An antistatic nylon 5X resin and its preparation method

Abstract

This invention discloses an antistatic nylon 5X resin and its preparation method. The preparation method includes: reacting bio-based pentanediamine with a diacid to form a salt, obtaining nylon 5X salt; subjecting the nylon 5X salt to a prepolymerization reaction under the action of a catalyst to obtain a prepolymer; introducing the prepolymer into a microreactor and adding antistatic agent A to conduct a final polymerization reaction to obtain nylon 5X resin; pressurizing the nylon 5X resin into an extruder, adding antistatic agent B and a tackifier for solid-phase tackification, then drawing the resin into strips and feeding them into a pelletizer for pelletizing; and drying the pellets to obtain antistatic nylon 5X resin chips. This invention solves the problems of inaccurate control of polymerization temperature and poor coupling stability between antistatic agents and nylon, and the antistatic nylon 5X resin obtained by this invention further improves antistatic properties.

Description

Technical Field

[0001] This invention relates to the field of nylon preparation, specifically to an antistatic nylon 5X resin and its preparation method. Background Technology

[0002] Currently, the raw materials for nylon 6 and nylon 66 products widely used in industry are mainly derived from the reprocessing of petroleum refining byproducts, resulting in a high dependence on petroleum and environmental pollution problems during the manufacturing process. The synthesis of novel, green, and sustainable nylons has become a research hotspot in recent years. Utilizing inexpensive and renewable biomass resources as raw materials and employing bioengineering methods to synthesize the raw materials needed for nylon to prepare bio-based nylon products is one of the future development trends for nylon.

[0003] Bio-based nylon materials refer to those produced using renewable biomass resources, such as glucose, cellulose, and vegetable oils (including castor oil, oleic acid, and linoleic acid), through bioengineering methods. The raw materials needed for nylon production (generally diacids, diamines, or lactams) are typically derived from these resources. Common bio-based nylon materials include nylon 56, nylon 510, nylon 5T, nylon 11, nylon 1010, nylon 610, nylon 410, and nylon 1012. Bio-based nylon has numerous applications in clothing fibers, natural gas pipelines, medical protective goggles, metal protective coatings, high-end fire-resistant oil-gas separators and crankshaft end caps, food packaging, automotive fuel lines, LED packaging components, and sporting goods.

[0004] Bio-based nylon 5X, comparable to petroleum-derived nylon 6 and nylon 66, boasts superior heat resistance, abrasion resistance, impact resistance, and tensile strength, making it widely applicable across various fields, with its production increasing year by year. Traditional nylon 6 and nylon 66 are obtained through petroleum cracking. The raw material for synthesizing bio-based nylons like nylon 56 is 1,5-pentanediamine, which can be converted from lysine through bioengineering, significantly reducing dependence on petroleum. Nylon 56 possesses high tensile strength and heat resistance, making it a viable alternative to nylon 6 in the textile, automotive, and electrical / electronic industries. Nylon 56 fibers exhibit high moisture absorption and release, good contact coolness, good abrasion resistance, strong spinnability, and high strength. However, the application of nylon 5X in the textile industry still requires addressing the issue of high static electricity content in fabrics. Its surface easily accumulates large amounts of static charge after contact or friction, and the generated charge cannot be released promptly, easily leading to static electricity hazards and even catastrophic accidents such as explosions. Therefore, the application of nylon 5X is limited by static electricity. Nylon 56 needs antistatic modification to give it a lower resistivity, reducing surface and volume resistivity to eliminate static electricity hazards. Antistatic Nylon 5X products can replace traditional Nylon 6 and Nylon 66 and will shine in the textile industry. If 40% of Nylon 66 is replaced by bio-based Nylon 56 in the future, the market size will reach 1.4 million tons per year, indicating a broad market prospect. Research and development of bio-based antistatic Nylon 5X product preparation technology is of great significance.

[0005] CN202211443232 discloses a halogen-free flame-retardant permanent antistatic polyamide composition, in which a compatibilizer, a composite permanent antistatic masterbatch, a halogen-free flame retardant, a synergistic flame retardant, an antioxidant, and a lubricant are added to a polyamide resin in a weight ratio, and then blended and extruded to obtain the corresponding antistatic nylon composition.

[0006] CN202210979614 discloses an antistatic halogen-free flame-retardant reinforced nylon composite material. The preparation method is as follows: conductive microencapsulated hypophosphite flame retardant, antioxidant, glass fiber and nylon resin are uniformly mixed according to the required weight parts, and then added to a twin-screw extruder for melt blending, extrusion granulation, and thus obtained antistatic halogen-free flame-retardant reinforced nylon composite material.

[0007] CN202211358594 discloses a low-temperature wear-resistant and antistatic polyamide composite material for ski board soles. First, wear-resistant fillers and elastomers are kneaded, extruded, and pelletized to prepare a wear-resistant modified elastomer. Then, inorganic nanofillers, conductive fillers, and antioxidants are added to a high-speed mixer for mixing. Next, polyamide matrix resin, wear-resistant modified elastomer, compatibilizer, and wear-resistant polymer are added and mixed evenly to obtain a mixture. Finally, the mixture and inorganic fibers are added to a twin-screw extruder for melt blending, extrusion, cooling, air drying, pelletizing, and drying to prepare the low-temperature wear-resistant and antistatic polyamide composite material.

[0008] Although the above-mentioned existing technologies provide a method for preparing antistatic nylon, the following problems still exist: (1) The nylon polymerization in the early stage needs to be carried out at high temperature. The reaction temperature of the reactor polymerization cannot be precisely controlled, which will lead to uneven molecular weight distribution of nylon products and generate more energy consumption; (2) The antistatic nylon currently prepared is prepared by first preparing an antistatic agent and then blending and extruding it with nylon material. The degree of crosslinking between the antistatic agent and the nylon material is still low, and the stability needs to be further improved; (3) The preparation method of the antistatic agent is still relatively complicated, and the antistatic performance still needs to be improved. Summary of the Invention

[0009] The purpose of this invention is to provide an antistatic nylon 5X resin and its preparation method, so as to solve the problems of inaccurate control of polymerization temperature and poor coupling stability between antistatic agent and nylon in the prior art. Furthermore, the antistatic nylon 5X resin obtained by this invention further improves the antistatic performance.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] This invention provides a method for preparing antistatic nylon 5X resin, which includes the following steps:

[0012] Bio-based pentanediamine reacts with a dicarboxylic acid to form a salt, yielding nylon 5X salt;

[0013] The nylon 5X salt undergoes a prepolymerization reaction under the action of a catalyst to obtain a prepolymer;

[0014] The prepolymer is introduced into a microreactor and antistatic agent A is added to carry out a final polymerization reaction to obtain nylon 5X resin.

[0015] The nylon 5X resin is pressurized and fed into an extruder, and antistatic agent B and tackifier are added for solid-phase tackification. Then, it is drawn into strips and fed into a pelletizer for pelletizing. After drying, antistatic nylon 5X resin chips are obtained.

[0016] In some embodiments of the present invention, the antistatic agent A, calculated based on a total weight of 100 parts, comprises: 45-60 parts graphene, 5-10 parts carbon black, 5-20 parts nano calcium carbonate, 0.5-2 parts antioxidant, 1-5 parts dispersant, and 5-20 parts compatibilizer.

[0017] In some embodiments of the present invention, the amount of antistatic agent A added is 20% to 30% of the mass of nylon 5X salt solution.

[0018] In some embodiments of the present invention, the antioxidant may be selected from phosphite antioxidants, such as tris[2,4-di-tert-butylphenyl]phosphite.

[0019] In some embodiments of the present invention, the dispersant may be polyethylene low molecular weight wax, etc.

[0020] In some embodiments of the present invention, the compatibilizer may be maleic anhydride grafted with POE, etc.

[0021] In some embodiments of the present invention, the antistatic agent B, calculated based on a total weight of 100 parts, comprises: 80-90 parts of carbon nanotubes, 1-5 parts of dispersant, and 5-20 parts of compatibilizer.

[0022] In some embodiments of the present invention, the amount of antistatic agent B added is 15 to 25% of the mass of nylon 5X resin.

[0023] In some embodiments of the present invention, the dispersant may be polyethylene low molecular weight wax, etc.

[0024] In some embodiments of the present invention, the compatibilizer may be maleic anhydride grafted with POE, etc.

[0025] In some embodiments of the present invention, the molar ratio of the bio-based pentanediamine to the dicarboxylic acid is 1:(1 to 1.2).

[0026] In some embodiments of the present invention, the dicarboxylic acid is an aromatic or aliphatic dicarboxylic acid with C4 or more carbon atoms.

[0027] In some embodiments of the present invention, the dicarboxylic acid is selected from one of bisaccharide, undecanoic acid, azelaic acid, and terephthalic acid.

[0028] In some embodiments of the present invention, the salt formation reaction is carried out in an alcohol solvent.

[0029] In some embodiments of the present invention, the alcohol solvent is selected from one or more combinations of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, and octanol.

[0030] In some embodiments of the present invention, the temperature of the salt formation reaction is 6 to 80°C and the time is 0.5 to 2 hours.

[0031] In some embodiments of the present invention, the salt-forming reaction process includes:

[0032] In a protective atmosphere, bio-based pentanediamine and dicarboxylic acid are added to an alcohol solvent at a molar ratio of 1:(1-1.2), and a salt formation reaction is carried out at 6-80℃ to obtain a mixed solution of nylon 5X salt with a pH of 6.5-7.5.

[0033] The obtained nylon 5X salt mixture solution was dried after removing the solvent to obtain the nylon 5X salt.

[0034] In some embodiments of the present invention, the solvent removal process includes: after preliminary filtration of the obtained nylon 5X salt mixed solution, further solvent removal is performed using a centrifuge; the centrifuge speed is 3000-8000 r / min, and the centrifugation time is 1-60 min.

[0035] In some embodiments of the present invention, the drying temperature of the nylon 5X salt is 100-120°C, and the drying time is 1-6 hours.

[0036] In some embodiments of the present invention, the prepolymerization reaction is carried out in an aqueous solvent, and the reaction vessel is a reactor; the nylon 5X salt, water and catalyst are added together to the reactor to carry out the prepolymerization reaction.

[0037] In some embodiments of the present invention, in the prepolymerization reaction, the mass ratio of the nylon 5X salt to water is 1:(0.3 to 0.8).

[0038] In some embodiments of the present invention, the catalyst is anhydrous acetic acid, and the amount added is 0.3% to 2% of the mass of the nylon 5X salt solution.

[0039] In some embodiments of the present invention, the reaction temperature of the prepolymerization reaction is 120-160°C and the reaction time is 0.5-2 hours.

[0040] In some embodiments of the present invention, the microreactor is a falling film microreactor. Preferably, the falling film microreactor contains a multi-channel hollow structure made of stainless steel, with 20 to 50 channels, and is equipped with a pressure regulating device with a control range of 0 to 10 MPa.

[0041] In some embodiments of the present invention, the reaction temperature of the final polymerization reaction is 220–260°C, and the reaction time is 1.5–3 h.

[0042] In some embodiments of the present invention, the tackifier is selected from BASF nylon polyester tackifier ADR4370.

[0043] In some embodiments of the present invention, the amount of the tackifier added is 0.2% to 2% of the mass of the nylon 5X resin.

[0044] In some embodiments of the present invention, the solid phase thickening process is carried out at a temperature of 200–280°C for 1–6 hours and at an extruder speed of 100–800 rpm.

[0045] Another aspect of the present invention provides an antistatic nylon 5X resin, which is obtained by any of the above preparation methods.

[0046] In some embodiments of the present invention, the surface resistivity of the antistatic nylon 5X resin is 10 Ω. 7 ~10 10 Ω.

[0047] In some embodiments of the present invention, the surface resistivity of the antistatic nylon 5X resin is 10 Ω. 7 ~10 9 Ω.

[0048] In some embodiments of the present invention, the tensile strength of the antistatic nylon 5X resin is 80-100 GPa.

[0049] In some embodiments of the present invention, the tensile strength of the antistatic nylon 5X resin is 83-86 GPa.

[0050] In some embodiments of the present invention, the number-average molecular weight of the antistatic nylon 5X resin is 20,000 to 40,000.

[0051] In some embodiments of the present invention, the molecular weight of the antistatic nylon 5X resin is 36,000 to 39,000.

[0052] The beneficial effects of this invention include:

[0053] 1) Addressing the characteristics of nylon dehydration and polycondensation, this invention introduces a microreactor into the nylon polycondensation reaction. Compared to a reaction vessel, the microreactor can effectively remove reaction heat, precisely control the reaction temperature, effectively meet residence time requirements, control the concentration distribution of reactants, and simultaneously allow for better cross-linking of the antistatic agent and nylon prepolymer, ultimately producing nylon resin with uniform molecular weight. Furthermore, it saves energy, improves reaction efficiency, and reduces reaction time. This invention also employs a combination of a reaction vessel and a microreactor, which effectively controls the reaction rhythm, making the reaction more complete and safer.

[0054] 2) To address the problem that excessive nylon viscosity can easily cause it to stick to the walls and clog the reactor, this invention introduces the solid-phase viscosity enhancement process of nylon into the extruder. Compared to the reactor, the reaction conditions in the extruder are milder and more controllable, which allows the molecular weight of nylon to increase stably. Subsequently, it can be directly traction extruded without causing clogging.

[0055] 3) To address the issue of unstable antistatic effect of nylon, this invention designs two antistatic agents and adds them separately, in batches, and in quantitative amounts to the final polymerization and solid-phase thickening steps of nylon. This allows the antistatic agents to better couple with nylon, resulting in better antistatic effect and more stable antistatic performance. Detailed Implementation

[0056] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0057] This invention provides a novel polymerization method for antistatic nylon 5X. By using a reactor with a microreactor, the time, temperature, and reactant concentration distribution of the nylon polycondensation reaction are controlled, resulting in a more uniform molecular weight distribution of nylon, higher polymerization efficiency, and more stable antistatic properties. This improves reaction efficiency and reduces reaction energy consumption. The risk of reaction equipment blockage is reduced by using solid-phase thickening in the extruder. The antistatic ability and stability of nylon 5X are enhanced by adding different types of antistatic agents in batches during the nylon polymerization reaction. This provides a more feasible method for the efficient production of superior antistatic nylon 5X resin.

[0058] The method for preparing antistatic nylon 5X resin provided by this invention includes the following steps:

[0059] S1. Bio-based pentanediamine reacts with a dicarboxylic acid to form a salt, yielding nylon 5X salt.

[0060] S2. The nylon 5X salt undergoes a prepolymerization reaction under the action of a catalyst to obtain a prepolymer;

[0061] S3. The prepolymer is introduced into a microreactor and antistatic agent A is added to carry out a final polymerization reaction to obtain nylon 5X resin.

[0062] S4. The nylon 5X resin is pressurized and fed into an extruder, and antistatic agent B and tackifier are added for solid-phase tackification. Then, it is drawn into strips and fed into a pelletizer for pelletizing. After drying, antistatic nylon 5X resin chips are obtained.

[0063] The following provides a detailed explanation of each step:

[0064] S1, bio-based pentanediamine reacts with a dicarboxylic acid to form a salt, yielding nylon 5X salt.

[0065] The preferred molar ratio of the bio-based pentanediamine to the dicarboxylic acid is 1:(1-1.2).

[0066] Preferably, the dicarboxylic acid is an aromatic or aliphatic dicarboxylic acid with four or more carbon atoms; for example, one of bisaccharide, undecanoic acid, azelaic acid, or terephthalic acid can be selected.

[0067] In some specific embodiments of the present invention, the salt formation reaction is carried out in an alcohol solvent. Preferably, the alcohol solvent is selected from one or more combinations of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, and octanol.

[0068] In some specific embodiments of the present invention, the temperature of the salt formation reaction is 6 to 80°C and the time is 0.5 to 2 hours.

[0069] In some specific embodiments of the present invention, the salt-forming reaction process includes:

[0070] In a protective atmosphere, bio-based pentanediamine and dicarboxylic acid are added to an alcohol solvent at a molar ratio of 1:(1-1.2), and a salt formation reaction is carried out at 6-80℃ to obtain a mixed solution of nylon 5X salt with a pH of 6.5-7.5.

[0071] The obtained nylon 5X salt mixture solution was dried after removing the solvent to obtain the nylon 5X salt.

[0072] Specifically, solvent removal can be achieved through filtration, centrifugation, or other methods. Drying can be carried out using an oven, with the drying temperature determined by the solvent used. The protective atmosphere can be formed by repeatedly replacing the reaction vessel with a protective gas, by continuously introducing a protective gas during the reaction process, or by any other method that can create a protective atmosphere. The protective gas is a rare gas such as nitrogen or argon.

[0073] In some specific embodiments of the present invention, the solvent removal process includes: after preliminary filtration of the obtained nylon 5X salt mixed solution, further solvent removal is performed using a centrifuge; the centrifuge speed is 3000-8000 r / min, and the centrifugation time is 1-60 min.

[0074] In some specific embodiments of the present invention, the drying temperature of the nylon 5X salt is 100-120°C, and the drying time is 1-6 hours.

[0075] S2. The nylon 5X salt undergoes a prepolymerization reaction under the action of a catalyst to obtain a prepolymer.

[0076] Preferably, the prepolymerization reaction is carried out in an aqueous solvent, and the reaction vessel is a reactor; the nylon 5X salt, water, and catalyst are added together to the reactor to carry out the prepolymerization reaction. The mass ratio of the nylon 5X salt to water is preferably 1:(0.3-0.8).

[0077] In some specific embodiments of the present invention, the catalyst is anhydrous acetic acid, and the amount added is 0.3% to 2% of the mass of the nylon 5X salt solution.

[0078] In some specific embodiments of the present invention, the reaction temperature of the prepolymerization reaction is 120-160°C and the reaction time is 0.5-2 hours.

[0079] In some specific embodiments of the present invention, the antistatic agent A, calculated based on a total weight of 100 parts, comprises: 45-60 parts graphene, 5-10 parts carbon black, 5-20 parts nano-calcium carbonate, 0.5-2 parts antioxidant, 1-5 parts dispersant, and 5-20 parts compatibilizer. In some specific embodiments of the present invention, the antioxidant is selected from phosphite antioxidants, such as tris[2,4-di-tert-butylphenyl]phosphite; the dispersant is polyethylene low-molecular-weight wax, etc.; and the compatibilizer is maleic anhydride-grafted POE, etc.

[0080] The nano-calcium carbonate itself has electrical conductivity and a certain compatibility effect, which promotes its compatibility with graphene and carbon black, increases compatibility, and can increase the antistatic effect.

[0081] In some specific embodiments of the present invention, the amount of antistatic agent A added is 20% to 30% of the mass of nylon 5X salt solution.

[0082] S3. The prepolymer is introduced into a microreactor, and antistatic agent A is added to carry out a final polymerization reaction to obtain nylon 5X resin.

[0083] The microreactor is preferably a falling film microreactor. More preferably, the falling film microreactor contains a multi-channel hollow structure made of stainless steel, with 20 to 50 channels, and is equipped with a pressure regulating device with a control range of 0 to 10 MPa.

[0084] In some specific embodiments of the present invention, the reaction temperature of the final polymerization reaction is 220–260°C, and the reaction time is 1.5–3 h.

[0085] S4. The nylon 5X resin is pressurized and fed into an extruder, and antistatic agent B and tackifier are added for solid-phase tackification. Then, it is drawn into strips and fed into a pelletizer for pelletizing. After drying, antistatic nylon 5X resin chips are obtained.

[0086] In some specific embodiments of the present invention, the amount of the tackifier added is 0.2% to 2% of the mass of the nylon 5X resin.

[0087] In some specific embodiments of the present invention, during the solid-phase thickening process, the temperature is 200-280°C, the time is 1-6 hours, and the extruder speed is 100-800 rpm.

[0088] The tackifier can be any conventional tackifier in the art, such as BASF nylon polyester tackifier ADR4370 selected in some specific embodiments of the present invention.

[0089] In some specific embodiments of the present invention, the antistatic agent B, calculated based on a total weight of 100 parts, comprises: 80-90 parts of carbon nanotubes, 1-5 parts of dispersant, and 5-20 parts of compatibilizer. In some specific embodiments of the present invention, the dispersant is polyethylene low molecular weight wax, etc., and the compatibilizer is maleic anhydride-grafted POE, etc.

[0090] In this invention, antistatic agent A and antistatic agent B are designed to be added separately during the prepolymerization reaction and solid-phase thickening. The carbon nanotubes in antistatic agent B have poor compatibility with the carbon black and graphene in antistatic agent A; in addition, if antistatic agent A and antistatic agent B are added together in the early stage, the reaction environment is unfavorable to carbon nanotubes, making it difficult for them to exert their antistatic properties.

[0091] In some specific embodiments of the present invention, the amount of antistatic agent B added is 15-25% of the mass of nylon 5X resin.

[0092] The surface resistivity of the antistatic nylon 5X resin obtained by any of the above preparation methods is preferably 10 Ω·cm. 7 ~10 10 Ω, more preferably 10 7 ~10 9 Ω; the tensile strength of the antistatic nylon 5X resin is preferably 80-100 GPa, more preferably 83-86 GPa; the number average molecular weight of the antistatic nylon 5X resin is preferably 20000-40000, more preferably 36000-39000.

[0093] The following specific examples are provided for illustration, wherein all numerical specifications (e.g., temperature, time, concentration, and weight, including ranges for each) are generally approximate values ​​that may be changed in increments of 0.1 or 1.0 (+) or (-). All numerical specifications are to be understood as being preceded by the term "about".

[0094] The formulation of antistatic agent A used in Examples 1-12 and the comparative examples is as follows: 60 parts graphene, 10 parts carbon black, 10 parts nano-calcium carbonate, 2 parts antioxidant, 3 parts dispersant, and 15 parts compatibilizer. The antioxidant is tris[2,4-di-tert-butylphenyl] phosphite, the dispersant is low molecular weight polyethylene wax, and the compatibilizer is maleic anhydride-grafted POE.

[0095] The formulation of antistatic agent B is as follows: 90 parts carbon nanotubes, 5 parts dispersant, and 5 parts compatibilizer. The dispersant is low molecular weight polyethylene wax, and the compatibilizer is maleic anhydride-grafted POE.

[0096] The tackifier is specifically BASF nylon polyester tackifier ADR4370.

[0097] Example 1

[0098] The following embodiments are all based on this experimental procedure, including:

[0099] S1. 73.07 g (0.5 mol) of adipic acid was placed in 400 mL of anhydrous ethanol. The temperature was raised to 65 °C, and stirring was started. After the adipic acid dissolved, 51.09 g (0.5 mol) of bio-based pentanediamine was slowly added dropwise under nitrogen protection. The reaction was continued at 65 °C with stirring for 1 hour. The reaction was stopped when the solution became turbid. At this time, the pH value of the solution was measured to be 6.9.

[0100] The solution was slowly poured into a funnel with filter paper for preliminary filtration. The filtered mixture was then poured into a centrifuge for further centrifugation and filtration. The centrifuge speed was 6000 r / min and the centrifugation time was 40 min. The resulting white powder was collected and placed in an oven at 100℃ for 3 h to obtain white granular nylon 56 salt.

[0101] S2. Place 100g of nylon 56 salt and 50g of purified water into a reaction vessel, and add 1.5g of anhydrous acetic acid dropwise. Purge with nitrogen three times until there is no air in the vessel. Under nitrogen protection, carry out the prepolymerization reaction at 140℃. After reacting for 1 hour, the prepolymerized nylon 56 melt is obtained.

[0102] S3. The nylon 56 melt is introduced into a falling film microreactor, and 45g of antistatic agent A is added. After reacting at 240℃ for 3h, nylon 56 molten resin is obtained.

[0103] S4. Continue to feed the molten nylon 56 resin into the extruder, and add 2.8g of tackifier and 45g of antistatic agent B. Perform solid-phase tackification in the extruder. During solid-phase tackification, the extruder speed is 500rpm and the reaction is carried out in the extruder for 5 hours. Then, feed it into a pelletizer for pelleting and drying to obtain antistatic nylon 5X resin chips.

[0104] Table 1 shows the final mass, number-average molecular weight, and tensile strength of the nylon product obtained by changing the molar ratio of adipic acid and pentanediamine under the experimental conditions described above.

[0105] Table 1

[0106]

[0107]

[0108] As shown in Table 1, when the molar ratio of diamine to diacid is 1:(1.1 to 1.2), the molecular weight of the resulting nylon resin ranges from 35,000 to 39,000, and the tensile strength is in the range of 83 to 86 GPa.

[0109] Example 2

[0110] Example 2 is similar to Examples 1-2, except that the mass ratio of nylon 56 salt to pure water placed in the reactor is different. In Example 2, the mass ratio of nylon 56 salt to pure water was changed, and the data of the final nylon product mass, number-average molecular weight and tensile strength are shown in Table 2.

[0111] Table 2

[0112]

[0113] As shown in Table 2, when the mass ratio of nylon 56 salt to pure water is 1:(0.5 to 0.8), the molecular weight of the resulting nylon resin ranges from 37,000 to 39,000, and the tensile strength is in the range of 83 to 86 GPa.

[0114] Example 3

[0115] Example 3 is similar to Examples 2-2, except that the mass of anhydrous acetic acid catalyst added to the reactor is different. In Example 3, the mass of the final nylon product, its number-average molecular weight, and tensile strength are shown in Table 3 by changing the amount of anhydrous acetic acid added.

[0116] Table 3

[0117]

[0118] As shown in Table 3, when the ratio of anhydrous acetic acid to the mass of nylon 56 salt solution is 1%, the molecular weight of nylon resin is in the range of 38,000 to 39,000, and the tensile strength is in the range of 84 to 86 GPa.

[0119] Example 4

[0120] Example 4 is similar to Examples 3-2, except that the reaction temperature of the prepolymerization reaction in the reactor is different. In Example 4, the reaction temperature of the prepolymerization reaction in the reactor, the pressure in the reactor, and the data of the final nylon product mass, number-average molecular weight and tensile strength are shown in Table 4.

[0121] Table 4

[0122]

[0123] As shown in Table 4, when the prepolymerization temperature in the reactor is 120-140℃, the molecular weight of the nylon resin ranges from 38,000 to 39,000, and the tensile strength is in the range of 84-86 GPa.

[0124] Example 5

[0125] Example 5 is similar to Example 4-2, except that the reaction time of the prepolymerization reaction in the reactor is different. In Example 4, the reaction time of the prepolymerization reaction in the reactor was changed, and the data of the final nylon product mass, number-average molecular weight and tensile strength are shown in Table 5.

[0126] Table 5

[0127]

[0128] As shown in Table 5, when the prepolymerization reaction time in the reactor is 0.5 to 2 hours, the molecular weight of the nylon resin ranges from 37,000 to 39,000, and the tensile strength is in the range of 83 to 86 GPa.

[0129] Example 6

[0130] Example 6 is similar to Examples 5-3, except that the mass of antistatic agent A added in the falling film microreactor is different. In Example 6, the mass of antistatic agent A added in the falling film microreactor was changed. The data of the final nylon product mass, its number-average molecular weight, tensile strength and surface resistivity of the resin material are shown in Table 6.

[0131] Table 6

[0132]

[0133] As shown in Table 6, when the amount of antistatic agent A added is 20%–30% of the nylon salt solution, the molecular weight of the nylon resin ranges from 37,000 to 39,000, the tensile strength is in the range of 85–86 GPa, and the resistivity of the nylon resin is 10 Ω·cm. 8 ~10 10 Ω.

[0134] Example 7

[0135] Example 7 is similar to Examples 6-3, except that the reaction temperature of the final polymerization reaction in the falling film microreactor is different. In Example 7, the reaction temperature of the final polymerization reaction in the falling film microreactor, the pressure in the reaction tube, and the data of the final nylon product mass, number-average molecular weight, and tensile strength are shown in Table 7.

[0136] Table 7

[0137]

[0138] As shown in Table 7, when the reaction temperature for the final polymerization reaction in the microreactor is 220–260℃, the molecular weight of the nylon resin ranges from 38,000 to 39,000, and the tensile strength is in the range of 84–86 GPa.

[0139] Example 8

[0140] Example 8 is similar to Examples 7-2, except that the reaction time of the final polymerization reaction in the falling film microreactor is different. In Example 8, the reaction time of the final polymerization reaction in the reaction tube was changed, and the data of the final nylon product mass, its number-average molecular weight and tensile strength are shown in Table 8.

[0141] Table 8

[0142]

[0143] As shown in Table 8, when the reaction time for the final polymerization reaction in the microreactor is 1.5 to 3 hours, the molecular weight of the nylon resin ranges from 37,000 to 39,000, and the tensile strength is in the range of 84 to 86 GPa.

[0144] Example 9

[0145] Example 9 is similar to Examples 8-3, except that the mass of the thickener added during solid-phase thickening in the extruder is different. In Example 9, the mass of the thickener added was changed, and the data of the final nylon product mass, its number-average molecular weight and tensile strength are shown in Table 9.

[0146] Table 9

[0147]

[0148] As shown in Table 9, when the tackifier content accounts for 2% of the nylon 56 resin, the molecular weight of the nylon resin ranges from 36,000 to 39,000, and the tensile strength is in the range of 84 to 87 GPa.

[0149] Example 10

[0150] Example 10 is similar to Examples 9-3, except that the reaction temperature during solid-phase thickening in the extruder is different. In Example 10, the reaction temperature of the extruder was changed, and the data on the final nylon product mass, number-average molecular weight, and tensile strength are shown in Table 10.

[0151] Table 10

[0152]

[0153] As shown in Table 10, when the solid-phase thickening reaction temperature is 240℃, the molecular weight of nylon resin ranges from 38,000 to 39,000, and the tensile strength is in the range of 84 to 86 GPa.

[0154] Example 11

[0155] Example 11 is similar to Examples 10-2, except that the reaction time for solid-phase thickening in the extruder is different. In Example 11, the reaction time for solid-phase thickening in the extruder was changed, and the final nylon product mass, number-average molecular weight, and tensile strength data are shown in Table 11.

[0156] Table 11

[0157]

[0158] As shown in Table 11, when the solid-phase thickening reaction time is 1 to 5 hours, the molecular weight of the nylon resin ranges from 36,000 to 39,000, and the tensile strength is in the range of 83 to 86 GPa.

[0159] Example 12

[0160] Example 12 is similar to Examples 11-3, except that the mass of antistatic agent B added in the extruder is different. In Example 12, the mass of antistatic agent B added in the extruder was changed. The data of the final nylon product mass, its number-average molecular weight, tensile strength and surface resistivity of the resin material are shown in Table 12.

[0161] Table 12

[0162]

[0163] As shown in Table 12, when the amount of antistatic agent B added is 15%–25% of the nylon salt solution, the molecular weight of the nylon resin ranges from 37,000 to 39,000, the tensile strength is in the range of 85–86 GPa, and the resistivity is 10 Ω·cm. 7 ~10 10 Ω.

[0164] Example 13

[0165] Example 13 is similar to Examples 6-3, except that the composition ratio of antistatic agent A added in the falling film microreactor is different. In Example 13, the composition ratio of antistatic agent A added in the falling film microreactor is changed, that is, the ratio of graphene, carbon black and nano calcium carbonate in antistatic agent A is changed. The final nylon product mass, its number-average molecular weight, tensile strength and surface resistivity of resin material are shown in Tables 13 and 14.

[0166] Table 13

[0167]

[0168] In Table 13, the ratio of graphene to carbon black in antistatic agent A remains constant at 6:1. The data in Table 13 show that when the amount of antistatic agent A added is 55%–70%, the molecular weight of the nylon resin ranges from 38,000 to 39,000, the tensile strength is in the range of 85–86 GPa, and the resistivity is 10 Ω·cm. 8 ~10 10 Ω.

[0169] Table 14

[0170]

[0171] As shown in Table 14, when the calcium carbonate content in antistatic agent A is 5%–20%, the molecular weight of the nylon resin ranges from 38,000 to 39,000, the tensile strength is in the range of 85–86 GPa, and the resistivity is 10 Ω·cm. 8 ~10 10 Ω.

[0172] Example 14

[0173] Example 14 is similar to Examples 12-3, except that the composition ratio of antistatic agent B added in the extruder is different. In Example 14, the composition ratio of antistatic agent B added in the extruder is changed, that is, the ratio of carbon nanotubes in antistatic agent B is changed. The final nylon product mass, its number-average molecular weight, tensile strength and surface resistivity of the resin material are shown in Table 15.

[0174] Table 15

[0175]

[0176] As shown in Table 14, when the proportion of carbon nanotubes in antistatic agent B is 80%–90%, the molecular weight of the nylon resin is 38,000–39,000, the tensile strength is in the range of 85–86 GPa, and the resistivity is 10 Ω·cm. 7 ~10 8 Ω.

[0177] Comparative Example 1

[0178] In this comparative example, the final polymerization reaction was carried out in a reactor.

[0179] S1. Dissolve 73.07g of adipic acid in 400mL of anhydrous ethanol. Heat the solution to 65℃ and stir. Once the adipic acid has dissolved, slowly add 51.09g of bio-based pentanediamine under nitrogen protection. Continue stirring at 65℃ for 1 hour. Stop the reaction when the solution becomes cloudy. At this point, the pH of the solution is measured to be 6.9.

[0180] The solution was slowly poured into a funnel with filter paper for preliminary filtration. The filtered mixture was then poured into a centrifuge for further centrifugation and filtration. The centrifuge speed was 6000 r / min and the centrifugation time was 40 min. The resulting white powder was collected and placed in an oven at 100℃ for 3 h to obtain white granular nylon 56 salt.

[0181] S2. Place 100g of nylon 56 salt, 50g of purified water, and 45g of antistatic agent A into a reaction vessel, and add 1.5g of anhydrous acetic acid dropwise. Purge with nitrogen three times until there is no air in the vessel. Under nitrogen protection, carry out a prepolymerization reaction at 140℃. After reacting for 1 hour, raise the temperature to 240℃ and continue the polymerization reaction for 3 hours to obtain nylon 56 molten resin.

[0182] S3. Continue to feed nylon 56 molten resin into the extruder, add 2.8g of tackifier and 45g of antistatic agent B, and carry out solid-phase tackification in the extruder. During solid-phase tackification, the extruder speed is 500rpm, and the reaction is carried out in the extruder for 5h. Then, pressurize and feed it into a pelletizer for pelleting. After drying, antistatic nylon 5X resin chips are obtained.

[0183] Under the same conditions as above, only the final polymerization reaction steps were changed in this comparative example. The resulting nylon 56 resin had a mass of 134.12 g, a number-average molecular weight of 37,000, and a tensile strength of 80.43 GPa.

[0184] As can be seen from the comparison with Example 1, under the same conditions except that the final polymerization reaction is carried out in the reactor, the yield of the final nylon product, as well as the number-average molecular weight and tensile strength, will be reduced.

[0185] Comparative Example 2

[0186] This comparative example only involved solid-phase thickening in a falling film microreactor with the addition of antistatic agent B.

[0187] S1. Dissolve 73.07g of adipic acid in 400mL of anhydrous ethanol. Heat the solution to 65℃ and stir. Once the adipic acid has dissolved, slowly add 51.09g of bio-based pentanediamine under nitrogen protection. Continue stirring at 65℃ for 1 hour. Stop the reaction when the solution becomes cloudy. At this point, the pH of the solution is measured to be 6.9.

[0188] The solution was slowly poured into a funnel with filter paper for preliminary filtration. The filtered mixture was then poured into a centrifuge for further centrifugation and filtration. The centrifuge speed was 6000 r / min and the centrifugation time was 40 min. The resulting white powder was collected and placed in an oven at 100℃ for 3 h to obtain white granular nylon 56 salt.

[0189] S2. Place 100g of nylon 56 salt and 50g of purified water into a reaction vessel, and add 1.5g of anhydrous acetic acid dropwise. Purge with nitrogen three times until there is no air in the vessel. Under nitrogen protection, carry out the prepolymerization reaction. After 1 hour of reaction, the prepolymerized nylon 56 melt is obtained.

[0190] S3. The nylon 56 melt is fed into a falling film microreactor, and 45g of antistatic agent A, 45g of antistatic agent B and 2.8g of tackifier are added. After reacting in the falling film microreactor for 3 hours, antistatic nylon 56 molten resin is obtained.

[0191] S4. Continue to pressurize the molten antistatic nylon 56 resin into the extruder at a speed of 500 rpm and a temperature of 240°C. After 5 hours in the extruder, the resin is then fed into a pelletizer for pelletizing. After drying, antistatic nylon 5X resin chips are obtained.

[0192] In this comparative example, under the same conditions as above, only the solid-phase thickening and antistatic agent B addition steps were changed. Antistatic agent B was added earlier, during the final polymerization reaction, along with antistatic agent A. The two antistatic agents showed poor compatibility when added together. The resulting nylon 56 resin had a mass of 137.12 g, a number-average molecular weight of 37000, a tensile strength of 81.77 GPa, and a surface resistivity of 10 Ω·cm. 9 Ω.

[0193] In this comparative example, under the same conditions as above, only the addition steps of tackifier and antistatic agent B were changed. The yield of the final nylon product, as well as the number-average molecular weight and tensile strength, were reduced, while the resin surface resistivity was increased.

[0194] Comparative Example 3

[0195] This comparative example does not include antistatic agent A, and all other processes remain unchanged.

[0196] S1. Dissolve 73.07g of adipic acid in 400mL of anhydrous ethanol. Heat the solution to 65℃ and stir. Once the adipic acid has dissolved, slowly add 51.09g of bio-based pentanediamine under nitrogen protection. Continue stirring at 65℃ for 1 hour. Stop the reaction when the solution becomes cloudy. At this point, the pH of the solution is measured to be 6.9.

[0197] The solution was slowly poured into a funnel with filter paper for preliminary filtration. The filtered mixture was then poured into a centrifuge for further centrifugation and filtration. The centrifuge speed was 6000 r / min and the centrifugation time was 40 min. The resulting white powder was collected and placed in an oven at 100℃ for 3 h to obtain white granular nylon 56 salt.

[0198] S2. Place 100g of nylon 56 salt and 50g of purified water into a reaction vessel, and add 1.5g of anhydrous acetic acid dropwise. Purge with nitrogen three times until there is no air in the vessel. Under nitrogen protection, carry out a preliminary pre-reaction at 140℃. After reacting for 1 hour, a preliminary nylon 56 melt is obtained.

[0199] S3. The nylon 56 melt is introduced into a falling film microreactor and reacted at 240°C for 3 hours to obtain nylon 56 molten resin.

[0200] S4. Continue to feed the molten nylon 56 resin into the extruder, and add 2.8g of tackifier and 45g of antistatic agent B. Perform solid-phase tackification in the extruder. During solid-phase tackification, the extruder speed is 500rpm and the reaction is carried out in the extruder for 5 hours. Then, feed it into a pelletizer for pelleting and drying to obtain antistatic nylon 5X resin chips.

[0201] Under the same conditions as above, without the addition of antistatic agent A, the surface resistivity of the nylon 56 resin obtained in this comparative example was 10 Ω·cm. 10 Ω, proving that antistatic agent A can more effectively reduce the surface resistance of nylon 56 resin.

[0202] Comparative Example 4

[0203] This comparative example does not include antistatic agent B, and all other processes remain unchanged.

[0204] S1. Dissolve 73.07g of adipic acid in 400mL of anhydrous ethanol. Heat the solution to 65℃ and stir. Once the adipic acid has dissolved, slowly add 51.09g of bio-based pentanediamine under nitrogen protection. Continue stirring at 65℃ for 1 hour. Stop the reaction when the solution becomes cloudy. At this point, the pH of the solution is measured to be 6.9.

[0205] The solution was slowly poured into a funnel with filter paper for preliminary filtration. The filtered mixture was then poured into a centrifuge for further centrifugation and filtration. The centrifuge speed was 6000 r / min and the centrifugation time was 40 min. The resulting white powder was collected and placed in an oven at 100℃ for 3 h to obtain white granular nylon 56 salt.

[0206] S2. Place 100g of nylon 56 salt and 50g of purified water into a reaction vessel, and add 1.5g of anhydrous acetic acid dropwise. Purge with nitrogen three times until there is no air in the vessel. Under nitrogen protection, carry out a preliminary pre-reaction at 140℃. After reacting for 1 hour, a preliminary nylon 56 melt is obtained.

[0207] S3. The nylon 56 melt is introduced into a falling film microreactor, and 45g of antistatic agent A is added. After reacting at 240℃ for 3h, nylon 56 molten resin is obtained.

[0208] S4. Continue to feed the molten nylon 56 resin into the extruder and add 2.8g of tackifier. Perform solid-phase tackification in the extruder. During solid-phase tackification, the extruder speed is 500rpm and the reaction is carried out in the extruder for 5 hours. Then, feed it into a pelletizer for pelletizing and drying to obtain antistatic nylon 5X resin chips.

[0209] Under the same conditions as above, without the addition of antistatic agent B, the surface resistivity of the nylon 56 resin obtained in this comparative example was 10 Ω·cm. 10 Ω, proving that antistatic agent B can more effectively reduce the surface resistance of nylon 56 resin.

[0210] The tensile strength involved in the above embodiments and comparative examples was measured using a universal tensile testing machine, the number-average molecular weight was measured using GPC gel chromatography, and the surface resistivity of the resin material was measured using a surface resistivity tester.

[0211] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A process for the preparation of an antistatic nylon 5X resin wherein, The preparation method comprises the following steps: The bio-based pentanediamine is subjected to a salt formation reaction with a dibasic acid to obtain a nylon 5X salt; The nylon 5X salt is subjected to a prepolymerization reaction under the action of a catalyst to obtain a prepolymer; The prepolymer is introduced into a microreactor and an antistatic agent A is added to perform a final polymerization reaction to obtain a nylon 5X resin; The nylon 5X resin is introduced into an extruder under pressure and an antistatic agent B and a tackifier are added to perform solid-phase tackification, followed by traction and introduction into a pelletizer to perform pelletization, and after drying, an antistatic nylon 5X resin chip is obtained; The antistatic agent A comprises, calculated based on a total weight of 100 parts, 45-60 parts of graphene, 5-10 parts of carbon black, 5-20 parts of nano calcium carbonate, 0.5-2 parts of an antioxidant, 1-5 parts of a dispersant and 5-20 parts of a compatibilizer; The antistatic agent B comprises, calculated based on a total weight of 100 parts, 80-90 parts of carbon nanotubes, 1-5 parts of a dispersant and 5-20 parts of a compatibilizer; The microreactor is a falling film type microreactor.

2. The production method according to claim 1, wherein The addition amount of the antistatic agent B is 15-25% of the mass of the nylon 5X resin.

3. The production method according to claim 1, wherein, The molar ratio of the bio-based pentanediamine to the dibasic acid is 1:(1-1.2).

4. The production method according to claim 1, wherein The dibasic acid is a C4 and above aromatic or aliphatic dibasic carboxylic acid.

5. The production method according to claim 1, wherein The dibasic acid is selected from one of adipic acid, undecanedioic acid, azelaic acid and terephthalic acid.

6. The production method according to claim 1, wherein The salt formation reaction is performed in an alcohol solvent selected from one or a combination of two or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol and octanol.

7. The production method according to claim 1, wherein The salt formation reaction process comprises: In a protective atmosphere, bio-based pentanediamine and a dibasic acid are added to an alcohol solvent in a molar ratio of 1:(1-1.2) to perform a salt formation reaction at 6-80℃ for 0.5-2 h to obtain a nylon 5X salt mixed solution with a pH value of 6.5-7.5; The obtained nylon 5X salt mixed solution is dried after solvent removal to obtain the nylon 5X salt.

8. The production method according to claim 1, wherein The prepolymerization reaction is performed in an aqueous solvent and the reaction container is a reaction kettle; The nylon 5X salt and water are added to the reaction kettle to obtain a nylon 5X salt solution, a catalyst is added and a prepolymerization reaction is performed; the mass ratio of the nylon 5X salt to water is 1:(0.3-0.8).

9. The production method according to claim 8, wherein The addition amount of the antistatic agent A is 20%-30% of the mass of the nylon 5X salt solution.

10. The production method according to claim 8, wherein The catalyst is anhydrous acetic acid and the addition amount is 0.3%-2% of the mass of the nylon 5X salt solution.

11. The method of making according to claim 1, wherein, The reaction temperature of the prepolymerization reaction is 120-160℃ and the reaction time is 0.5-2 h.

12. The method of making according to claim 1, wherein, The reaction temperature of the final polymerization reaction is 220-260℃ and the reaction time is 1.5-3 h.

13. The method of producing according to claim 1, wherein, The addition amount of the tackifier is 0.2%-2% of the mass of the nylon 5X resin.

14. The method of producing according to claim 1, wherein, In the solid-phase tackification process, the temperature is 200-280℃ and the time is 1-6 h. 15.An antistatic nylon 5X resin obtained by the preparation method of any one of claims 1-14.

16. The antistatic nylon 5X resin according to claim 15, wherein, The antistatic nylon 5X resin has a surface resistance value of 10 7 ~10 10 Ω, a tensile strength of 80-100 GPa, and a number average molecular weight of 20,000-40,000.

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