High-temperature resistant nylon resin and its synthesis method

Abstract

This invention discloses a high-temperature resistant nylon resin and its synthesis method. The high-temperature resistant nylon resin is synthesized from the following raw materials: 1,5-pentanediamine, terephthalic acid, glutaric acid, phosphoramide salt, toluene diisocyanate, organic copper chrome black, acrylate copolymer, and a high-temperature antioxidant. This high-temperature resistant nylon resin possesses excellent mechanical properties, flame retardant properties, and laser direct forming properties, and can be widely used in communication fields requiring flame retardancy and laser direct forming capabilities.

Description

Technical Field

[0001] This invention belongs to the field of materials, and in particular relates to a high-temperature resistant nylon resin and its synthesis method. Background Technology

[0002] The synthesis of nylon resin is mainly achieved through the self-polymerization of lactams or the condensation reaction of diamines with diacids. Based on the main chain chemical structure, nylon materials can be divided into three main categories: aliphatic nylons, semi-aromatic nylons, and fully aromatic nylons. Currently, the most widely used aliphatic nylons, nylon 6 and nylon 66, possess excellent mechanical strength, wear resistance, and self-lubricating properties, but their flame retardant properties are poor (only reaching UL94 V-2 level) and they lack laser direct forming (LDS) capabilities. With the increasing demands for temperature resistance (≥270℃) in surface mount technology and the rising comprehensive performance standards in aerospace and other fields, the limitations of traditional nylon materials are becoming increasingly apparent: they are prone to thermal decomposition at high temperatures (thermal weight loss initiation temperature below 300℃) and produce molten droplets during combustion. While fully aromatic nylons exhibit outstanding heat resistance, they suffer from complex processing, high costs for flame retardant modification, and also lack laser direct forming (LDS) capabilities. Semi-aromatic nylon improves heat resistance by introducing benzene rings; however, its flame retardancy (oxygen index of about 27%) is still far below the standard for engineering plastics and cannot meet the requirements of modern electronic devices for LDS processing.

[0003] In terms of flame retardant modification, nylon mainly employs three types of technologies: additive, reactive, and composite flame retardant systems. Among additive flame retardants, halogen-antimony synergistic systems (such as decabromodiphenyl ethane and antimony oxide) have high flame retardant efficiency but lack environmental friendliness; phosphorus-based flame retardants (such as ammonium polyphosphate) exert a barrier effect by forming a dense char layer; inorganic hydroxides (such as aluminum hydroxide and magnesium hydroxide) are environmentally friendly, but the addition amount often needs to be above 50%, which can easily damage the material's mechanical properties. Reactive flame retardants incorporate flame retardant elements (such as phosphorus and nitrogen) into the polymer chain through copolymerization; representative substances include bis(hydroxyethyl)methylphosphine oxide, which can achieve a long-lasting flame retardant effect, but the process is relatively complex. Composite flame retardant systems integrate multiple methods, such as combining glass fiber reinforcement with flame retardants, or introducing nanomaterials such as carbon nanotubes and layered silicates, which can improve both flame retardant performance and mechanical properties, thus becoming a current research hotspot.

[0004] Currently, some research has been conducted on copolymer flame-retardant polyamide resins in existing technologies. For example, Chinese patent CN112048061A uses N,N-bis(6-aminohexyl)phenylphosphamide and diacid to synthesize flame retardant salts, which are then directly polycondensed with PA6 / PA66 oligomers; CN104231262A prepares textile flame-retardant polyamides via a prepolymer method, first reacting the flame retardant with diamine to generate a prepolymer before copolymerization; CN112144141A uses DOPO derivative-based flame retardant salts to produce... The material is a spinning raw material; CN112048779A and CN112048061A have similar technical routes but optimized reaction conditions (210-220℃ / 1.7-1.9MPa); CN115894903A innovatively uses DOPO-barium itaconic acid flame retardant and prepares PA66 through a post-feeding process; CN105131280A prepares halogen-free flame-retardant PA66 resin through phosphine oxide dicarboxylic acid; CN116789959A solves the molecular weight distribution problem of flame-retardant polyamide through solid-phase thickening polymerization. In summary, the existing patented technologies mainly exhibit three characteristics: First, the process routes are divided into two categories: prepolymer method and direct copolymerization method, the core of which is the polycondensation reaction of phosphorus-based flame retardant salts and PA6 / PA66 oligomers; second, the technological innovations are concentrated in flame retardant structure design (such as DOPO derivatives, organophosphorus ammonium salts), process optimization (solid phase thickening, post-feeding) and halogen-free direction; third, the applications cover engineering plastics, fibers and films, among which fiber preparation mostly adopts the process route of direct spinning of flame retardant copolymers. Summary of the Invention

[0005] Based on this, one of the objectives of the present invention is to provide a high-temperature resistant nylon resin, which has excellent mechanical properties, flame retardant properties and laser direct forming properties, and can be widely used in the communication field that requires flame retardancy and laser direct forming.

[0006] The specific technical solution to achieve the above-mentioned objectives is as follows:

[0007] A high-temperature resistant nylon resin is prepared from raw materials comprising the following parts by weight:

[0008] 102.2 parts of 1,5-pentanediamine

[0009] Terephthalic acid 66.5–99.7 parts,

[0010] Glutaric acid 52.9–79.3 parts,

[0011] Contains 32-62 parts of phosphoramide salt,

[0012] Toluene diisocyanate 4.7–5.7 parts,

[0013] Organic copper chromium black, 25-37 parts.

[0014] 6-14 parts of acrylate copolymers,

[0015] 0.6–1.6 parts of high-temperature resistant antioxidant;

[0016] The diamine (1,5-pentanediamine) and the dicarboxylic acid (the molar sum of terephthalic acid and glutaric acid) are in an equimolar ratio; the phosphoramide salt is obtained by a salt-forming reaction of 2-carboxyethylphenyl hypophosphite and 1,5-pentanediamine; the organic copper chromate black is obtained by organic modification of copper chromate black with γ-aminopropyltriethoxysilane; the acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0017] In some embodiments, the high-temperature resistant nylon resin is prepared from raw materials comprising the following parts by weight:

[0018] 102.2 parts of 1,5-pentanediamine

[0019] Terephthalic acid 74.8–91.4 parts,

[0020] Glutaric acid 59.5–72.7 parts,

[0021] Contains 37–57 parts of phosphoramide salt.

[0022] Toluene diisocyanate 4.9–5.5 parts,

[0023] Organic copper chromium black, 27-35 parts.

[0024] 7-13 parts of acrylate copolymers,

[0025] 0.8 to 1.4 parts of high-temperature resistant antioxidant.

[0026] In some embodiments, the high-temperature resistant nylon resin is prepared from raw materials comprising the following parts by weight:

[0027] 102.2 parts of 1,5-pentanediamine

[0028] 78.1–88 parts of terephthalic acid

[0029] Glutaric acid 62.1–70 parts,

[0030] Contains 42-52 parts of phosphoramide salt,

[0031] Toluene diisocyanate 5.1–5.3 parts,

[0032] Organic copper chromium black, 29–33 parts.

[0033] 9-11 parts of acrylate copolymers,

[0034] 0.9 to 1.3 parts of high-temperature resistant antioxidant.

[0035] In some embodiments, the preparation method of the phosphoramide salt includes the following steps: 214.16 g of 2-carboxyethylphenyl hypophosphite and 102.18 g of 1,5-pentanediamine are added to a stirred polymerization reactor, followed by the addition of 150 mL to 200 mL of deionized water. The reactor is then evacuated for 2 to 6 minutes and purged with nitrogen for 2 to 6 minutes, repeated 3 to 5 times, with the system pressure inside the stirred polymerization reactor controlled at 0.1 MPa to 0.3 MPa. The stirred polymerization reactor is then heated to 85°C to 95°C in a sealed environment for 0.5 to 1.5 hours, with the stirring speed controlled at 50 r / min to 100 r / min, and the salt formation reaction is carried out for 1 to 2 hours. After the reaction is completed, the pressure inside the reactor is reduced to 0.1 MPa, the material is discharged, and vacuum dried for later use.

[0036] In some embodiments, the preparation method of the organic copper chromium black includes the following steps: adding 100 g of copper chromium black and 2.7 g to 3.7 g of γ-aminopropyltriethoxysilane into a high-speed stirrer, and stirring at room temperature for 6 min to 10 min to obtain organic copper chromium black.

[0037] In some embodiments, the average particle size of the copper chromium black in the organic copper chromium black is 1.4 μm to 1.6 μm; and the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer is 7% to 9%.

[0038] Another object of the present invention is to provide a method for preparing the above-mentioned high-temperature resistant nylon resin.

[0039] The specific technical solution to achieve the above-mentioned objectives is as follows:

[0040] A method for preparing a high-temperature resistant nylon resin includes the following steps:

[0041] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromate black, acrylate copolymer, high-temperature antioxidant and appropriate amount of water. Then, vacuum is applied for 2 min to 6 min, and nitrogen is purged for 2 min to 6 min. This cycle is repeated 3 to 5 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.1 MPa to 0.3 MPa.

[0042] (2) Adjust the stirring speed of the stirred polymerization reactor to 20 r / min to 40 r / min, and heat the stirred polymerization reactor to 280℃ to 284℃ in a closed and uniform manner for 2 to 4 hours. When the temperature of the stirred polymerization reactor reaches 213℃, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1 to 2 hours (prepolymerization reaction), release the gas to atmospheric pressure and raise the temperature to 314℃ to 318℃. Continue to react for 1 to 2 hours (postpolymerization reaction). Maintain constant temperature and vacuum for 15 min to 45 min (viscosification reaction). When the reaction is completed, add nitrogen gas when discharging to obtain the product.

[0043] In some embodiments, the method for preparing the high-temperature resistant nylon resin includes the following steps:

[0044] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and appropriate amount of water. Then, vacuum is applied for 3 min to 5 min, and nitrogen is purged for 3 min to 5 min. This cycle is repeated 3 to 5 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.15 MPa to 0.25 MPa.

[0045] (2) Adjust the stirring speed of the stirred polymerization reactor to 25 r / min to 35 r / min, and heat the stirred polymerization reactor to 281℃ to 283℃ in a closed and uniform manner for 2.5 hours to 3.5 hours. When the temperature of the stirred polymerization reactor reaches 213℃, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.3 hours to 1.7 hours (prepolymerization reaction), release the gas to atmospheric pressure and simultaneously raise the temperature to 315℃ to 317℃. Continue to react for 1.3 hours to 1.7 hours (postpolymerization reaction). Maintain constant temperature and vacuum for 20 min to 40 min (viscosification reaction). When the reaction is completed, add nitrogen gas when discharging to obtain the final product.

[0046] The functions of each raw material in the high-temperature resistant nylon resin of this invention are as follows:

[0047] This invention introduces glutaric acid as a comonomer to prepare PA5T / 55 copolymer, which can effectively reduce the melting point of PA5T resin. Its mechanism of action is mainly based on the following three aspects: (1) Glutaric acid is an aliphatic diacid, and the PA55 chain segment formed after polymerization with pentanediamine is highly flexible. Its random embedding in the PA5T molecular chain destroys the regular arrangement of the benzene ring structure in the original terephthalic acid unit, weakens the inter-chain interaction force, and at the same time leads to a decrease in the crystallinity of the copolymer, thereby significantly reducing the melting point. (2) The addition of glutaric acid helps to reduce the piperidine cyclization side reaction of pentanediamine in the terephthalic acid system and avoids the decrease in viscosity caused by end capping of the molecular chain. (3) By adjusting the feeding ratio of glutaric acid and terephthalic acid, the distribution of aromatic and aliphatic chain segments in the copolymer can be controlled. This random copolymer structure destroys the symmetry and regularity of the molecular chain, reduces its crystallinity, and thus achieves controllable adjustment of the melting point.

[0048] The flame-retardant mechanism of the phosphorus-containing amide salt used in this invention is mainly based on the synergistic effect of phosphorus (P) and nitrogen (N) elements in its molecular structure. Under high temperature or combustion conditions, the compound first decomposes, and its phosphorus component can be converted into highly dehydrating substances such as polyphosphoric acid, catalyzing the dehydration and carbonization of the nylon resin matrix to form a dense and stable expanded char layer on the material surface. At the same time, its nitrogen-containing component can release non-combustible gases such as nitrogen and ammonia when heated and decomposed. These gases can dilute the concentration of combustible gases and oxygen, inhibiting the combustion chain reaction (gas-phase flame retardancy), and also help promote the expansion and foaming of the char layer, forming a more effective heat insulation and oxygen barrier (condensed-phase flame retardancy). Therefore, this phosphorus-containing amide salt achieves efficient and synergistic flame-retardant protection for nylon resin through a dual approach of gas-phase dilution to inhibit flame and condensed-phase char formation for heat insulation.

[0049] In this invention, toluene diisocyanate (TDI) primarily functions as a reactive compatibilizer. Its highly reactive isocyanate groups (-NCO) chemically react with the organic functional groups on the surface of the organic copper chromate black and the molecular chains of the nylon resin, respectively, thus constructing a robust chemical "bridge" at the interface between the two phases. The mechanism is as follows: During the processing and melting process, the isocyanate groups of TDI first undergo an addition reaction with the amino groups (-NH2) introduced after silane modification on the surface of the organic copper chromate black, forming covalent bonds. Simultaneously, the isocyanate groups at the other end can react with the amino groups (-NH2) at the ends of the nylon resin molecular chains or the amide bonds (-NH-CO-) on the main chain, generating urea bonds or other chemical bonds. This bifunctional chemical bonding fundamentally strengthens the interfacial adhesion between the inorganic filler particles and the organic nylon matrix, effectively preventing filler agglomeration, promoting its uniform dispersion in the resin, thereby significantly improving the compatibility of the two and contributing to the improvement of the mechanical properties and stability of the final composite material.

[0050] This invention utilizes organic copper chromium black as a functional additive for laser direct forming (LDS) in nylon resin. Its mechanism of action is based on the dual effects of its composite metal oxide properties and surface organic modification: Under near-infrared laser irradiation, the copper, chromium, and other metal components in copper chromium black can efficiently absorb laser energy due to their internal free electrons and lattice vibrations, resulting in localized high temperatures on the particle surface and changes in physicochemical structure. This decomposes or reduces highly catalytically active metal nanoparticles (especially copper particles). These metal particles exposed on the resin surface provide the necessary catalytic activation centers for subsequent electroless plating, guiding the selective deposition of metal in the laser scanning area, thereby forming a precise conductive pattern. Simultaneously, the amino functional groups introduced into the surface of the γ-aminopropyltriethoxysilane-modified copper chromium black can interact or react with the terminal carboxyl groups or amide bonds of the nylon resin, significantly improving the uniformity of filler dispersion and interfacial adhesion strength in the matrix. This not only improves the mechanical properties of the composite material but also ensures a strong bond between the laser-activated area and the matrix, giving the electroless plating layer excellent adhesion, thus achieving efficient and reliable laser direct forming functionality.

[0051] The acrylate copolymer (in this system, a styrene-acrylonitrile-glycidyl methacrylate copolymer) used in this invention serves as a reactive molecular weight regulator. Its mechanism of action primarily relies on the active epoxy groups contained in its side chains. Under the high-temperature conditions of the polycondensation reaction, the epoxy groups can undergo ring-opening addition reactions with the amino (-NH2) or carboxyl (-COOH) groups at the ends of the nylon prepolymer molecular chains. Specifically, they react with amino groups to generate secondary hydroxyl groups and form new CN bonds, while reacting with carboxyl groups to generate ester bonds. This process effectively "end-capsulates" the growing molecular chains, thereby actively terminating chain growth and achieving precise control over the polymer's molecular weight and its distribution. Furthermore, the styrene-acrylonitrile segments in the copolymer backbone have a certain degree of compatibility with the nylon matrix, which helps the regulator to disperse uniformly in the melt, ensuring the uniformity of the regulating effect. Therefore, this component, through chemical end-capping, helps to obtain a suitable and stable molecular weight while inhibiting excessive molecular weight growth and preventing gelation, thus optimizing the melt flowability and processing window of the final resin.

[0052] The mechanism of action of the high-temperature antioxidant in nylon resin employed in this invention is based on its unique molecular structure, which provides dual protection. On one hand, the 2,2,6,6-tetramethylpiperidine group in its molecule, through its significant steric hindrance, can efficiently capture alkyl free radicals generated during high-temperature processing or use of nylon, interrupting the free radical chain oxidation reaction and thus delaying the thermo-oxidative aging of the material. On the other hand, the amide bonds (-CONH-) at both ends can chemically react with the amino or carboxyl groups at the ends of the nylon resin molecular chain, allowing the antioxidant to be chemically grafted onto the polymer backbone in a covalent form. This reactive fixation not only prevents the antioxidant from volatilizing or migrating at high temperatures but also significantly improves its dispersibility and compatibility in the matrix, achieving long-lasting and stable antioxidant protection. Therefore, this antioxidant provides long-lasting and efficient thermal stability protection for high-temperature nylon at the molecular level through a synergistic mechanism of free radical capture and chemical bonding fixation.

[0053] Compared with the prior art, the high-temperature resistant nylon resin and its synthesis method provided by the present invention have the following beneficial effects:

[0054] (1) A phosphoramide salt prepared by reacting 2-carboxyethylphenyl hypophosphoric acid with 1,5-pentanediamine was used as a reactive flame retardant. Combined with copper chromium black modified with silane surface organication, the phosphoramide salt was uniformly dispersed in a nylon matrix using an in-situ polymerization process, achieving an organic integration of flame retardant and laser direct forming (LDS) functions. The phosphoramide salt promotes char formation in the condensed phase and inhibits combustion in the gas phase through dilution. This synergistic effect with the role of copper chromium black in providing catalytic centers for chemical plating after laser activation results in a resin that simultaneously possesses excellent flame retardant properties and reliable LDS performance, meeting the requirements of modern communication electronic devices for multifunctional integrated materials.

[0055] (2) Organic copper chromium black not only serves as a functional filler for LDS, but its surface amino functional groups can also form strong chemical bonds with nylon molecular chains through the compatibilizing and bridging effect of toluene diisocyanate (TDI), significantly enhancing the interfacial adhesion between the inorganic filler and the organic matrix. This strong interfacial bonding effectively prevents filler agglomeration and promotes its nanoscale dispersion in the resin. Thus, while endowing the material with LDS functionality, it significantly improves the mechanical strength, toughness, and dimensional stability of the composite material, overcoming the problem of decreased mechanical properties caused by traditional additive fillers.

[0056] (3) The in-situ polymerization method directly introduces the functional components during the polymerization process, ensuring the molecular-level dispersion and stable bonding of functional additives in the nylon matrix. This method not only avoids material degradation and performance inhomogeneity that may result from subsequent melt blending, but also, through the chemical bond network formed during the reaction, makes the flame retardants, LDS additives, antioxidants, etc., more durable and robustly bonded to the resin matrix, significantly improving the material's heat aging resistance, flame retardant durability, and coating adhesion in the laser-activated area. The resulting nylon resin has excellent comprehensive performance and is particularly suitable for communication equipment structural components requiring high heat resistance, high flame retardancy, and precision circuit molding. Attached Figure Description

[0057] Figure 1 This is a process flow diagram for preparing the high-temperature resistant nylon resin of the present invention. Detailed Implementation

[0058] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0059] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. The term "and / or" as used in this invention includes any and all combinations of one or more of the associated listed items.

[0060] The reaction mechanism of the high-temperature resistant nylon resin of this invention is as follows (see the preparation process flow chart). Figure 1 ):

[0061]

[0062] Where a = 20~60, b = 20~60, c = 1~10, d = 1~3.

[0063] Reaction mechanism

[0064] As can be seen from the above reaction formula, the terminal carboxyl group of 2-carboxyethylphenyl hypophosphite reacts with the terminal amino group of 1,5-pentanediamine to obtain a phosphoramide salt. Then, the phosphoramide salt, terephthalic acid, 1,5-pentanediamine, glutaric acid, and toluene diisocyanate react to obtain a high-temperature resistant nylon resin.

[0065] The raw materials used in the embodiments of the present invention are as follows:

[0066] 1,5-Pentanediamine was selected from Shanghai Kaisai Biotechnology Co., Ltd.

[0067] Terephthalic acid, selected from Beijing Yanshan Petrochemical Company.

[0068] Glutaric acid, selected from Liaoyang Hengye Chemical Co., Ltd.

[0069] Contains phosphoramide salts, self-made; the 2-carboxyethylphenyl hypophosphite in the raw materials is selected from Zhejiang Jiaxing Alpha Fine Chemical Co., Ltd.

[0070] Toluene diisocyanate, selected from Jiangsu Haolong Chemical Co., Ltd.

[0071] Organic copper chromium black, self-made, with copper chromium black in the raw materials having an average particle size of 1.5 μm, selected from Schott Pigment Company, USA, and γ-aminopropyltriethoxysilane selected from Nanjing Youpu Chemical Co., Ltd.

[0072] The styrene-acrylonitrile-glycidyl methacrylate copolymer, wherein the mass fraction of glycidyl methacrylate is 8%, is selected from Jia Yi Rong Compatibilizer Jiangsu Co., Ltd.

[0073] N,N'-Bis(2,2,6,6-Tetramethyl-4-piperidinyl)-1,3-phenylenediamide, selected from Clariant Chemicals (China) Co., Ltd.

[0074] The phosphoramide salts used in the following examples were prepared by the following steps: 214.16 g of 2-carboxyethylphenyl hypophosphite and 102.18 g of 1,5-pentanediamine were added to a stirred polymerization reactor, followed by the addition of 175 mL of deionized water. The reactor was evacuated for 4 min, then purged with nitrogen for 4 min, and this cycle was repeated 4 times, maintaining the system pressure in the stirred polymerization reactor at 0.2 MPa. The stirred polymerization reactor was then heated to 90°C in a sealed environment within 1 hour, with the stirring speed controlled at 75 r / min. After a 1.5-hour salt formation reaction, the reaction was completed, the pressure inside the reactor was reduced to 0.1 MPa, the product was discharged, and vacuum dried for later use.

[0075] The organic copper chromium black used in the following examples is prepared by the following steps: 100 g of copper chromium black and 3.2 g of γ-aminopropyltriethoxysilane are added to a high-speed stirrer and stirred at room temperature for 8 min to obtain organic copper chromium black.

[0076] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0077] Example 1 High-temperature resistant nylon resin and its synthesis method

[0078] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0079] 102.2 parts of 1,5-pentanediamine

[0080] 99.7 parts of terephthalic acid

[0081] Glutaric acid 52.9 parts,

[0082] Contains 32 parts of phosphoramide salt,

[0083] 4.7 parts of toluene diisocyanate,

[0084] 25 parts of organic copper chromium black,

[0085] 6 parts of acrylate copolymer,

[0086] 0.6 parts of high-temperature resistant antioxidant;

[0087] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0088] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0089] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. Then, the reactor is evacuated for 2 min and purged with nitrogen for 2 min. This cycle is repeated 5 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.1 MPa.

[0090] (2) Adjust the stirring speed of the stirred polymerization reactor to 20 r / min, and heat the stirred polymerization reactor to 280°C in a closed and uniform manner within 2 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 2 hours, release the gas to atmospheric pressure and raise the temperature to 314°C. Continue to react for 2 hours, maintain the temperature and continuously evacuate for 15 min. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0091] Example 2 High-temperature resistant nylon resin and its synthesis method

[0092] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0093] 102.2 parts of 1,5-pentanediamine

[0094] 91.4 parts of terephthalic acid

[0095] Glutaric acid 59.5 parts,

[0096] Contains 37 parts of phosphoramide salt,

[0097] 4.9 parts of toluene diisocyanate

[0098] 27 parts of organic copper chromium black,

[0099] 7 parts of acrylate copolymer,

[0100] 0.8 parts of high-temperature resistant antioxidant;

[0101] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0102] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0103] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. Then, the reactor is evacuated for 6 min and purged with nitrogen for 6 min. This cycle is repeated 3 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.3 MPa.

[0104] (2) Adjust the stirring speed of the stirred polymerization reactor to 40 r / min, and heat the stirred polymerization reactor to 284°C in a closed and uniform manner within 4 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1 hour, release the gas to atmospheric pressure and raise the temperature to 318°C. Continue to react for 1 hour, maintain the temperature and continuously evacuate for 45 min. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0105] Example 3 High-temperature resistant nylon resin and its synthesis method

[0106] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0107] 102.2 parts of 1,5-pentanediamine

[0108] 88 parts of terephthalic acid

[0109] 62.1 parts of glutaric acid

[0110] Contains 42 parts of phosphoramide salt,

[0111] 5.1 parts of toluene diisocyanate,

[0112] 29 parts of organic copper chromium black,

[0113] 9 parts of acrylate copolymer,

[0114] 0.9 parts of high-temperature resistant antioxidant;

[0115] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0116] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0117] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromate black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. Then, the reactor is evacuated for 3 min and purged with nitrogen for 3 min. This cycle is repeated 5 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.15 MPa.

[0118] (2) Adjust the stirring speed of the stirred polymerization reactor to 25 r / min, and heat the stirred polymerization reactor to 281°C in a closed and uniform manner within 2.5 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.7 hours, release the gas to atmospheric pressure and raise the temperature to 315°C. Continue to react for 1.7 hours, maintain the temperature and continuously evacuate for 20 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0119] Example 4 High-temperature resistant nylon resin and its synthesis method

[0120] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0121] 102.2 parts of 1,5-pentanediamine

[0122] 83.1 parts of terephthalic acid

[0123] 66.1 parts of glutaric acid

[0124] Contains 47 parts of phosphoramide salt,

[0125] 5.2 parts of toluene diisocyanate,

[0126] 31 parts of organic copper chromium black,

[0127] 10 parts of acrylate copolymer,

[0128] 1.1 parts of high-temperature resistant antioxidant;

[0129] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0130] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0131] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. Then, the reactor is evacuated for 5 min and purged with nitrogen for 5 min. This cycle is repeated 3 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.25 MPa.

[0132] (2) Adjust the stirring speed of the stirred polymerization reactor to 35 r / min, and heat the stirred polymerization reactor to 283°C in a closed and uniform manner within 3.5 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.3 hours, release the gas to atmospheric pressure and raise the temperature to 317°C. Continue to react for 1.3 hours, maintain the temperature and continuously evacuate for 40 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0133] Example 5 High-temperature resistant nylon resin and its synthesis method

[0134] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0135] 102.2 parts of 1,5-pentanediamine

[0136] 78.1 parts of terephthalic acid

[0137] 70 parts of glutaric acid

[0138] Contains 52 parts of phosphoramide salt,

[0139] 5.3 parts of toluene diisocyanate,

[0140] 33 parts of organic copper chromium black,

[0141] 11 parts of acrylate copolymer,

[0142] 1.3 parts of high-temperature resistant antioxidant;

[0143] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0144] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0145] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0146] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0147] Example 6 High-temperature resistant nylon resin and its synthesis method

[0148] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0149] 102.2 parts of 1,5-pentanediamine

[0150] 74.8 parts of terephthalic acid

[0151] 72.7 parts of glutaric acid

[0152] Contains 57 parts of phosphoramide salt,

[0153] 5.5 parts of toluene diisocyanate,

[0154] 35 parts of organic copper chromium black,

[0155] 13 parts of acrylate copolymer,

[0156] 1.4 parts of high-temperature resistant antioxidant;

[0157] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0158] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0159] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0160] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0161] Example 7 High-temperature resistant nylon resin and its synthesis method

[0162] The high-temperature resistant nylon resin of this embodiment is prepared from raw materials comprising the following parts by weight:

[0163] 102.2 parts of 1,5-pentanediamine

[0164] 66.5 parts of terephthalic acid

[0165] Glutaric acid 79.3 parts,

[0166] Contains 62 parts of phosphoramide salt,

[0167] 5.7 parts of toluene diisocyanate,

[0168] 37 parts of organic copper chromium black,

[0169] 14 parts of acrylate copolymer,

[0170] 1.6 parts of high-temperature resistant antioxidant;

[0171] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0172] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0173] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromium black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0174] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0175] Comparative Example 1

[0176] The high-temperature resistant nylon resin of this comparative example is prepared from raw materials comprising the following parts by weight:

[0177] 102.2 parts of 1,5-pentanediamine

[0178] 66.5 parts of terephthalic acid

[0179] Glutaric acid 79.3 parts,

[0180] 5.7 parts of toluene diisocyanate,

[0181] 37 parts of organic copper chromium black,

[0182] 14 parts of acrylate copolymer,

[0183] 1.6 parts of high-temperature resistant antioxidant;

[0184] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0185] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0186] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with toluene diisocyanate, organic copper chromate black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0187] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0188] Comparative Example 2

[0189] The high-temperature resistant nylon resin of this comparative example is prepared from raw materials comprising the following parts by weight:

[0190] 102.2 parts of 1,5-pentanediamine

[0191] 66.5 parts of terephthalic acid

[0192] Glutaric acid 79.3 parts,

[0193] Contains 62 parts of phosphoramide salt,

[0194] 37 parts of organic copper chromium black,

[0195] 14 parts of acrylate copolymer,

[0196] 1.6 parts of high-temperature resistant antioxidant;

[0197] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0198] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0199] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, organic copper chromate black, acrylate copolymer, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0200] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0201] Comparative Example 3

[0202] The high-temperature resistant nylon resin of this comparative example is prepared from raw materials comprising the following parts by weight:

[0203] 102.2 parts of 1,5-pentanediamine

[0204] 66.5 parts of terephthalic acid

[0205] Glutaric acid 79.3 parts,

[0206] Contains 62 parts of phosphoramide salt,

[0207] 5.7 parts of toluene diisocyanate,

[0208] 14 parts of acrylate copolymer,

[0209] 1.6 parts of high-temperature resistant antioxidant;

[0210] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0211] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0212] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, acrylate copolymer, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0213] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0214] Comparative Example 4

[0215] The high-temperature resistant nylon resin of this comparative example is prepared from raw materials comprising the following parts by weight:

[0216] 102.2 parts of 1,5-pentanediamine

[0217] 66.5 parts of terephthalic acid

[0218] Glutaric acid 79.3 parts,

[0219] Contains 62 parts of phosphoramide salt,

[0220] 5.7 parts of toluene diisocyanate,

[0221] 37 parts of organic copper chromium black,

[0222] 1.6 parts of high-temperature resistant antioxidant;

[0223] The high-temperature resistant antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0224] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0225] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromate black, high-temperature antioxidant and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0226] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0227] Comparative Example 5

[0228] The high-temperature resistant nylon resin of this comparative example is prepared from raw materials comprising the following parts by weight:

[0229] 102.2 parts of 1,5-pentanediamine

[0230] 66.5 parts of terephthalic acid

[0231] Glutaric acid 79.3 parts,

[0232] Contains 62 parts of phosphoramide salt,

[0233] 5.7 parts of toluene diisocyanate,

[0234] 37 parts of organic copper chromium black,

[0235] 14 parts of acrylate copolymer;

[0236] The acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer.

[0237] The preparation method of the above-mentioned high-temperature resistant nylon resin includes the following steps:

[0238] (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromate black, acrylate copolymer and 200 mL of water. The reactor is then evacuated for 4 min and purged with nitrogen for 4 min. This cycle is repeated 4 times to control the system pressure in the stirred polymerization reactor to 0.2 MPa.

[0239] (2) Adjust the stirring speed of the stirred polymerization reactor to 30 r / min, and heat the stirred polymerization reactor to 282°C in a closed and uniform manner within 3 hours. When the temperature of the stirred polymerization reactor reaches 213°C, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1.5 hours, release the gas to atmospheric pressure and raise the temperature to 316°C. Continue to react for 1.5 hours, maintain the temperature and continuously evacuate for 30 minutes. When the reaction ends, add nitrogen gas when discharging to obtain the final product.

[0240] The following is a list of the raw material composition of Examples 1-7 and Comparative Examples 1-5.

[0241] Table 1. Summary of raw material composition for Examples 1-7 and Comparative Examples 1-5

[0242]

[0243] In the above examples and comparative examples, the amount of 1,5-pentanediamine added was 102.2 parts; the acrylate copolymer was styrene-acrylonitrile-glycidyl methacrylate copolymer; and the high-temperature antioxidant was N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0244] Examples 1-7 were used to prepare high-temperature resistant nylon resins by adjusting the amounts of terephthalic acid, glutaric acid, phosphoramide salt, toluene diisocyanate, organic copper chromate black, acrylate copolymer, and high-temperature antioxidant. Comparative Examples 1-5 were used to prepare high-temperature resistant nylon resins based on the raw materials of Example 7. Comparative Example 1 prepared a high-temperature resistant nylon resin without adding phosphoramide salt; Comparative Example 2 prepared a high-temperature resistant nylon resin without adding toluene diisocyanate; Comparative Example 3 prepared a high-temperature resistant nylon resin without adding organic copper chromate black; Comparative Example 4 prepared a high-temperature resistant nylon resin without adding acrylate copolymer; and Comparative Example 5 prepared a high-temperature resistant nylon resin without adding high-temperature antioxidant. The high-temperature resistant nylon resins prepared in the above examples and comparative examples were subjected to the following performance tests:

[0245] Tensile properties: Tested according to GB / T 1040-2006 standard, the tensile rate is 50 mm / min.

[0246] Notched impact performance: tested according to GB / T 1843-2008 standard.

[0247] Flame retardant performance: According to GB / T 2406.2-2009 standard, the limiting oxygen index of the sample was determined using an oxygen index meter. The sample size was 100 mm × 10 mm × 4 mm.

[0248] Laser direct formability: The adhesion of the metal coating on the plastic part surface (or called cross-cut test) is tested according to the ASTM D3359 standard, specifically as follows: Under the conditions of room temperature 23±2°C and relative humidity 50±5%, use a sharp blade (blade angle is 15° - 30°) to draw 10×10 small grids of 1mm×1mm on the surface of the test sample, and each scratch reaches the bottom layer of the coating; use a brush to clean the test area; firmly stick the 3M No. 600 tape to the tested small grid, and use an eraser to wipe the tape forcefully to increase the contact area and force between the tape and the tested area; hold one end of the tape by hand and quickly tear off the transparent tape at a 60° angle in the vertical direction, and conduct the same test 2 times at the same position. Result judgment: When the adhesion ≥ 4B is required to be qualified; 5B - The edge of the scratch is smooth, and there is no paint peeling off at the edge and intersection of the scratch; 4B - There are small pieces of paint peeling off at the intersection of the scratches, and the total peeling area is less than 5%; 3B - There are small pieces of paint peeling off at the edge and intersection of the scratches, and the total peeling area is between 5% and 15%; 2B - There are成片 of paint peeling off at the edge and intersection of the scratches, and the total peeling area is between 15% and 35%; 1B - There are成片 of paint peeling off at the edge and intersection of the scratches, and the total peeling area is between 35% and 65%; 0B - There are成片 of paint peeling off at the edge and intersection of the scratches, and the total peeling area is greater than 65%.

[0249] Limiting viscosity number: Tested according to the GB / T 1632-2008 standard, and the solvent is concentrated sulfuric acid.

[0250] Melting temperature: Tested according to the GB / T 19466.3-2004 standard.

[0251] The performance test results are shown in Table 2.

[0252] Table 2 Performance table of high-temperature resistant nylon resins of Examples 1-7 and Comparative Examples 1-5

[0253]

[0254]

[0255] It can be seen from Table 2 that:

[0256] As the addition amount of glutaric acid increases, the tensile strength of the high-temperature resistant nylon resin shows a decreasing trend, while the notch impact performance shows an increasing trend. This is because glutaric acid is an aliphatic diacid, and the PA55 chain segment formed after polymerization with pentamethylenediamine has strong flexibility. Its random embedding in the PA5T molecular chain destroys the regular arrangement of the benzene ring structure in the original terephthalic acid unit and weakens the intermolecular interaction force.

[0257] With increasing amounts of phosphoramide salt, the flame retardant properties of high-temperature resistant nylon resin show an increasing trend. This is due to the synergistic effect of phosphorus (P) and nitrogen (N) elements in the molecular structure of the phosphoramide salt. Under high temperature or combustion conditions, the compound decomposes first, and its phosphorus component can be converted into highly dehydrating substances such as polyphosphoric acid, catalyzing the dehydration and carbonization of the nylon resin matrix, forming a dense and stable expanded char layer on the material surface. At the same time, its nitrogen component can release non-combustible gases such as nitrogen and ammonia when heated and decomposed. These gases can dilute the concentration of combustible gases and oxygen, inhibiting the combustion chain reaction (gas-phase flame retardancy), and also help promote the expansion and foaming of the char layer, forming a more effective heat insulation and oxygen barrier (condensed-phase flame retardancy). Therefore, the phosphoramide salt achieves efficient and synergistic flame retardant protection for nylon resin through a dual approach of gas-phase dilution to inhibit flame and condensed-phase charring for heat insulation.

[0258] With the increase of the amount of organic copper chromium black added, the laser direct molding property of high-temperature resistant nylon resin reached 5B. This is because organic copper chromium black acts as a functional additive for laser direct forming (LDS) in nylon resin. Its mechanism of action is based on the dual effects of the characteristics of its composite metal oxide and the organic modification of its surface: Under near-infrared laser irradiation, the copper, chromium and other metal components in copper chromium black can efficiently absorb laser energy due to their internal free electrons and lattice vibrations, resulting in local high temperature on the particle surface and changes in physicochemical structure. This decomposes or reduces to highly catalytically active metal nanoparticles (especially copper particles). These metal particles exposed on the resin surface provide the necessary catalytic activation centers for subsequent electroless plating, guiding the selective deposition of metal in the laser scanning area, thereby forming a precise conductive pattern. At the same time, the amino functional groups introduced into the surface of copper chromium black modified with γ-aminopropyltriethoxysilane can interact or react with the terminal carboxyl groups or amide bonds of nylon resin, significantly improving the uniformity of filler dispersion and interfacial bonding strength in the matrix. This not only improves the mechanical properties of the composite material, but also ensures that the laser-activated area is firmly bonded to the matrix, giving the electroless plating layer excellent adhesion, thereby achieving efficient and reliable laser direct forming function.

[0259] As the amount of acrylate copolymer added increases, the intrinsic viscosity of the high-temperature resistant nylon resin shows a decreasing trend. This is because the acrylate copolymer (in this system, it is a styrene-acrylonitrile-glycidyl methacrylate copolymer) acts as a reactive molecular weight regulator, and its mechanism of action mainly relies on the active epoxy groups contained in its side chains. Under the high-temperature conditions of polycondensation reaction, the epoxy groups can undergo ring-opening addition reactions with the amino (-NH2) or carboxyl (-COOH) groups at the ends of the nylon prepolymer molecular chains. Specifically, it reacts with the amino group to generate secondary hydroxyl groups and form new CN bonds, and reacts with the carboxyl group to generate ester bonds. This process can effectively "end-cap" the growing molecular chains, thereby actively terminating chain growth and achieving precise control over the polymer molecular weight and its distribution. In addition, the styrene-acrylonitrile segments in the copolymer backbone have a certain degree of compatibility with the nylon matrix, which helps the regulator to be uniformly dispersed in the melt and ensures the uniformity of the regulating effect. Therefore, this component, through chemical end-capping, helps to obtain a suitable and stable molecular weight while inhibiting excessive molecular weight growth and preventing gelation, thereby optimizing the melt flow and processing window of the final resin.

[0260] As the amount of glutaric acid added increases, the melting temperature of the high-temperature resistant nylon resin shows a decreasing trend. This is because glutaric acid, an aliphatic diacid, forms the highly flexible PA55 chain segment after polymerization with pentanediamine. Its random embedding within the PA5T molecular chain disrupts the regular arrangement of the benzene ring structure in the original terephthalic acid unit, weakening the interchain interactions and leading to a decrease in the crystallinity of the copolymer, thus significantly lowering the melting point. By adjusting the ratio of glutaric acid to terephthalic acid, the distribution of aromatic and aliphatic segments in the copolymer can be controlled. This random copolymerization structure disrupts the symmetry and regularity of the molecular chain, reducing its crystallinity and thus enabling controllable adjustment of the melting point.

[0261] In summary, by adjusting the amounts of terephthalic acid, glutaric acid, phosphoramide salt, toluene diisocyanate, organic copper chrome black, acrylate copolymers, and high-temperature antioxidants, the high-temperature resistant nylon resin of this invention, with its excellent mechanical properties, flame retardant properties, and laser direct molding properties, can be obtained under the synergistic effect of these additives.

[0262] Compared to Example 7, Comparative Example 1 prepared a high-temperature resistant nylon resin without the addition of phosphoramide salt. The flame-retardant mechanism of phosphoramide salt is mainly based on the synergistic effect of phosphorus (P) and nitrogen (N) elements in its molecular structure. Under high temperature or combustion conditions, this compound first decomposes, and its phosphorus component can be converted into highly dehydrating substances such as polyphosphoric acid, catalyzing the dehydration and carbonization of the nylon resin matrix, forming a dense and stable expanded char layer on the material surface. Simultaneously, its nitrogen component releases non-combustible gases such as nitrogen and ammonia upon thermal decomposition. These gases dilute the concentration of combustible gases and oxygen, inhibiting the combustion chain reaction (gas-phase flame retardancy), and also help promote the expansion and foaming of the char layer, forming a more effective heat insulation and oxygen barrier (condensed-phase flame retardancy). Therefore, this phosphoramide salt achieves efficient and synergistic flame-retardant protection for nylon resin through a dual pathway of gas-phase dilution to inhibit flame and condensed-phase charring for heat insulation. Therefore, the flame-retardant performance of Comparative Example 1 is lower than that of Example 7.

[0263] Compared to Example 7, Comparative Example 2 prepared high-temperature resistant nylon resin without the addition of toluene diisocyanate. Since toluene diisocyanate (TDI) mainly acts as a reactive compatibilizer in the system, its highly reactive isocyanate groups (-NCO) react chemically with the organic functional groups on the surface of the organic copper chromate black and the molecular chains of the nylon resin, respectively, thereby constructing a strong chemical "bridge" at the interface between the two phases. The mechanism is as follows: During the processing and melting process, the isocyanate groups of TDI first undergo an addition reaction with the amino groups (-NH2) introduced after silane modification on the surface of the organic copper chromate black, forming covalent bonds; simultaneously, the isocyanate groups at the other end can react with the amino groups (-NH2) at the end of the nylon resin molecular chain or the amide bonds (-NH-CO-) on the main chain to generate urea bonds or other chemical connections. This bifunctional chemical bonding fundamentally strengthens the interfacial adhesion between the inorganic filler particles and the organic nylon matrix, effectively preventing filler agglomeration and promoting its uniform dispersion in the resin. This significantly improves the compatibility of the two materials and helps improve the mechanical properties and stability of the final composite material. Therefore, the tensile strength, notched impact resistance, and laser direct forming properties of Comparative Example 2 are lower than those of Example 7.

[0264] Compared with Example 7, Comparative Example 3 prepared high-temperature resistant nylon resin without adding organic copper chromium black. As an organic copper chromium black (CChH) functional additive in nylon resin for laser direct forming (LDS), its mechanism of action is based on the dual effects of its composite metal oxide properties and surface organic modification: Under near-infrared laser irradiation, the copper, chromium, and other metal components in CChH can efficiently absorb laser energy due to their internal free electrons and lattice vibrations, resulting in local high temperatures on the particle surface and changes in physicochemical structure. This decomposes or reduces highly catalytically active metal nanoparticles (especially copper particles). These metal particles exposed on the resin surface provide the necessary catalytic activation centers for subsequent electroless plating, guiding the selective deposition of metals in the laser scanning area, thereby forming precise conductive patterns. At the same time, the amino functional groups introduced into the surface of CChH modified with γ-aminopropyltriethoxysilane can interact or react with the terminal carboxyl groups or amide bonds of nylon resin, significantly improving the uniformity of filler dispersion and interfacial bonding strength in the matrix. This not only improves the mechanical properties of the composite material but also ensures a strong bond between the laser-activated area and the matrix, giving the electroless plating layer excellent adhesion, thus achieving efficient and reliable laser direct forming functionality. Therefore, Comparative Example 3 does not have laser direct forming capability.

[0265] Compared to Example 7, Comparative Example 4 prepared a high-temperature resistant nylon resin without the addition of acrylate copolymers. Since the acrylate copolymer (in this system, it is a styrene-acrylonitrile-glycidyl methacrylate copolymer) acts as a reactive molecular weight regulator, its mechanism of action mainly relies on the active epoxy groups contained in its side chains. Under the high-temperature conditions of the polycondensation reaction, the epoxy groups can undergo ring-opening addition reactions with the amino (-NH2) or carboxyl (-COOH) groups at the ends of the nylon prepolymer molecular chains. Specifically, it reacts with the amino group to generate a secondary hydroxyl group and form a new CN bond, and reacts with the carboxyl group to generate an ester bond. This process can effectively "end-cap" the growing molecular chains, thereby actively terminating chain growth and achieving precise control over the polymer molecular weight and its distribution. Furthermore, the styrene-acrylonitrile segments in the copolymer backbone have a certain degree of compatibility with the nylon matrix, which helps the regulator to be uniformly dispersed in the melt, ensuring the uniformity of the regulating effect. Therefore, this component, through chemical end-capping, helps to achieve a suitable and stable molecular weight while inhibiting excessive molecular weight growth and preventing gelation, thereby optimizing the melt flow and processing window of the final resin. Consequently, the intrinsic viscosity of Comparative Example 4 is higher than that of Example 7.

[0266] Compared to Example 7, Comparative Example 5 prepared a high-temperature resistant nylon resin without the addition of a high-temperature antioxidant. The mechanism of action of the high-temperature antioxidant in nylon resin is based on its unique molecular structure, achieving dual protection. On one hand, the 2,2,6,6-tetramethylpiperidine group in its molecule, through its large steric hindrance effect, can efficiently capture alkyl free radicals generated during high-temperature processing or use of nylon, interrupting the free radical chain oxidation reaction and thus delaying the thermo-oxidative aging of the material. On the other hand, the amide bonds (-CONH-) at both ends can chemically react with the amino or carboxyl groups at the ends of the nylon resin molecular chain, allowing the antioxidant to be chemically grafted onto the polymer backbone in the form of covalent bonds. This reactive fixation not only avoids the volatilization or migration loss of the antioxidant at high temperatures but also significantly improves its dispersibility and compatibility in the matrix, achieving long-lasting and stable antioxidant protection. Therefore, this antioxidant provides long-lasting and efficient thermal stability protection for high-temperature resistant nylon at the molecular level through a synergistic mechanism of free radical capture and chemical bonding fixation. Therefore, the tensile strength and notched impact performance of Comparative Example 5 are lower than those of Example 7.

[0267] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0268] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A high-temperature resistant nylon resin, characterized in that, It is prepared from the following raw materials in parts by weight: 102.2 parts of 1,5-pentanediamine Terephthalic acid 66.5–99.7 parts, Glutaric acid 52.9–79.3 parts, Contains 32-62 parts of phosphoramide salt, Toluene diisocyanate 4.7–5.7 parts, Organic copper chromium black, 25-37 parts. 6-14 parts of acrylate copolymers, 0.6–1.6 parts of high-temperature resistant antioxidant; The molar ratio of 1,5-pentanediamine to terephthalic acid and glutaric acid is equimolar; and / or, the phosphoramide salt is obtained by a salt-forming reaction of 2-carboxyethylphenyl hypophosphite and 1,5-pentanediamine; and / or, the organic copper chromate black is obtained by organic modification of copper chromate black with γ-aminopropyltriethoxysilane; and / or, the acrylate copolymer is a styrene-acrylonitrile-glycidyl methacrylate copolymer; and / or, the high-temperature antioxidant is N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

2. The high-temperature resistant nylon resin according to claim 1, characterized in that, It is prepared from the following raw materials in parts by weight: 102.2 parts of 1,5-pentanediamine Terephthalic acid 74.8–91.4 parts, Glutaric acid 59.5–72.7 parts, Contains 37–57 parts of phosphoramide salt. Toluene diisocyanate 4.9–5.5 parts, Organic copper chromium black, 27-35 parts. 7-13 parts of acrylate copolymers, 0.8 to 1.4 parts of high-temperature resistant antioxidant.

3. The high-temperature resistant nylon resin according to claim 2, characterized in that, It is prepared from the following raw materials in parts by weight: 102.2 parts of 1,5-pentanediamine 78.1–88 parts of terephthalic acid Glutaric acid 62.1–70 parts, Contains 42-52 parts of phosphoramide salt, Toluene diisocyanate 5.1–5.3 parts, Organic copper chromium black, 29–33 parts. 9-11 parts of acrylate copolymers, 0.9 to 1.3 parts of high-temperature resistant antioxidant.

4. The high-temperature resistant nylon resin according to any one of claims 1 to 3, characterized in that, The preparation method of the phosphoramide salt includes the following steps: 214.16 g of 2-carboxyethylphenyl hypophosphite and 102.18 g of 1,5-pentanediamine are added to a stirred polymerization reactor, followed by the addition of 150 mL to 200 mL of deionized water. The reactor is then evacuated for 2 to 6 minutes and purged with nitrogen for 2 to 6 minutes. This cycle is repeated 3 to 5 times, and the system pressure inside the stirred polymerization reactor is controlled at 0.1 MPa to 0.3 MPa. The stirred polymerization reactor is then sealed and heated to 85°C to 95°C for 0.5 to 1.5 hours, with the stirring speed controlled at 50 r / min to 100 r / min. After the salt formation reaction is carried out for 1 to 2 hours, the reaction is completed, the pressure inside the reactor is reduced to 0.1 MPa, the material is discharged, and vacuum dried.

5. The high-temperature resistant nylon resin according to any one of claims 1 to 3, characterized in that, The preparation method of the organic copper chromium black includes the following steps: 100 g of copper chromium black and 2.7 g to 3.7 g of γ-aminopropyltriethoxysilane are added to a high-speed stirrer and stirred at room temperature for 6 min to 10 min to obtain the product.

6. The high-temperature resistant nylon resin according to any one of claims 1 to 3, characterized in that, The average particle size of the copper chromium black in the organic copper chromium black is 1.4 μm to 1.6 μm; and / or, the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer is 7% to 9%.

7. The method for preparing the high-temperature resistant nylon resin according to any one of claims 1 to 6, characterized in that, Includes the following steps: (1) Vacuum-dried 1,5-pentanediamine, terephthalic acid and glutaric acid are added to a stirred polymerization reactor, along with phosphoramide salt, toluene diisocyanate, organic copper chromate black, acrylate copolymer, high-temperature antioxidant and appropriate amount of water. Then, vacuum is applied for 2 min to 6 min, and nitrogen is purged for 2 min to 6 min. This cycle is repeated 3 to 5 times, and the system pressure in the stirred polymerization reactor is controlled to be 0.1 MPa to 0.3 MPa. (2) Adjust the stirring speed of the stirred polymerization reactor to 20 r / min to 40 r / min, and heat the stirred polymerization reactor to 280℃ to 284℃ in a closed and uniform manner for 2 to 4 hours. When the temperature of the stirred polymerization reactor reaches 213℃, release the gas to 2.05 MPa and maintain the pressure at 2.05 MPa. After reacting for 1 to 2 hours, release the gas to atmospheric pressure and raise the temperature to 314℃ to 318℃. Continue to react for 1 to 2 hours, and maintain the constant temperature and vacuum for 15 to 45 minutes. When the reaction is completed, add nitrogen gas when discharging to obtain the final product.

8. The method for preparing high-temperature resistant nylon resin according to claim 7, characterized in that, In step (1), the vacuum is drawn for 3 min to 5 min, and nitrogen is purged for 3 min to 5 min. This cycle is repeated 3 to 5 times to control the system pressure inside the stirred polymerization reactor to be 0.15 MPa to 0.25 MPa.

9. The method for preparing high-temperature resistant nylon resin according to claim 7, characterized in that, In step (2), the stirring speed of the stirred polymerization reactor is adjusted to 25 r / min to 35 r / min. The stirred polymerization reactor is heated to 281℃ to 283℃ in a closed and uniform manner for 2.5 hours to 3.5 hours. When the temperature of the stirred polymerization reactor reaches 213℃, the pressure is released to 2.05 MPa and maintained at 2.05 MPa. After reacting for 1.3 hours to 1.7 hours, the pressure is released to atmospheric pressure, and the temperature is raised to 315℃ to 317℃. The reaction continues for 1.3 hours to 1.7 hours. The temperature is kept constant and the vacuum is continuously applied for 20 minutes to 40 minutes. When the reaction ends, nitrogen is added when discharging the product to obtain the final product.

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