poor flame retardancy, poor physical and mechanical properties, and dripping during combustion of the current ABS modified TPU alloy material.

[0005] To achieve the above objectives, this invention proposes an ABS-modified TPU alloy material. The raw materials of the ABS-modified TPU alloy material, by weight, include 40-50 parts of thermoplastic polyurethane elastomer (TPU), 20-30 parts of ABS resin, and 10-30 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. 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.

[0006] Optionally, the structure of silsesquioxane A includes at least one of fully cage-like silsesquioxanes, and its structural formula includes at least one... , In the case of 6≥n≥, 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 ABS modified TPU alloy material, by weight, include 40-45 parts of thermoplastic polyurethane elastomer (TPU), 20-25 parts of ABS resin, and 15-30 parts of modified polysilsesquioxane flame retardant.

[0014] Optionally, the thermoplastic polyurethane elastomer includes at least one of polyester-type thermoplastic polyurethane elastomer or polyether-type thermoplastic polyurethane elastomer.

[0015] Optionally, the raw materials of the ABS modified TPU alloy material further include at least one of a compatibilizer, lubricant, antioxidant, anti-hydrolysis agent, and matting agent; wherein, by weight, the raw materials are 3-8 parts of the compatibilizer, 0.5-1 part of the lubricant, 0.5-2 parts of the antioxidant, 0.5-2 parts of the anti-hydrolysis agent, and 2-10 parts of the matting agent.

[0016] This invention provides a method for preparing ABS-modified TPU alloy material, comprising the following steps: mixing the raw materials evenly, extruding and granulating them through an extruder to obtain granules, namely the ABS-modified TPU alloy material.

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

[0018] In this invention, the ABS-modified TPU alloy material includes TPU, ABS resin, and modified polysilsesquioxane flame retardant. It does not require plasticizers and possesses excellent elasticity, chemical resistance, and abrasion resistance. Because the modified polysilsesquioxane flame retardant contains P, N elements, a cyclic structure D with a carbon-to-hydrogen ratio greater than 1, and at least one inorganic silicon cage core, a large number of Si-O bonds decompose upon heating to form a dense ceramic barrier layer. Simultaneously, the P element in the modified polysilsesquioxane flame retardant provides an acid source, and the N element provides non-combustible gas, resulting in stronger flame retardancy. 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 ABS-modified TPU alloy materials, it has little impact on the material's performance, and excellent flame retardancy can be obtained without a high addition amount. The prepared ABS-modified TPU alloy materials can maintain the original good processing performance, elasticity, and flame retardant properties, improve the crack resistance of TPU alloy materials, and greatly enhance the crack resistance and anti-dripping effect of ABS-modified TPU alloy 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 resin) is a thermoplastic polymer material with high strength, good toughness, and easy processing and molding. ABS resin is a terpolymer composed of acrylonitrile, butadiene, and styrene. This material combines the advantages of the three monomers, exhibiting excellent properties such as high surface hardness, toughness, good low-temperature impact resistance, good creep resistance, good dimensional stability, and low molding shrinkage.

[0023] Thermoplastic polyurethane elastomers (TPUs) are mainly of polyester and polyether types. They have a wide range of hardness, excellent mechanical properties, wear resistance, oil resistance, and excellent elasticity. Currently, TPU materials are widely used in footwear, pipes, tires, film materials, and cable materials.

[0024] 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.

[0025] ABS-modified TPU alloys, combining the rigidity of ABS with the toughness of TPU, have seen continuous development in the field of materials science, particularly in additive manufacturing technologies such as 3D printing. By blending rigid ABS with elastic TPU, the impact resistance and damping performance of the material can be significantly improved. Due to its combination of toughness and processability, it has application potential in automotive parts, sporting goods, and durable consumer products. However, because ABS-modified TPU alloys have poor flame retardancy and the addition of TPU sacrifices some of the original tensile strength and stiffness of ABS, it is essential to develop a new type of ABS-modified TPU alloy material that possesses halogen-free high flame retardancy, anti-dripping effect, high physical and mechanical properties, and crack resistance.

[0026] To address the aforementioned problems, in a first aspect, this invention provides an ABS-modified TPU alloy material. The raw materials of the ABS-modified TPU alloy material, by weight, include 40-50 parts of thermoplastic polyurethane elastomer (TPU), 20-30 parts of ABS resin, and 10-30 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.

[0027] Understandably, in ABS modified TPU alloy materials, TPU is any number of parts between 40 and 50, such as 40, 45, or 50; ABS resin is any number of parts between 20 and 30, such as 20, 25, or 30; and modified polysilsesquioxane flame retardant is any number of parts between 10 and 30, such as 10, 15, 20, 25, or 30.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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. This non-combustible gas causes the incompletely carbonized portion of the ABS-modified TPU alloy material 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.

[0032] ABS-modified TPU alloy material includes TPU, ABS resin, and modified polysilsesquioxane flame retardant. It does not require plasticizers and possesses excellent elasticity, chemical resistance, and abrasion resistance. Because the modified polysilsesquioxane flame retardant contains phosphorus (P), nitrogen (N), a cyclic structure D with a carbon-to-hydrogen ratio greater than 1, and at least one inorganic silicon cage core, a large number of Si-O bonds decompose upon heating to form a dense ceramic barrier layer. Simultaneously, the P element in the modified polysilsesquioxane flame retardant provides an acid source, and the N element provides non-combustible gas, resulting in stronger flame retardancy. 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 ABS-modified TPU alloy materials, it has little impact on the material's performance, and excellent flame retardancy can be obtained without a high addition amount. The prepared ABS-modified TPU alloy materials can maintain the original good processing performance, elasticity, and flame retardant properties, improve the crack resistance of TPU alloy materials, and greatly enhance the crack resistance and anti-dripping effect of ABS-modified TPU alloy materials, while being safe and environmentally friendly.

[0033] Furthermore, the structure of silsesquioxane A includes at least one of fully cage-like silsesquioxanes, and its structural formula includes at least one... , In the case of 6≥n≥, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] Understandably, the structural formula of octa[(3-glycidylpropyl)dimethylsiloxy]-substituted PSS is... , where n is 2, and R1, R2, R3, R4, R5, R6, R7, and R8 include 7 epoxy groups D.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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. The above structure, through the formation of a carbon layer during combustion, Protective layers such as ceramic barrier layers, protective films, or heat-insulating coke layers greatly improve the anti-dripping effect. At the same time, they isolate heat and oxygen transfer and reduce the release of flammable gases. The combined effect of multiple mechanisms significantly improves the flame retardant performance of the material. 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 is extremely difficult to carry out. 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 ABS modified TPU alloy materials.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

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

[0052] Understandably, the structural formula of bis(4-nitrobenzyl)chlorophosphate is... .

[0053] Understandably, the structural formula of di[2-(p-nitrophenyl)ethyl]chlorophosphate is... .

[0054] Understandably, the structural formula of 3-nitro-N-(2,2,2-trichloro-1-Diethoxy-phosphorylethyl)benzamide is... .

[0055] Understandably, the structural formula of Bis(3-chloropropyl)p-nitrophenyl phosphate is... .

[0056] Understandably, the structural formula of DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE is... .

[0057] Understandably, the structural formula of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryldichloro is... .

[0058] 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.

[0059] 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: .

[0060] 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.

[0061] 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.

[0062] 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.

[0063] Furthermore, the molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:1.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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-(TRIFLUOROME) [THYL)BENZOHYDRAZONOYL]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 and DIETHYL[2-(2,4-DINITROPHENYL)- During the reaction of 3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE, 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 in one molecule can react with DIETHYL[2-(2,4-DINITROPHENYL)-3- The three F-terminal groups in [TRIFLUOROMETHYL]BENZOHYDRAZONOYL]PHOSPHONATE 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] In some embodiments, the catalyst is preferably sodium hydroxide.

[0079] In some embodiments, the organic solvent is preferably ethanol.

[0080] In some embodiments, the alkaline agent is preferably triethylamine.

[0081] Furthermore, the raw materials of the ABS modified TPU alloy material, by weight, include 40-45 parts of thermoplastic polyurethane elastomer (TPU), 20-25 parts of ABS resin, and 15-30 parts of modified polysilsesquioxane flame retardant.

[0082] Reducing the proportions of TPU and ABS resin in ABS-modified TPU alloy materials can further improve their mechanical and flame-retardant properties.

[0083] Furthermore, the thermoplastic polyurethane elastomer includes at least one of polyester-type thermoplastic polyurethane elastomer or polyether-type thermoplastic polyurethane elastomer.

[0084] In some embodiments, the thermoplastic polyurethane elastomer is preferably a polyester-type thermoplastic polyurethane elastomer.

[0085] Furthermore, the raw materials for ABS modified TPU alloy materials also include at least one of compatibilizer, lubricant, antioxidant, anti-hydrolysis agent, and matting agent; wherein, by weight, the raw materials are 3-8 parts compatibilizer, 0.5-1 part lubricant, 0.5-2 parts antioxidant, 0.5-2 parts anti-hydrolysis agent, and 2-10 parts matting agent.

[0086] Anti-hydrolysis agents can improve the long-term stability of insulation materials in humid and hot environments, prevent polymer chains from degrading and deteriorating due to hydrolysis, and thus ensure the electrical reliability and service life of cables. Lubricants can improve the flowability of ABS modified TPU alloy 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 thus extending their service life. Matting agents can be uniformly dispersed in the matrix, so that the surface of the extruded cable will form a micro-uneven rough structure. When light shines on it, this micro-rough surface will cause strong diffuse reflection, which will greatly reduce the inherent specular reflection of high-gloss materials, thereby obtaining a visually soft and comfortable matte effect.

[0087] In some embodiments, the compatibilizer includes at least one of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride, with POE being the preferred compatibilizer.

[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] In some embodiments, the anti-hydrolysis agent is at least one of monocarbodiimide, polycarbodiimide (or polycarbodiimide) and sterically hindered aromatic carbodiimide, preferably monocarbodiimide.

[0091] In some embodiments, the matting agent is at least one selected from kaolin, silica, montmorillonite, and calcium carbonate, preferably calcium carbonate.

[0092] To address the above problems, this invention also proposes a method for preparing ABS-modified TPU alloy 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 ABS modified TPU alloy material.

[0093] In some embodiments, extrusion granulation is achieved using a twin-screw extruder.

[0094] The processing temperatures of each temperature 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.

[0095] In some embodiments, the temperature at which ABS-modified TPU alloy material is obtained by extrusion granulation is 170°C-190°C.

[0096] In some embodiments, the drying time is preferably 8-12 hours.

[0097] Furthermore, the raw materials also include at least one of the following: compatibilizer, lubricant, antioxidant, anti-hydrolysis agent, and matting agent.

[0098] The following specific embodiments and data explain the content of the present invention.

[0099] 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

[0100]

[0101] 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. 40 parts of polyether-type TPU, 20 parts of ABS, 15 parts of modified polysilsesquioxane flame retardant, 1.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0102] Example 2: The preparation method is the same as in Example 1, except that: 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 1.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0103] Example 3: The preparation method is the same as in Example 1, except that: 50 parts of polyether-type TPU, 30 parts of ABS, 10 parts of modified polysilsesquioxane flame retardant, 1.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material is obtained.

[0104] Example 4: The preparation method is the same as in Example 1, except that: 40 parts of polyether-type TPU, 25 parts of ABS, 30 parts of modified polysilsesquioxane flame retardant, 1.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0105] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 2.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0106] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 3 and 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0107] 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 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 through a constant-pressure dropping funnel to the ethanol solution of acryloyloxypropyl-glycidyl etheroxypropyl cage-type 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 4. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 4 and 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0108] 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 mixture was then placed in an ice-water bath and stirred. 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 through a constant-pressure dropping funnel to the ethanol solution of glycidyl etheroxypropyl-isooctyl 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 5. 45 parts of polyester-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0109] 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 in the reaction solution, 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 6 parts of compatibilizer, 5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0110] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 7.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0111] Comparative Example 1: The preparation method is the same as in Example 1, except that: 45 parts of polyether-type TPU, 25 parts of ABS, 40 parts of modified polysilsesquioxane flame retardant, 1.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0112] Comparative Example 2: The preparation method is the same as in Example 1, except that: 45 parts of polyether-type TPU, 25 parts of ABS, 3 parts of modified polysilsesquioxane flame retardant, 1.5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0113] Comparative Example 3: The preparation method is the same as in Example 8, except that: 45 parts of polyether-type TPU, 25 parts of ABS, 40 parts of modified polysilsesquioxane flame retardant, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0114] Comparative Example 4: The preparation method is the same as in Example 8, except that: 45 parts of polyether-type TPU, 25 parts of ABS, 3 parts of modified polysilsesquioxane flame retardant, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0115] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 8 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0116] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 9 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0117] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 10 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0118] 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. 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of modified polysilsesquioxane flame retardant, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0119] Comparative Example 9: 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of glycidyl etheroxypropyl-isooctyl polysilsesquioxane, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0120] Comparative Example 10: 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of di(4-nitrophenyl)phosphoyl chloride, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0121] Comparative Example 11: 45 parts of polyether-type TPU, 25 parts of ABS, 10 parts of P-type flame retardant, 10 parts of N-type flame retardant, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0122] Comparative Example 12: 45 parts of polyether-type TPU, 25 parts of ABS, 20 parts of aluminum hydroxide, 5 parts of compatibilizer, 0.5 parts of lubricant, 0.5 parts of antioxidant, 1 part of anti-hydrolysis agent, and 5 parts of matting agent were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain ABS-modified TPU alloy material preform. After drying at 80°C, a high flame-retardant and crack-resistant ABS-modified TPU alloy material was obtained.

[0123] Table 2 summarizes the components and key preparation variables of Examples 1-10 and Comparative Examples 1-12.

[0124] The ABS-modified TPU alloy materials obtained in the above examples and comparative examples were injection molded or pressed into sheets, and then subjected to tests for flame retardancy rating, oxygen index, tensile strength, elongation at break, thermal shock at 110°C, thermal shock at 130°C, thermal shock at 150°C, halogen acid gas content, and dielectric constant. The test standards are as follows: (1) Flame retardancy rating test According to GB / T 5455-2014, the samples were subjected to vertical flammability testing. The samples were cut to the specified dimensions and tested under the specified conditions, and key parameters such as flammability time and residual substances were monitored.

[0125] (2) 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.

[0126] (3) Oxygen index According to GB / T 2406.2-2009, the sample size was prepared according to Type IV sample size. The test was conducted according to Method A - Top Surface Ignition Method. The oxygen index tester was performed using a device from Nanjing Jiangning District Fangshang Analytical Instrument Equipment Factory.

[0127] (4) Tensile strength and elongation at break The test was conducted according to Clause 9 of GB 1040—2008, with a test temperature of 23±2℃. The tensile test used a standard dumbbell-shaped specimen with a tensile speed of 250 mm / min. The tensile strength and elongation at break of five specimens were tested using a micro-controlled electronic universal tensile testing machine from Dongguan High-Speed ​​Railway Testing Co., Ltd., and the average value of the results was taken.

[0128] (5) Thermal shock at 110-150℃ The tests were conducted according to Appendix A of GB / T 32129-2015 standard, with a test temperature of 23±2℃ and a weight of 2kg. Three samples were tested at each temperature using the thermal shock resistance testing apparatus from Hebei Zhongke Beigong Test Instrument Co., Ltd.

[0129] (6) 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.

[0130] (7) Tensile strength at 100% elongation The test was conducted in accordance with Clause 9 of GB 1040—2008, and the experimental data shows that...

[0131] (8) Elastic modulus The test was conducted in accordance with Clause 9 of GB 1040—2008, and the experimental data shows that...

[0132] The test results are detailed in Table 3.

[0133] Table 2 shows the components of Examples 1-10 and Comparative Examples 1-12 of the present invention.

[0134]

[0135]

[0136] According to the specifications in GB / T 1040-2008, GB / T 5455, GB / T 2406.2, GB / T32129, UL94, and GB / T 17650-1-2021, the ABS modified TPU alloy materials in Examples 1-10 and Comparative Examples 1-12 were tested for tensile strength, elongation at break, tensile strength at 100% elongation, modulus of elasticity, flame retardancy rating, oxygen index, thermal shock at 110℃, thermal shock at 130℃, thermal shock at 150℃, whether it drips during combustion, and halogen acid gas content. The test results are recorded in Table 3 below: Table 3 Performance test table of Examples 1-10 and Comparative Examples 1-12 of the present invention

[0137]

[0138] 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 25-32%. Examples 1-4 exhibited good 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, a Si-O skeleton, and a cyclic structure with a carbon-hydrogen ratio of not less than 1. The ABS-modified TPU alloy materials obtained in Examples 5 to 10 all exhibited high tensile strength. The ABS-modified TPU alloy materials obtained in Examples 5 to 10 exhibit good physical and mechanical properties, with low elongation at break. Furthermore, these materials demonstrate excellent flame retardancy, indicating that changes in the substrate and the type of modified polysilsesquioxane flame retardant do not affect the performance of the prepared ABS-modified TPU alloy materials. The modified polysilsesquioxane flame retardant provided by this invention can stably improve the flame retardancy of the prepared materials. The ABS-modified TPU alloy materials obtained in Examples 5 to 10 did not exhibit dripping during flame retardancy testing, and did not crack during thermal shock tests at 110°C, 130°C, and 150°C. This indicates that the ABS-modified TPU alloy 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.

[0139] In Comparative Examples 1 and 3, the amount of the modified polysilsesquioxane flame retardant of the present invention was increased to 40 parts, while in Comparative Examples 2 and 4, the amount of the modified polysilsesquioxane flame retardant of the present invention was reduced to 3 parts. In all four comparative examples, the amount of modified polysilsesquioxane flame retardant was outside the range proposed in the present invention. Experimental data shows that the tensile strength of the ABS-modified TPU alloy materials prepared in Comparative Examples 1 and 3 was less than 20 MPa. This indicates that when the amount of modified polysilsesquioxane flame retardant exceeds the range proposed in the present invention, it indicates that excessive modified polysilsesquioxane flame retardant... The excessive plasticizing effect of the flame retardant on the ABS-modified TPU alloy material weakens the entanglement between molecules in the ABS-modified TPU alloy material and disrupts the effective aggregation between the hard segments of the molecules, reducing crystallization and thus reducing the mechanical properties of the prepared ABS-modified TPU alloy material. In contrast, the ABS-modified TPU alloy materials prepared in Comparative Examples 2 and 4 both had a flame retardant rating of V2, indicating that when the amount of modified polysilsesquioxane flame retardant added is too small, the flame retardant performance of the prepared ABS-modified TPU alloy material is insufficient.

[0140] The modified polysilsesquioxane flame retardant 8 added in Comparative Example 5 contains no nitrogen (N) element, and the modified polysilsesquioxane flame retardant 10 added in Comparative Example 7 contains no phosphorus (P) element. Experimental data shows that both Comparative Example 5 and Comparative Example 7 have a flame retardant rating of V1, 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. Therefore, it cannot rapidly generate a large number of Si-C bonds during combustion, resulting in insufficient char layer. During flame retardancy testing, dripping occurred. In Comparative Example 8, the modified polysilsesquioxane flame retardant 11 lacked nitrogen (N) and contained excess halogens, producing halogen acid gases during combustion, which is environmentally unfriendly. In Comparative Example 9, glycidyl etheroxypropyl-isooctyl polysilsesquioxane was added instead of the modified polysilsesquioxane flame retardant as the flame retardant component. While glycidyl etheroxypropyl-isooctyl polysilsesquioxane has numerous Si-O bonds, it does not contain phosphorus (P), nitrogen (N), or cyclic compounds with a carbon-to-hydrogen ratio of at least 1. Based on the experimental data, the flame retardant performance of the ABS-modified TPU alloy material prepared in Comparative Example 9 is insufficient. Comparative Example 10 added bis(4-nitrophenyl)phosphoryl chloride to replace the modified polysilsesquioxane flame retardant as the flame retardant component. While bis(4-nitrophenyl)phosphoryl chloride contains P, N, halogens, and a cyclic structure with a carbon-to-hydrogen ratio of not less than 1, it failed to form a char layer during combustion. Therefore, the experimental data indicates that Comparative Example 10 exhibits poor flame retardant performance. During combustion, dripping occurred, and because it contains halogens, halogen acid gas was produced during combustion, which is environmentally unfriendly. Furthermore, after a period of time, precipitation occurred. Comparative Example 11 added 10 parts of P-based flame retardant and 10 parts of N-based flame retardant to replace the modified polysilsesquioxane flame retardant of this invention. Experimental data showed that Comparative Example 11 had a flame retardant rating of V1, and the flame retardant performance of the prepared ABS-modified TPU alloy material was insufficient. This reflects that when adding equal parts of flame retardant, P-based and N-based flame retardants cannot achieve the same flame retardant effect as the modified polysilsesquioxane flame retardant of this invention. The dripping phenomenon observed in Comparative Example 11 during combustion indicates that the modified polysilsesquioxane flame retardant of this invention has a good anti-dripping effect. Comparative Example 12 only added 20 parts of aluminum hydroxide as a flame retardant component. Experimental data showed that the flame retardant rating of the ABS-modified TPU alloy material prepared in Comparative Example 12 was V2, and its anti-dripping performance was poor.

[0141] Therefore, this invention verifies that modifying polysilsesquioxane flame retardants improves the flame retardancy of ABS-modified TPU alloy materials, giving them excellent physical and mechanical properties and superior anti-dripping effect during combustion. Furthermore, it is safe and environmentally friendly, possessing extremely high industrial value and can be widely applied and promoted.

[0142] 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 ABS-modified TPU alloy material, characterized in that, The raw materials of the ABS-modified TPU alloy material, by weight, include: 40-50 parts of thermoplastic polyurethane elastomer (TPU) 20-30 parts of ABS resin 10-30 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 ABS-modified TPU alloy 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 ， In the case of 6≥n≥, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

3. The ABS-modified TPU alloy 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 ABS-modified TPU alloy 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 ABS-modified TPU alloy 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 ABS-modified TPU alloy 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 ABS-modified TPU alloy 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 ABS-modified TPU alloy 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 ABS-modified TPU alloy material as described in claim 1, characterized in that, The raw materials of the ABS-modified TPU alloy material, by weight, include: 40-45 parts of thermoplastic polyurethane elastomer (TPU) 20-25 parts of ABS resin 15-30 parts of modified polysilsesquioxane flame retardant.

10. The ABS-modified TPU alloy material as described in claim 1, characterized in that, The thermoplastic polyurethane elastomer includes at least one of polyester-type thermoplastic polyurethane elastomer or polyether-type thermoplastic polyurethane elastomer.

11. The ABS-modified TPU alloy material as described in claim 1, characterized in that, The raw materials of the ABS modified TPU alloy material also include at least one of the following: compatibilizer, lubricant, antioxidant, anti-hydrolysis agent, and matting agent; wherein, by weight, the raw materials are: 3-8 parts of compatibilizer, 0.5-1 part of lubricant, 0.5-2 parts of antioxidant, 0.5-2 parts of anti-hydrolysis agent, and 2-10 parts of matting agent.

12. A method for preparing the ABS-modified TPU alloy 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, which are the ABS modified TPU alloy materials.

13. The method for preparing the ABS-modified TPU alloy material as described in claim 12, characterized in that, The raw materials also include at least one of the following: compatibilizer, lubricant, antioxidant, anti-hydrolysis agent, and matting agent.

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