Flame-retardant nylon material and preparation method thereof

Abstract

The invention discloses a flame-retardant nylon material which comprises 50-70 parts of PA (polyamide), 1-5 parts of a toughening agent, 3-5 parts of a P-series flame retardant, 3-5 parts of an N-series flame retardant and 10-20 parts of a modified polysilsesquioxane flame retardant, and 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 flame-retardant nylon material provided by the invention is excellent in flame retardant property and dielectric property, has good processability and mechanical property, greatly improves the anti-cracking property and anti-dripping effect of the flame-retardant nylon material, and is safe and environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of materials, specifically to a flame-retardant nylon 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] Nylon (PA) is a highly polar polymer material. Its molecules can form hydrogen bonds, resulting in a high melting temperature and a narrow melting range, with a distinct melting point. It is widely used in various industries. However, because nylon lacks flame-retardant properties, flame-retardant modification has become a new direction for nylon materials. Currently, there are two main types of flame-retardant modification for nylon: chemical modification and physical modification. Chemical flame-retardant modification involves introducing flame-retardant components into the main chain or side chains of nylon through chemical reactions, thereby endowing the molecular chain itself with flame-retardant properties. Physical flame-retardant modification involves introducing flame-retardant components or flame retardants into the nylon matrix, followed by mixing and granulation to prepare flame-retardant modified nylon materials. Blending flame-retardant modification is the most convenient and widely used method. Melamine polyphosphate (MPP) is a relatively ideal flame retardant for nylon, with a chemical composition similar to nylon and good compatibility with the nylon matrix. Meanwhile, melamine polyphosphate molecules contain nitrogen and phosphorus elements, resulting in high flame retardant efficiency. Flame-retardant and antistatic nylon materials are produced by melt blending nylon with alkyl phosphinates and melamine polyphosphate as flame retardants and nylon as the matrix through an extruder. Although this method produces flame-retardant and antistatic nylon, the amount of melamine polyphosphate added as a flame retardant is large. The introduction of a large amount of flame retardant will reduce the mechanical properties of the material. Therefore, it is essential to develop a new type of flame-retardant nylon material that has 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 a flame-retardant nylon material and its preparation method, aiming to solve the problems of poor flame retardancy, poor physical and mechanical properties, and dripping during combustion of current flame-retardant nylon materials.

[0005] To achieve the above objectives, the present invention proposes a flame-retardant nylon material. The raw materials of the flame-retardant nylon material, by weight, include 50-70 parts of PA, 1-5 parts of toughening agent, 3-5 parts of P-based flame retardant, 3-5 parts of N-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 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... , 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 flame-retardant nylon material, by weight, include 50-60 parts of PA, 1-3 parts of toughening agent, 3-5 parts of P-based flame retardant, 3-5 parts of N-based flame retardant, and 13-18 parts of modified polysilsesquioxane flame retardant.

[0014] Optionally, the toughening agent includes at least one of vinyl polymer-grafted polyether polyol (POP), polyolefin elastomer (POE), olefin block copolymer (OBC), and ethylene-vinyl acetate copolymer (EVA); the P-based flame retardant includes at least one of diethylaluminum hypophosphite, aluminum hypophosphite, phosphate ester, phosphite ester, and phosphonate ester; and the N-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0015] Optionally, the raw materials of the flame-retardant nylon 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 flame-retardant nylon material, comprising the following steps: mixing the raw materials evenly, extruding and granulating them through an extruder to obtain granules, i.e., the flame-retardant nylon material.

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

[0018] In this invention, the flame-retardant nylon material includes PA, phosphorus-based flame retardant, nitrogen-based flame retardant, and modified polysilsesquioxane flame retardant. 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. The inorganic silicon cage core decomposes 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 D with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio and contains a large amount of carbon. During combustion, this large amount of carbon forms a glassy protective film or a heat-insulating coke layer. These protective films or coke layers can isolate air, prevent heat transfer, and reduce the release of combustible gases. These structures, through the formation of protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, significantly improve the anti-dripping effect. Simultaneously, they isolate heat and oxygen transfer and reduce the release of combustible gases. The combined effect of these multiple mechanisms significantly enhances the flame-retardant performance of the material. Simultaneously, the numerous Si-O bonds decompose upon heating to form a dense ceramic barrier layer. The P element in the modified polysilsesquioxane flame retardant, together with the P-based flame retardant, provides an acid source, while the N element and the N-based flame retardant provide non-combustible gases, 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 various flame-retardant elements work together synergistically to retard flames, reducing the amount of flame retardant required while improving the flame-retardant, dielectric, and mechanical properties of the flame-retardant nylon material. The flame-retardant nylon material provided by this invention exhibits excellent flame-retardant and dielectric properties, as well as good processing and mechanical properties. It also significantly improves the crack resistance and anti-dripping effect of the flame-retardant nylon material, making it 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: PA: Polyamide, also known as nylon or polyamide fiber, is a general term for thermoplastic resins containing repeating amide groups (-NHCO-) ​​in their molecular chains. It includes aliphatic PA, aliphatic-aromatic PA, and aromatic PA. Aliphatic PA has the most varieties and the largest production volume, and is mainly used in the automotive, electrical and electronic, transportation, and machinery manufacturing industries to manufacture various bearings, gears, oil pipes, oil reservoirs, protective covers, and other components.

[0023] POE: Polyolefin elastomer is a thermoplastic elastomer that is polymerized in situ using metallocene catalysts to polymerize ethylene and octene. It has excellent toughness, processability, weather resistance, heat aging resistance and UV resistance. Its molecular structure gives it a narrow relative molecular mass distribution and a uniform short branch distribution, resulting in excellent physical and mechanical properties (such as high elasticity, high strength and high elongation) and good low-temperature performance.

[0024] EMA-grafted maleic anhydride (EMA-g-MAH) is an important polymer modifier. It is produced by grafting maleic anhydride (MAH) functional groups onto the molecular chain of ethylene-methyl acrylate copolymer (EMA) through a chemical reaction. EMA-g-MAH plays a crucial role in automotive parts, packaging materials, polymer alloys, and adhesives due to its balanced flexibility, polarity, and processability.

[0025] POE-grafted maleic anhydride (POE-g-MAH) is a high-performance polymer material prepared through chemical modification. It uses polyolefin elastomer (POE) as the main chain and introduces highly active maleic anhydride (MAH) functional groups into the molecular chain through a grafting reaction. This not only retains the high elasticity, excellent impact resistance and low-temperature toughness of the POE matrix, but also significantly improves its compatibility and adhesion with polar materials through the polar MAH groups.

[0026] 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.

[0027] Nylon (PA) is a highly polar polymer material. Its molecules can form hydrogen bonds, resulting in a high melting temperature and a narrow melting range, with a distinct melting point. It is widely used in various industries. However, because nylon lacks flame-retardant properties, flame-retardant modification has become a new direction for nylon materials. Currently, there are two main types of flame-retardant modification for nylon: chemical modification and physical modification. Chemical flame-retardant modification involves introducing flame-retardant components into the main chain or side chains of nylon through chemical reactions, thereby endowing the molecular chain itself with flame-retardant properties. Physical flame-retardant modification involves introducing flame-retardant components or flame retardants into the nylon matrix, followed by mixing and granulation to prepare flame-retardant modified nylon materials. Blending flame-retardant modification is the most convenient and widely used method. Melamine polyphosphate (MPP) is a relatively ideal flame retardant for nylon, with a chemical composition similar to nylon and good compatibility with the nylon matrix. Meanwhile, melamine polyphosphate molecules contain nitrogen and phosphorus elements, resulting in high flame retardant efficiency. Flame-retardant and antistatic nylon materials are produced by melt blending nylon with alkyl phosphinates and melamine polyphosphate as flame retardants and nylon as the matrix through an extruder. Although this method produces flame-retardant and antistatic nylon, the amount of melamine polyphosphate added as a flame retardant is large. The introduction of a large amount of flame retardant will reduce the mechanical properties of the material. Therefore, it is essential to develop a new type of flame-retardant nylon material that has halogen-free high flame retardancy, anti-dripping effect, high physical and mechanical properties, and crack resistance.

[0028] To address the aforementioned problems, in a first aspect, this invention provides a flame-retardant nylon material. The raw materials of the flame-retardant nylon material, by weight, include 50-70 parts PA, 1-5 parts toughening agent, 3-5 parts P-based flame retardant, 3-5 parts N-based flame retardant, and 10-20 parts 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.

[0029] Understandably, in flame-retardant nylon materials, PA is any number between 50 and 70 parts, such as 50 parts, 55 parts, 60 parts, 65 parts, or 70 parts; P-series flame retardants are any number between 3 and 5 parts, such as 3 parts, 4 parts, or 5 parts; N-series flame retardants are any number between 3 and 5 parts, such as 3 parts, 4 parts, or 5 parts; and modified polysilsesquioxane flame retardants are any number between 10 and 20 parts, such as 10 parts, 13 parts, 16 parts, or 20 parts.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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 portions of the flame-retardant nylon 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.

[0034] Flame-retardant nylon materials include PA, phosphorus-based flame retardants, nitrogen-based flame retardants, and modified polysilsesquioxane flame retardants. Modified polysilsesquioxane flame retardants contain 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. The inorganic silicon cage core decomposes 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 D with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio and contains a large amount of carbon. During combustion, this large amount of carbon forms a glassy protective film or a heat-insulating coke layer. These protective films or coke layers can isolate air, prevent heat transfer, and reduce the release of combustible gases. These structures, through the formation of protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, significantly improve the anti-dripping effect. Simultaneously, they isolate heat and oxygen transfer and reduce the release of combustible gases. The combined effect of these multiple mechanisms significantly enhances the flame-retardant performance of the material. Simultaneously, the numerous Si-O bonds decompose upon heating to form a dense ceramic barrier layer. The P element in the modified polysilsesquioxane flame retardant, together with the P-based flame retardant, provides an acid source, while the N element and the N-based flame retardant provide non-combustible gases, 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 various flame-retardant elements work together synergistically to retard flames, reducing the amount of flame retardant required while improving the flame-retardant, dielectric, and mechanical properties of the flame-retardant nylon material. The flame-retardant nylon material provided by this invention exhibits excellent flame-retardant and dielectric properties, as well as good processing and mechanical properties. It also significantly improves the crack resistance and anti-dripping effect of the flame-retardant nylon material, making it safe and environmentally friendly.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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. This large amount of carbon forms a heat-insulating coke layer during combustion. This coke layer isolates air, prevents heat transfer, and reduces the release of combustible gases. The above structure, through the formation of [the following text is incomplete and requires further context:] during combustion... Protective layers such as carbon layers, 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 the flame-retardant nylon material.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] Understandably, the structural formula of bis(4-nitrophenyl)phosphochloride is... .

[0054] Understandably, the structural formula of bis(4-nitrobenzyl)chlorophosphate is... .

[0055] Understandably, the structural formula of di[2-(p-nitrophenyl)ethyl]chlorophosphate is... .

[0056] Understandable, 3-nitro-N-(2,2,2-trichloro-1- The structural formula of Diethoxy-phosphorylethyl)benzamide is: .

[0057] Understandably, the structural formula of Bis(3-chloropropyl)p-nitrophenyl phosphate is... .

[0058] Understandably, the structural formula of DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE is... .

[0059] Understandably, the structural formula of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryldichloro is... .

[0060] 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.

[0061] 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: .

[0062] 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.

[0063] 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.

[0064] 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.

[0065] Furthermore, the molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:1.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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 heptasiloxane [15,11] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] In some embodiments, the catalyst is preferably sodium hydroxide.

[0081] In some embodiments, the organic solvent is preferably ethanol.

[0082] In some embodiments, the alkaline agent is preferably triethylamine.

[0083] Furthermore, the raw materials of the flame-retardant nylon material, by weight, include 50-60 parts of PA, 1-3 parts of toughening agent, 3-5 parts of P-based flame retardant, 3-5 parts of N-based flame retardant, and 13-18 parts of modified polysilsesquioxane flame retardant.

[0084] Reducing the amount of PA in flame-retardant nylon materials can further improve their mechanical and flame-retardant properties.

[0085] Furthermore, the toughening agent includes at least one of vinyl polymer-grafted polyether polyol (POP), polyolefin elastomer (POE), olefin block copolymer (OBC), and ethylene-vinyl acetate copolymer (EVA); the P-series flame retardant includes at least one of diethyl aluminum hypophosphite, aluminum hypophosphite, phosphate ester, phosphite ester, and phosphonate ester; and the N-series flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0086] In some embodiments, the toughening agent is preferably POE.

[0087] In some embodiments, the P-based flame retardant is preferably diethyl aluminum hypophosphite.

[0088] In some embodiments, N-series flame retardants are preferably MCA flame retardants.

[0089] Furthermore, the raw materials for flame-retardant nylon materials also include at least one of lubricant and antioxidant; wherein, by weight, the raw materials are 0.5-1 parts lubricant and 0.5-1 parts antioxidant.

[0090] Lubricants can improve the flowability of flame-retardant nylon 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.

[0091] 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.

[0092] 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.

[0093] To address the above problems, this invention also proposes a method for preparing flame-retardant nylon 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 flame-retardant nylon material.

[0094] In some embodiments, extrusion granulation is achieved using a twin-screw extruder.

[0095] 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.

[0096] In some embodiments, the temperature at which flame-retardant nylon material is obtained by extrusion granulation is 170°C-190°C.

[0097] In some embodiments, the drying time is preferably 8-12 hours.

[0098] Furthermore, the raw materials also include at least one of lubricants and antioxidants.

[0099] The following specific embodiments and data explain the content of the present invention.

[0100] 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:

[0101]

[0102] 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 PA, 1 part POE, 3 parts P-series flame retardant, 3 parts N-series flame retardant, 10 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material is obtained.

[0103] Example 2: The preparation method is the same as in Example 1, except that: 70 parts PA, 4 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 18 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0104] Example 3: The preparation method is the same as in Example 1, except that: 60 parts PA, 5 parts POE, 4 parts P-series flame retardant, 4 parts N-series flame retardant, 16 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0105] Example 4: The preparation method is the same as in Example 1, except that: 60 parts PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0106] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0107] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0108] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0109] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0110] Example 9: 1 mol of epoxycyclohexyl ethyl-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 with the catalyst, a trace amount of water was added. The mixture was stirred continuously for 4-8 hours, and then placed in an ice-water bath for further 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 through a constant-pressure dropping funnel to epoxycyclohexyl ethyl-glycidyl oxypropyl cage-like polysilsesquioxane. 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.

[0111] 60 parts PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0112] 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. 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. 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 to the ethanol solution of octacyclohexylethyl cage-like polysilsesquioxane 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 7. 60 parts PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0113] Comparative Example 1: The preparation method is the same as in Example 1, except that: 60 parts PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 30 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0114] Comparative Example 2: The preparation method is the same as in Example 1, except that: 60 parts PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 3 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0115] Comparative Example 3: The preparation method is the same as in Example 1, except that: 60 parts PA, 3 parts POE, 10 parts P-series flame retardant, 10 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0116] Comparative Example 4: The preparation method is the same as in Example 1, except that: 60 parts PA, 3 parts POE, 1 part P-series flame retardant, 1 part N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0117] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0118] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0119] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0120] 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 PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0121] Comparative Example 9: 60 parts PA, 3 parts POE, 5 parts P-series flame retardant, 5 parts N-series flame retardant, 20 parts glycidyl ether oxypropyl-isooctyl polysilsesquioxane, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0122] Comparative Example 10: 60 parts PA, 3 parts POE, 5 parts P-based flame retardant, 5 parts N-based flame retardant, 20 parts di(4-nitrophenyl)phosphoyl chloride, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0123] Comparative Example 11: The preparation method is the same as in Example 1, except that: 60 parts PA, 3 parts POE, 20 parts modified polysilsesquioxane flame retardant, 10 parts aluminum hydroxide, 0.5 parts lubricant, and 0.5 parts antioxidant were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material was obtained.

[0124] Comparative Example 12: 60 parts PA, 3 parts POE, 30 parts aluminum hydroxide, 0.5 parts lubricant, and 0.5 parts antioxidant are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a flame-retardant nylon material preform. After drying at 80°C, a high flame-retardant and crack-resistant flame-retardant nylon material is obtained.

[0125] Table 2 summarizes the components and key preparation variables of Examples 1-10 and Comparative Examples 1-12.

[0126] The flame-retardant nylon materials prepared in the above embodiments 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.

[0127] (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.

[0128] (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.

[0129] (4) Tensile strength The test was conducted according to Clause 9 of GB 1040—2008, with a test temperature of 23±2℃. The tensile test used a standard dumbbell-shaped specimen with a tensile speed of 250 mm / min. The tensile strength of five specimens was tested using a micro-controlled electronic universal tensile testing machine from Dongguan High-Speed ​​Railway Testing Co., Ltd., and the average value of the results was taken.

[0130] (5) Impact strength of cantilever beam notch: 110-150℃ thermal shock The test was conducted according to Type A of GB / T1843-2008, with a test temperature of 23±2°C. The cantilever pendulum impact strength of three specimens was tested using a cantilever beam impact tester from Guangdong Aisrui Instrument Technology Co., Ltd., and the average value was taken. The test was conducted according to Appendix A of GB / T 32129-2015, with a test temperature of 23±2°C and a weight of 2 kg. Three samples were tested at each temperature using a thermal shock resistance testing device from Hebei Zhongke Beigong Test Instrument Co., Ltd.

[0131] (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.

[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 / T1843, UL94, and GB / T 17650-1-2021, the flame-retardant nylon materials in Examples 1-10 and Comparative Examples 1-12 were tested for tensile strength, notched beam impact strength, flame retardancy rating, oxygen index, 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 Tensile strength / MPa Impact strength of cantilever beam with notch (J / m) Flame retardant rating Oxygen index (%) Does it drip? Halogen-free environmental protection requirements Precipitation status Example 1 83 15.8 V0 25.5 No dripping Environmental friendly No precipitation Example 2 75 18.6 V0 29 No dripping Environmental friendly No precipitation Example 3 79 17.4 V0 28 No dripping Environmental friendly No precipitation Example 4 66 20.6 V0 30 No dripping Environmental friendly No precipitation Example 5 68 19.4 V0 31 No dripping Environmental friendly No precipitation Example 6 65 21.4 V0 29 No dripping Environmental friendly No precipitation Example 7 69 18.9 V0 26 No dripping Environmental friendly No precipitation Example 8 70 17.4 V0 30 No dripping Environmental friendly No precipitation Example 9 72 17.6 V0 31 No dripping Environmental friendly No precipitation Example 10 75 17.2 V0 33 No dripping Environmental friendly No precipitation Comparative Example 1 54 24.3 V0 35 No dripping Environmental friendly No precipitation Comparative Example 2 96 13.4 V1 22 dripping Environmental friendly No precipitation Comparative Example 3 85 12.3 V0 33 No dripping Environmental friendly No precipitation Comparative Example 4 84 19.5 V2 28 No dripping Environmental friendly No precipitation Comparative Example 5 78 18.4 V1 30 No dripping Environmental friendly No precipitation Comparative Example 6 76 19.2 V0 30 dripping Environmental friendly No precipitation Comparative Example 7 77 18.3 V2 24 No dripping Environmental friendly No precipitation Comparative Example 8 77 17.3 V0 27 No dripping Not environmentally friendly No precipitation Comparative Example 9 78 18.3 V2 24 No dripping Environmental friendly No precipitation Comparative Example 10 48 22.8 V2 31 dripping Not environmentally friendly Precipitation Comparative Example 11 74 18.1 V2 26 No dripping Environmental friendly No precipitation Comparative Example 12 49 12.4 V2 24 dripping Environmental friendly No precipitation 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 25-30%. 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 elements, a Si-O skeleton, and a cyclic structure with a carbon-hydrogen ratio of not less than 1. The flame-retardant nylon materials obtained in Examples 5 to 10... All of them have high tensile strength and elongation at break, and their physical and mechanical properties are good. At the same time, the flame-retardant nylon materials obtained in Examples 5 to 10 have excellent flame-retardant effects, indicating that in this invention, changes in the substrate and the type of modified polysilsesquioxane flame retardant do not affect the performance of the prepared flame-retardant nylon materials. The modified polysilsesquioxane flame retardant provided by this invention can stably improve the flame retardancy of the prepared materials. The flame-retardant nylon materials obtained in Examples 5 to 10 did not drip when the flame retardant level was tested, and they did not crack in the thermal shock tests at 110°C, 130°C and 150°C. This shows that the flame-retardant nylon materials prepared with the added modified polysilsesquioxane flame retardant have excellent adaptability and reliability in environments with rapid temperature changes, and can provide protection for use in harsh environments.

[0137] In Comparative Example 1, the amount of the modified polysilsesquioxane flame retardant of the present invention was increased to 30 parts, while in Comparative Example 2, the amount of the modified polysilsesquioxane flame retardant of the present invention was reduced to 3 parts. 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 flame-retardant nylon material prepared in Comparative Example 1 had a tensile strength of less than 55 MPa, indicating that when the amount of modified polysilsesquioxane flame retardant exceeded the range proposed in the present invention, it indicated that excessive modification... The modified polysilsesquioxane flame retardant has an excessively strong plasticizing effect on the raw materials of flame-retardant nylon materials. This excessive plasticizing effect weakens the entanglement between molecules in the flame-retardant nylon materials and also disrupts the effective aggregation between the hard segments of the molecules, reducing crystallization and thus reducing the mechanical properties of the prepared flame-retardant nylon materials. In contrast, the flame-retardant nylon materials prepared in Comparative Example 2 all have a flame retardant rating of V1, indicating that when the amount of modified polysilsesquioxane flame retardant added is too small, the flame-retardant performance of the prepared flame-retardant nylon materials is insufficient.

[0138] Comparative Example 3 contained 10 parts of P-based flame retardant and 10 parts of N-based flame retardant. The proportions of 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 33%, indicating 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, with the notched impact strength of the cantilever beam being less than 13 kJ / m. 2 Comparative Example 4 added 1 part of P-based flame retardant and 1 part of N-based flame retardant. The proportions of P-based and N-based flame retardants were lower than the range proposed in this invention. As can be seen from the experimental data, the flame retardant rating of Comparative Example 4 was V2, which is insufficient. This indicates that during the combustion process, the P and N elements provided by the modified polysilsesquioxane flame retardant are insufficient to support the flame retardant performance of the flame-retardant nylon material. This reflects that the synergistic effect of the modified polysilsesquioxane flame retardant, P-based flame retardant, and N-based flame retardant ensures the excellent flame retardant effect of the prepared flame-retardant nylon material.

[0139] 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 retardancy rating of V2, and Comparative Example 7 has a flame retardancy rating of V1, indicating poor flame retardancy for both. 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 retardancy rating testing. The modified polysilsesquioxane flame retardant 11 added in Comparative Example 8 contains no nitrogen (N). Furthermore, it contains excess halogens, producing halogen acid gases during combustion, which is environmentally unfriendly. Comparative Example 9 added glycidyl etheroxypropyl-isooctyl polysilsesquioxane to replace the modified polysilsesquioxane flame retardant as the flame retardant component. 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 not less than 1. Experimental data shows that the flame-retardant nylon material prepared in Comparative Example 9 has insufficient flame-retardant performance. Comparative Example 10 added bis(4-nitrophenyl)phosphoryl chloride to replace the modified polysilsesquioxane flame retardant as the flame retardant component. bis(4-nitrophenyl)phosphoryl chloride... Acyl chlorides contain phosphorus (P), nitrogen (N), halogens, and a cyclic structure with a carbon-to-hydrogen ratio of not less than 1. However, during combustion, bis(4-nitrophenyl)phosphoryl chloride cannot form a char layer. Experimental data shows that Comparative Example 10 has poor flame retardant performance and exhibits dripping during combustion. Furthermore, due to the presence of halogens, it produces halogen acid gas during combustion, which is environmentally unfriendly. After a period of time, precipitation occurred. Comparative Example 11 added 10 parts of aluminum hydroxide to replace the P-based and N-based flame retardants of this invention, serving as a flame retardant component together with the modified polysilsesquioxane flame retardant of this invention. Experimental data shows that… Comparative Example 11 has a flame retardant rating of V2, indicating insufficient flame retardant performance of the prepared flame-retardant nylon material. This reflects that when adding the same amount of aluminum hydroxide flame retardant, compared with P-series and N-series flame retardants, inorganic flame retardants do not achieve the ideal flame retardant effect with the modified polysilsesquioxane flame retardant of this invention. However, no dripping phenomenon occurred during the combustion of Comparative Example 11, indicating that the modified polysilsesquioxane flame retardant of this invention has a good anti-dripping effect. Comparative Example 12 only added 30 parts of aluminum hydroxide as a flame retardant component. The experimental data shows that the flame retardant nylon material prepared in Comparative Example 12 has a flame retardant rating of V2 and poor anti-dripping performance.

[0140] Therefore, this invention verifies that modifying polysilsesquioxane flame retardants improves the flame retardancy of flame-retardant nylon 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.

[0141] 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. A flame-retardant nylon material, characterized in that, The raw materials of the flame-retardant nylon material, by weight, include: PA50-70 portions, 1-5 parts toughening agent 3-5 parts of P-series flame retardant 3-5 parts of N-series 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 flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon material as described in claim 1, characterized in that, The raw materials of the flame-retardant nylon material, by weight, include: PA50-60 portions, 1-3 parts toughening agent 3-5 parts of P-series flame retardant 3-5 parts of N-series flame retardant 13-18 parts of modified polysilsesquioxane flame retardant.

10. The flame-retardant nylon material as described in claim 1, characterized in that, The toughening agent includes at least one of vinyl polymer-grafted polyether polyol (POP), polyolefin elastomer (POE), olefin block copolymer (OBC), and ethylene-vinyl acetate copolymer (EVA); the P-series flame retardant includes at least one of diethylaluminum hypophosphite, aluminum hypophosphite, phosphate ester, phosphite ester, and phosphonate ester; the N-series flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

11. The flame-retardant nylon material as described in claim 1, characterized in that, The raw materials for the flame-retardant nylon 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 flame-retardant nylon 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 flame-retardant nylon materials.

13. The method for preparing the flame-retardant nylon material as described in claim 12, characterized in that, The raw materials also include at least one of lubricant and antioxidant.

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