Supercritical carbon dioxide-assisted functional master batch manufacturing process

Abstract

The invention relates to the technical field of functional master batch production and processing, and discloses a supercritical carbon dioxide-assisted functional master batch manufacturing process, which comprises the following steps: S1, nano metal oxide loading: uniformly dispersing nano metal oxide in a solvent; s2, in-situ polymerization: firstly, cleaning: putting the micro-nano porous material into a proper cleaning solution for cleaning, and removing impurities; s3, crushing treatment: pouring the composite functional powder obtained through in-situ polymerization treatment into a screen for screening; s4, master batch preparation: metering the crushed composite functional powder; and S5, functional fiber preparation: preheating the master batch. According to the functional master batch and the functional fiber, the nano metal oxide, the micro-nano porous material and the conductive polymer are ingeniously combined, the antibacterial function and the antistatic function are achieved, the antibacterial function can effectively inhibit bacterium breeding and reduce the disease transmission risk, and the antistatic function avoids the effects that dust is adsorbed by static electricity and slight electric shock is caused by the static electricity.

Description

Technical Field

[0001] The invention relates to the technical field of functional masterbatch production and processing, and in particular to a supercritical carbon dioxide-assisted functional masterbatch manufacturing process. Background Art

[0002] As people's living standards continue to improve, the requirements for clothing, home textiles, and medical and sanitary products are getting higher and higher. In daily life, bacteria breeding and static electricity problems have always troubled people.

[0003] Traditional clothing, home textiles and medical and health materials often have deficiencies in antibacterial and antistatic properties. For antibacterial properties, some materials may rely solely on the addition of chemical fungicides, but these fungicides may have problems such as toxicity, volatility or short-lasting antibacterial effects. Moreover, long-term use of a single chemical fungicide may cause bacteria to develop drug resistance. In terms of antistatic properties, traditional materials usually use the method of adding antistatic agents, but these antistatic agents may gradually become ineffective as the use time and number of washings increase. In addition, some antistatic agents may affect the mechanical properties and appearance quality of the material.

[0004] The antibacterial and anti-electrical properties of traditional antibacterial materials may gradually decrease after being used for a period of time. This is because bacteria may develop resistance to the bactericide, or the bactericide and anti-electrical properties may gradually evaporate, decompose or be washed away during use. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention provides a supercritical carbon dioxide-assisted functional masterbatch manufacturing process to solve the problem of the gradual decline in antibacterial and anti-electrical properties.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A supercritical carbon dioxide-assisted functional masterbatch manufacturing process comprises the following steps: S1. Nano-metal oxide loading: first, the nano-metal oxide is uniformly dispersed in a solvent, and then the nano-metal oxide is uniformly mixed with the solvent by a stirring device to form a dispersion of the nano-metal oxide, and then the micro-nano porous material is added to the dispersion, and the nano-metal oxide is uniformly loaded on the surface and pores of the porous material by ultrasound; S2, in-situ polymerization: first wash the micro-nano porous material in a suitable cleaning solution to remove impurities, then put the washed nanoporous material into a vacuum drying oven for drying, then prepare a monomer solution and an initiator solution, and then add a conductive polymer monomer to the porous material system loaded with nano metal oxides, and by adding an initiator, promote the conductive polymer monomer to polymerize in situ in the pores of the porous material, and stir at the same time to allow the monomer to fully diffuse into the pores of the porous material and adsorb on the surface of the pores; S3, pulverizing treatment: pouring the composite functional powder obtained by the in-situ polymerization treatment into a sieve for screening to remove large particle agglomerates or impurities, slowly adding the prepared composite functional powder into the feeding area of ​​the airflow pulverizer, and starting the airflow pulverizer; S4, masterbatch preparation: the composite functional powder after pulverization is measured, and then the resin matrix is ​​dried to remove moisture, and then the supercritical carbon dioxide injection equipment enters a supercritical state, and the pre-treated composite functional powder and resin matrix are respectively added to different hoppers of a reactive twin-screw extruder. During the extrusion process, supercritical carbon dioxide is injected into the twin-screw extruder, and then extruded, cooled and pelletized; S5. Preparation of functional fibers: First, the polymer is dried and the masterbatch is preheated. The functional masterbatch is added to the polymer spinning melt by a loss-in-weight feeder. After the functional masterbatch is added, the functional masterbatch and the spinning melt are fully mixed by the stirring and conveying action of the screw and the static mixer component in the pipeline. The fully mixed spinning melt containing the functional masterbatch is conveyed to the spinneret assembly, where it is extruded through the spinneret hole to form a thin stream. The functional fiber after drawing and cooling is wound onto the winding drum.

[0007] Preferably, in S1, the solvent is acetone and water in a ratio of 1:2, the initial stirring time of the nano metal oxide is 5-10 minutes, the stirring speed is 500-800 rpm, the continuous stirring is 200-300 rpm, the stirring time is 30-60 minutes, the frequency of the ultrasonic equipment is initially 20-100 kHz, the duration is 5-10 minutes, the high frequency is 80-170 kHz, and the duration is 15-60 minutes.

[0008] Preferably, the nano metal oxides in S1 include nano titanium dioxide, nano zinc oxide, nano iron oxide, nano copper oxide, nano cerium oxide, nano aluminum oxide and nano silicon dioxide, the particle sizes of the various materials in the nano metal oxides are nano titanium dioxide 10-50 nanometers, nano zinc oxide 20-80 nanometers, nano iron oxide 10-60 nanometers, nano copper oxide 15-70 nanometers, nano cerium oxide 10-50 nanometers, nano aluminum oxide 10-80 nanometers and nano silicon dioxide 10-80 nanometers, and the mass percentages of the various materials in the nano metal oxides are nano titanium dioxide 10%-15%, nano zinc oxide 10%-15%, nano iron oxide 10%-15%, nano copper oxide 8%-12%, nano cerium oxide 8%-12%, nano aluminum oxide 10%-15% and nano silicon dioxide 15%-22%; Micro-nano porous materials include porous silicon, porous silica, porous alumina, porous zinc oxide, conjugated microporous polymers, hyper-crosslinked polymers and organic framework materials. The pore size of each material in the micro-nano porous materials is 100-150 nanometers, porous silica 100-200 nanometers, porous alumina 150-200 nanometers, porous zinc oxide 100-150 nanometers, conjugated microporous polymers 100-200 nanometers, hyper-crosslinked polymers 100-200 nanometers and organic framework materials 110-200 nanometers. The mass percentage of each material is 5%-10% for porous silicon, 15%-20% for porous silica, 10%-15% for porous alumina, 8%-12% for porous zinc oxide, 15%-20% for conjugated microporous polymers, 12%-18% for hyper-crosslinked polymers and 10%-15% for organic framework materials.

[0009] Preferably, in S2, the initiator includes ammonium persulfate, p-toluenesulfonic acid and sodium dodecylbenzenesulfonate in a ratio of 1:2:1, the cleaning time of the cleaning device is 15-30 minutes, the ultrasonic frequency is 40-80kHz, the temperature of the vacuum drying oven is 60-80°C, the drying time is 12-24 hours, the stirring speed of the stirring device is 200-300 rpm, the stirring time is 1-2 hours, and the standing time after stirring is 30-60 minutes.

[0010] Preferably, in S2, the conductive polymer monomers include 3,4-ethylenedioxythiophene, 2,5-dimethylfuran and N-ethylcarbazole, and the amount of the conductive polymer used is 1-5g of 3,4-ethylenedioxythiophene, 1-10g of 2,5-dimethylfuran and 0.1-0.5g of N-ethylcarbazole.

[0011] Preferably, the fineness of the screen in S3 is 200-300 mesh, the crushing pressure of the above-mentioned crusher is 0.5-0.8 MPa, the air flow velocity is 200-300 m / s, the feed rate is 1-2 kg / h, the crushing time is 30-90 minutes, and the sampling frequency is 15-30 minutes / time.

[0012] Preferably, in S4, the resin matrix includes polyester or polyamide, the drying temperature during drying is 120-150°C, the drying time is 3-6 hours, the injection amount of supercritical carbon dioxide accounts for 10-50% of the total volume of the reaction system, the screw speed is 100-500 rpm, the temperature gradient from the hopper to the head is 200-280°C, and the internal residence time is 1-5 minutes.

[0013] Preferably, in S5, the temperature of the polymer drying treatment is 120-150°C, the drying time is 3-6 hours, the temperature of the masterbatch preheating treatment is 50-80°C, the preheating time is 1-2 hours, the minimum feed rate of the constant feeder is 0.01-0.1g / min, the maximum feed rate is 10-50g / min, the screw speed is 1-1000 rpm, the diameter of the spinneret hole is 0.1-0.3mm, the spinneret pressure is 10-20MPa, the cooling medium is cold air, the wind speed is 0.3-0.8m / s, the temperature is 18-25°C, and the humidity is 60-70%.

[0014] The present invention provides a supercritical carbon dioxide-assisted functional masterbatch manufacturing process, which has the following beneficial effects: 1. The functional masterbatch and functional fiber prepared by the material system of the present invention cleverly combine nano metal oxides, micro-nano porous materials and conductive polymers, achieving the dual functions of antibacterial and antistatic. In daily life, whether it is clothing, home textile products or medical and health care, it can provide a healthy, comfortable and safe use experience. The antibacterial function can effectively inhibit the growth of bacteria and reduce the risk of disease transmission. The antistatic function avoids the effect of static electricity on dust absorption and slight electric shock.

[0015] 2. The present invention achieves a more uniform dispersion of the functional components in the masterbatch and the fiber through the addition of supercritical fluid, thereby ensuring a high degree of consistency and stability in product performance. Whether it is large-scale production or small-batch customization, it can ensure that each product has excellent antibacterial and antistatic effects, thereby reducing production costs for enterprises, improving production efficiency, and providing the market with more competitive high-quality products.

[0016] 3. The functional fiber product of the present invention overcomes the defects of traditional functional fibers that are not resistant to water washing and easily lose functionality. The product can always maintain stable functionality during long-term use, providing users with lasting health and safety protection, and reducing the cost and trouble of users' frequent replacement due to reduced product functionality. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a flow chart of the present invention. DETAILED DESCRIPTION

[0018] The technical solution of the present invention will be described clearly and completely below in conjunction with the accompanying drawings of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example

[0020] Please see attached Figure 1 The embodiment of the present invention provides a supercritical carbon dioxide-assisted functional masterbatch manufacturing process, comprising the following steps: S1. Nano-metal oxide loading: first, the nano-metal oxide is uniformly dispersed in a solvent, and then the nano-metal oxide is uniformly mixed with the solvent by a stirring device to form a dispersion of the nano-metal oxide, and then the micro-nano porous material is added to the dispersion, and the nano-metal oxide is uniformly loaded on the surface and pores of the porous material by ultrasound; S2, in-situ polymerization: first wash the micro-nano porous material in a suitable cleaning solution to remove impurities, then put the washed nanoporous material into a vacuum drying oven for drying, then prepare a monomer solution and an initiator solution, and then add a conductive polymer monomer to the porous material system loaded with nano metal oxides, and by adding an initiator, promote the conductive polymer monomer to polymerize in situ in the pores of the porous material, and stir at the same time to allow the monomer to fully diffuse into the pores of the porous material and adsorb on the surface of the pores; S3, pulverizing treatment: pouring the composite functional powder obtained by the in-situ polymerization treatment into a sieve for screening to remove large particle agglomerates or impurities, slowly adding the prepared composite functional powder into the feeding area of ​​the airflow pulverizer, and starting the airflow pulverizer; S4, masterbatch preparation: the composite functional powder after pulverization is measured, and then the resin matrix is ​​dried to remove moisture, and then the supercritical carbon dioxide injection equipment enters a supercritical state, and the pre-treated composite functional powder and resin matrix are respectively added to different hoppers of a reactive twin-screw extruder. During the extrusion process, supercritical carbon dioxide is injected into the twin-screw extruder, and then extruded, cooled and pelletized; S5. Preparation of functional fibers: First, the polymer is dried and the masterbatch is preheated. The functional masterbatch is added to the polymer spinning melt by a loss-in-weight feeder. After the functional masterbatch is added, the functional masterbatch and the spinning melt are fully mixed by the stirring and conveying action of the screw and the static mixer component in the pipeline. The fully mixed spinning melt containing the functional masterbatch is conveyed to the spinneret assembly, where it is extruded through the spinneret hole to form a thin stream. The functional fiber after drawing and cooling is wound onto the winding drum.

[0021] In S1, the solvent is acetone and water in a ratio of 1:2. The initial stirring time of the nano-metal oxide is 5-10 minutes, the stirring speed is 500-800 rpm, the continuous stirring is 200-300 rpm, the stirring time is 30-60 minutes, the frequency of the ultrasonic equipment is initially 20-100 kHz, the duration is 5-10 minutes, the high frequency is 80-170 kHz, and the duration is 15-60 minutes.

[0022] Specifically, acetone has a strong polarity and can play a certain dispersing role on nano-metal oxides. Water can achieve dispersion through electrostatic effects and other methods, and can better meet the dispersion requirements of nano-metal oxides of different properties. The short stirring time of 5-10 minutes can quickly allow the nano-metal oxides to be initially dispersed in the newly added solvent system to avoid serious agglomeration caused by excessive local concentration. The high stirring speed of 500-800 rpm can quickly break the agglomeration state of the nano-metal oxides and quickly disperse the nanoparticles in the solvent. The long stirring time of 30-60 minutes can be used. The stirring time allows the nano-metal oxide to be fully dispersed in the solvent, so that the nanoparticles have enough time to separate from each other. The stirring speed of 200-300 rpm can avoid system instability or new agglomeration caused by excessive stirring during the continuous stirring stage. The initial frequency is 20-100 kHz, and the duration is 5-10 minutes. In this lower frequency range of ultrasonic treatment, the cavitation effect produced by ultrasound is relatively strong. The high frequency is 80-170 kHz, and the duration is 15-60 minutes. The cavitation bubbles produced by high-frequency ultrasound are smaller and more numerous, producing a milder microflow effect.

[0023] The nano metal oxides in S1 include nano titanium dioxide, nano zinc oxide, nano iron oxide, nano copper oxide, nano cerium oxide, nano aluminum oxide and nano silicon dioxide. The particle sizes of the various materials in the nano metal oxides are 10-50 nanometers for nano titanium dioxide, 20-80 nanometers for nano zinc oxide, 10-60 nanometers for nano iron oxide, 15-70 nanometers for nano copper oxide, 10-50 nanometers for nano cerium oxide, 10-80 nanometers for nano aluminum oxide and 10-80 nanometers for nano silicon dioxide. The mass percentages of the various materials in the nano metal oxides are 10%-15% for nano titanium dioxide, 10%-15% for nano zinc oxide, 10%-15% for nano iron oxide, 8%-12% for nano copper oxide, 8%-12% for nano cerium oxide, 10%-15% for nano aluminum oxide and 15%-22% for nano silicon dioxide. Micro-nano porous materials include porous silicon, porous silica, porous alumina, porous zinc oxide, conjugated microporous polymers, hyper-crosslinked polymers and organic framework materials. The pore size of each material in the micro-nano porous materials is 100-150 nanometers, porous silica 100-200 nanometers, porous alumina 150-200 nanometers, porous zinc oxide 100-150 nanometers, conjugated microporous polymers 100-200 nanometers, hyper-crosslinked polymers 100-200 nanometers and organic framework materials 110-200 nanometers. The mass percentage of each material is 5%-10% for porous silicon, 15%-20% for porous silica, 10%-15% for porous alumina, 8%-12% for porous zinc oxide, 15%-20% for conjugated microporous polymers, 12%-18% for hyper-crosslinked polymers and 10%-15% for organic framework materials.

[0024] Specifically, nano-titanium dioxide can produce hydroxyl radicals and superoxide anions with strong oxidative activity under light conditions. These active substances can destroy the cell walls and cell membranes of bacteria, causing the leakage of bacterial contents, thereby achieving a highly effective antibacterial effect, and has a significant inhibitory effect on common Gram-positive bacteria and Gram-negative bacteria such as Escherichia coli and Staphylococcus aureus. Nano zinc oxide can release zinc ions, which can combine with biological macromolecules such as proteins and nucleic acids in bacterial cells, interfere with the normal metabolic process of bacteria, inhibit the growth and reproduction of bacteria, and have good antibacterial activity against a variety of pathogenic bacteria such as Candida albicans and Salmonella; Nano-iron oxide can destroy the structure and function of bacteria by producing active oxygen species and interacting with bacterial cell membranes, and it also has a certain antibacterial ability against some drug-resistant bacteria; Nano copper oxide can release copper ions, which have antibacterial activity and can destroy the enzyme system and cell membrane of bacteria. It has a strong antibacterial effect on Escherichia coli, Pseudomonas aeruginosa, etc. Nano-cerium oxide has both antioxidant and antibacterial properties. It can interfere with the metabolic process of bacteria by regulating the redox state in cells, and has an inhibitory effect on some common pathogens such as Streptococcus and Klebsiella pneumoniae. Nano-alumina can absorb bacteria and destroy the cell membrane structure of bacteria, thus playing an antibacterial role and having a certain inhibitory effect on some common spoilage bacteria in food; Micro-nano porous materials such as porous silica, porous alumina, and porous zinc oxide can adsorb and fix nano-metal oxides, improve the stability and dispersibility of nano-metal oxides, and enable them to better play an antibacterial role; Although nano-silicon dioxide itself has weak antibacterial properties, it can be used as a carrier to load other antibacterial substances to enhance the overall antibacterial effect; Although nano-titanium dioxide and other materials have weak conductivity, they can improve the antistatic performance of materials by interacting with other conductive components. Nano-metal oxides such as nano-zinc oxide and nano-aluminum oxide have certain conductivity and can form a conductive network in the material to conduct away the static electricity generated on the surface of the material in time, thereby playing an antistatic role. Porous materials can be used as carriers of nano-metal oxides to improve the dispersibility and stability of nano-metal oxides, thereby enhancing the antistatic properties. The pore structure and surface properties of the porous material itself may also affect the antistatic properties of the material. Conductive polymers such as 3,4-ethylenedioxythiophene, 2,5-dimethylfuran and N-ethylcarbazole have good conductivity and can form continuous conductive channels in the material to quickly conduct static electricity and play a significant antistatic role. Conjugated microporous polymers, hyper-cross-linked polymers and organic framework materials have specific chemical structures and electronic properties. They can interact with nano-metal oxides and conductive polymers to adjust the conductive properties of the material and enhance the antistatic effect.

[0025] In S2, the initiator includes ammonium persulfate, p-toluenesulfonic acid and sodium dodecylbenzenesulfonate in a ratio of 1:2:1. The cleaning time of the cleaning device is 15-30 minutes, the ultrasonic frequency is 40-80kHz, the temperature of the vacuum drying oven is 60-80°C, the drying time is 12-24 hours, the stirring speed of the stirring device is 200-300 rpm, the stirring time is 1-2 hours, and the standing time after stirring is 30-60 minutes.

[0026] Specifically, ammonium persulfate, as a strong oxidant, can provide free radicals required for the reaction in the in-situ polymerization reaction, and initiate the polymerization reaction of the pyrrole monomer. On the one hand, p-toluenesulfonic acid, as a dopant, improves the conductivity of the polymer, and on the other hand, assists in initiating the polymerization reaction to a certain extent, improves the activity of the polymerization reaction and the performance of the polymer. Sodium dodecylbenzene sulfonate, as a surfactant, adjusts the surface activity of the reaction system, and helps to disperse the pyrrole monomer in the pores of the porous material and the uniformity of the polymerization reaction. The cleaning time of 15-30 minutes can ensure that unreacted monomers, initiators and other impurities are fully removed. The ultrasonic frequency is 40-80kHz. Ultrasonic waves in this frequency range can produce a certain intensity of cavitation effect and microflow effect, which helps to more thoroughly clean the product. impurities, temperature 60-80℃ this temperature range can not only effectively remove moisture and residual solvents in the product, but also avoid damage to the product structure and performance caused by excessively high temperature, drying time 12-24 hours longer drying time ensures that the product reaches constant weight, completely removes moisture and residual solvents, and ensures the stability and quality of the product, stirring speed 200-300 rpm this speed can make the monomer fully diffuse into the pores of the porous material and adsorb on the surface of the pores during the stirring process, stirring time 1-2 hours sufficient stirring time ensures that the monomer is fully adsorbed and diffused in the pores of the porous material, providing a good foundation for subsequent polymerization reactions, standing time 30-60 minutes standing time allows the monomer to further adsorb and balance in the pores to ensure uniform monomer concentration in the pores.

[0027] In S2, the conductive polymer monomers include 3,4-ethylenedioxythiophene, 2,5-dimethylfuran and N-ethylcarbazole, and the amount of the conductive polymer used is 1-5g of 3,4-ethylenedioxythiophene, 1-10g of 2,5-dimethylfuran and 0.1-0.5g of N-ethylcarbazole.

[0028] Specifically, although conductive polymers such as 3,4-ethylenedioxythiophene, 2,5-dimethylfuran, and N-ethylcarbazole are used in small amounts, they can synergize with nano-metal oxides and porous materials to enhance the overall antibacterial properties of the materials.

[0029] The fineness of the screen in S3 is 200-300 mesh, the crushing pressure of the above-mentioned crusher is 0.5-0.8MPa, the air flow velocity is 200-300m / s, the feed rate is 1-2kg / h, the crushing time is 30-90 minutes, and the sampling frequency is 15-30 minutes / time.

[0030] Specifically, the screen fineness is 200-300 mesh, and its function is to conduct preliminary screening of the composite functional powder obtained by in-situ polymerization treatment to remove possible large particle agglomerates or impurities. The crushing pressure is 0.5-0.8MPa. In the air flow mill, this pressure can make the high-pressure gas form a high-speed airflow in the crushing chamber. The airflow velocity is 200-300m / s, which can carry the powder particles in the crushing chamber at high speed, increase the collision frequency and intensity between the particles, and promote the crushing process. The feed rate is 1-2kg / h. Controlling the feed rate can ensure that the powder has enough time to interact with the high-speed airflow in the crushing chamber to achieve a good crushing effect. The crushing time is 30-90 minutes. The longer crushing time can ensure that the composite functional powder is fully affected by the high-speed airflow and is gradually crushed to the required particle size. The sampling frequency is 15-30 minutes / time. Regular sampling can timely understand the changes in the particle size of the powder during the crushing process, so as to adjust the crushing parameters to ensure that the required particle size requirements are met.

[0031] In S4, the resin matrix includes polyester or polyamide, the drying temperature during drying is 120-150°C, the drying time is 3-6 hours, the injection amount of supercritical carbon dioxide accounts for 10-50% of the total volume of the reaction system, the screw speed is 100-500 rpm, the temperature gradient from the hopper to the head is 200-280°C, and the internal residence time is 1-5 minutes.

[0032] Specifically, polyester usually has good mechanical properties, heat resistance and chemical stability, and is suitable for application scenarios with high requirements for strength and stability. Polyamide has excellent wear resistance, oil resistance and flexibility, and performs well in some occasions that require wear resistance and chemical corrosion resistance. The drying temperature is 120-150°C. This temperature range can effectively remove moisture from the resin matrix, and the drying time is 3-6 hours. Sufficient drying time ensures that the resin matrix reaches a fully dry state. The injection amount accounts for 10-50% of the total volume of the reaction system. Supercritical carbon dioxide plays an important role in the preparation of functional masterbatch. The basic and screw speed is 100-500 rpm. The screw speed has an important influence on the mixing effect and production efficiency in the twin-screw extruder. The temperature gradient from the hopper to the head is 200-280°C. During the extrusion process, the temperature of different parts needs to be gradually increased to ensure that the resin matrix can be fully melted and well mixed with the functional powder. The internal residence time is 1-5 minutes. Within this time range, the functional powder and the resin matrix can be fully mixed and reacted, and the supercritical carbon dioxide can play the best role.

[0033] In S5, the temperature of polymer drying treatment is 120-150℃, the drying time is 3-6 hours, the temperature of masterbatch preheating treatment is 50-80℃, the preheating time is 1-2 hours, the minimum feed rate of the constant feeder is 0.01-0.1g / min, the maximum feed rate is 10-50g / min, the screw speed is 1-1000 rpm, the diameter of the spinneret hole is 0.1-0.3mm, the spinneret pressure is 10-20MPa, the cooling medium is cold air, the wind speed is 0.3-0.8m / s, the temperature is 18-25℃, and the humidity is 60-70%.

[0034] Specifically, the drying temperature is 120-150℃, which can effectively remove moisture from the polymer. The drying time is 3-6 hours. Sufficient drying time ensures that the polymer reaches a fully dry state. The preheating temperature is 50-80℃, which can improve the fluidity of the functional masterbatch and make it easier to disperse evenly when mixed with the polymer. The preheating time is 1-2 hours. Appropriate preheating time can make the functional masterbatch fully heated and reach a stable temperature state. The minimum feed amount is 0.01-0.1g / min. This minimum feed amount determines the minimum amount of functional masterbatch that can be added under precise control. The maximum feed amount is 10-50g / min. The maximum feed amount limits the maximum amount of functional masterbatch that can be added within a certain period of time. Masterbatch, screw speed is 1-1000 rpm. The screw speed determines the delivery speed of the functional masterbatch. The diameter of the spinneret is 0.1-0.3mm. The diameter of the spinneret directly determines the fineness of the fiber. The spinneret pressure is 10-20MPa. The spinneret pressure affects the speed and shape of the spinning melt extruded from the spinneret. The cooling medium is cold air, and the wind speed is 0.3-0.8m / s. Cold air as a cooling medium can quickly reduce the temperature of the spinning melt extruded from the spinneret and solidify it into fiber. The temperature is 18-25℃. The temperature of the cooling air has an important influence on the cooling speed and performance of the fiber. The humidity is 60-70%. Appropriate humidity can prevent the fiber from generating static electricity during the cooling process, and also help to maintain the flexibility and strength of the fiber.

[0035] Table 1:

[0036] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A supercritical carbon dioxide-assisted functional masterbatch manufacturing process, characterized in that: The following steps are involved: S1. Nano-metal oxide loading: first, the nano-metal oxide is uniformly dispersed in a solvent, and then the nano-metal oxide is uniformly mixed with the solvent by a stirring device to form a dispersion of the nano-metal oxide, and then the micro-nano porous material is added to the dispersion, and the nano-metal oxide is uniformly loaded on the surface and pores of the porous material by ultrasound; S2, in-situ polymerization: first wash the micro-nano porous material in a suitable cleaning solution to remove impurities, then put the washed nanoporous material into a vacuum drying oven for drying, then prepare a monomer solution and an initiator solution, and then add a conductive polymer monomer to the porous material system loaded with nano metal oxides, and by adding an initiator, promote the conductive polymer monomer to polymerize in situ in the pores of the porous material, and stir at the same time to allow the monomer to fully diffuse into the pores of the porous material and adsorb on the surface of the pores; S3, pulverizing treatment: pouring the composite functional powder obtained by the in-situ polymerization treatment into a sieve for screening to remove large particle agglomerates or impurities, slowly adding the prepared composite functional powder into the feeding area of ​​the airflow pulverizer, and starting the airflow pulverizer; S4, masterbatch preparation: the composite functional powder after pulverization is measured, and then the resin matrix is ​​dried to remove moisture, and then the supercritical carbon dioxide injection equipment enters a supercritical state, and the pre-treated composite functional powder and resin matrix are respectively added to different hoppers of a reactive twin-screw extruder. During the extrusion process, supercritical carbon dioxide is injected into the twin-screw extruder, and then extruded, cooled and pelletized; S5. Preparation of functional fibers: First, the polymer is dried and the masterbatch is preheated. The functional masterbatch is added to the polymer spinning melt by a loss-in-weight feeder. After the functional masterbatch is added, the functional masterbatch and the spinning melt are fully mixed by the stirring and conveying action of the screw and the static mixer component in the pipeline. The fully mixed spinning melt containing the functional masterbatch is conveyed to the spinneret assembly, where it is extruded through the spinneret hole to form a thin stream. The functional fiber after drawing and cooling is wound onto the winding drum.

2. A supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: In S1, the solvent is acetone and water in a ratio of 1:

2. The initial stirring time of the nano metal oxide is 5-10 minutes, the stirring speed is 500-800 rpm, the continuous stirring is 200-300 rpm, the stirring time is 30-60 minutes, the frequency of the ultrasonic equipment is initially 20-100 kHz, the duration is 5-10 minutes, the high frequency is 80-170 kHz, and the duration is 15-60 minutes.

3. The supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: The nano metal oxides in S1 include nano titanium dioxide, nano zinc oxide, nano iron oxide, nano copper oxide, nano cerium oxide, nano aluminum oxide and nano silicon dioxide. The particle sizes of the various materials in the nano metal oxides are 10-50 nanometers for nano titanium dioxide, 20-80 nanometers for nano zinc oxide, 10-60 nanometers for nano iron oxide, 15-70 nanometers for nano copper oxide, 10-50 nanometers for nano cerium oxide, 10-80 nanometers for nano aluminum oxide and 10-80 nanometers for nano silicon dioxide. The mass percentages of the various materials in the nano metal oxides are 10%-15% for nano titanium dioxide, 10%-15% for nano zinc oxide, 10%-15% for nano iron oxide, 8%-12% for nano copper oxide, 8%-12% for nano cerium oxide, 10%-15% for nano aluminum oxide and 15%-22% for nano silicon dioxide. Micro-nano porous materials include porous silicon, porous silica, porous alumina, porous zinc oxide, conjugated microporous polymers, hyper-crosslinked polymers and organic framework materials. The pore size of each material in the micro-nano porous materials is 100-150 nanometers, porous silica 100-200 nanometers, porous alumina 150-200 nanometers, porous zinc oxide 100-150 nanometers, conjugated microporous polymers 100-200 nanometers, hyper-crosslinked polymers 100-200 nanometers and organic framework materials 110-200 nanometers. The mass percentage of each material is 5%-10% for porous silicon, 15%-20% for porous silica, 10%-15% for porous alumina, 8%-12% for porous zinc oxide, 15%-20% for conjugated microporous polymers, 12%-18% for hyper-crosslinked polymers and 10%-15% for organic framework materials.

4. The supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: In S2, the initiator includes ammonium persulfate, p-toluenesulfonic acid and sodium dodecylbenzenesulfonate in a ratio of 1:2:

1. The cleaning time of the cleaning device is 15-30 minutes, the ultrasonic frequency is 40-80kHz, the temperature of the vacuum drying oven is 60-80°C, the drying time is 12-24 hours, the stirring speed of the stirring device is 200-300 rpm, the stirring time is 1-2 hours, and the standing time after stirring is 30-60 minutes.

5. The supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: In S2, the conductive polymer monomers include 3,4-ethylenedioxythiophene, 2,5-dimethylfuran and N-ethylcarbazole, and the amount of the conductive polymer used is 1-5g of 3,4-ethylenedioxythiophene, 1-10g of 2,5-dimethylfuran and 0.1-0.5g of N-ethylcarbazole.

6. The supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: The fineness of the screen in S3 is 200-300 mesh, the crushing pressure of the above-mentioned crusher is 0.5-0.8MPa, the air flow velocity is 200-300m / s, the feed rate is 1-2kg / h, the crushing time is 30-90 minutes, and the sampling frequency is 15-30 minutes / time.

7. The supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: In S4, the resin matrix includes polyester or polyamide, the drying temperature during drying is 120-150°C, the drying time is 3-6 hours, the injection amount of supercritical carbon dioxide accounts for 10-50% of the total volume of the reaction system, the screw speed is 100-500 rpm, the temperature gradient from the hopper to the head is 200-280°C, and the internal residence time is 1-5 minutes.

8. The supercritical carbon dioxide-assisted functional masterbatch manufacturing process according to claim 1, characterized in that: In S5, the temperature of polymer drying treatment is 120-150℃, the drying time is 3-6 hours, the temperature of masterbatch preheating treatment is 50-80℃, the preheating time is 1-2 hours, the minimum feed rate of the constant feeder is 0.01-0.1g / min, the maximum feed rate is 10-50g / min, the screw speed is 1-1000 rpm, the diameter of the spinneret hole is 0.1-0.3mm, the spinneret pressure is 10-20MPa, the cooling medium is cold air, the wind speed is 0.3-0.8m / s, the temperature is 18-25℃, and the humidity is 60-70%.

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