WO2023030428A1 - 一种制备脂肪族二元酸尼龙的连续化工艺 - Google Patents

一种制备脂肪族二元酸尼龙的连续化工艺 Download PDF

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Publication number
WO2023030428A1
WO2023030428A1 PCT/CN2022/116429 CN2022116429W WO2023030428A1 WO 2023030428 A1 WO2023030428 A1 WO 2023030428A1 CN 2022116429 W CN2022116429 W CN 2022116429W WO 2023030428 A1 WO2023030428 A1 WO 2023030428A1
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dibasic acid
temperature
aliphatic dibasic
continuous process
polyamide
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PCT/CN2022/116429
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English (en)
French (fr)
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李洋
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成都肆零壹科技有限公司
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Publication of WO2023030428A1 publication Critical patent/WO2023030428A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a continuous process for preparing aliphatic dibasic acid nylon.
  • Nylon Nylon
  • nylon is a common name for polyamide, the English name is polyamide, and its molecular chain contains repeated amide functional groups.
  • the comprehensive advantages of nylon in terms of mechanical properties, weather resistance, corrosion resistance, high temperature resistance, and cost make it widely used in various fields such as electronics, machinery, fiber, and automobiles.
  • the raw materials used to synthesize nylon include diamines and dibasic acids, and dibasic acids include aliphatic and aromatic monomers.
  • the thermal stability of the aliphatic dibasic acid is poor, and it is easy to decompose at high temperature, which affects the occurrence of the polymerization reaction, thereby causing quality defects of the polymer, such as color changes, performance changes, and the like.
  • the most commonly used nylon polymerization process is to prepare a nylon salt with a dibasic acid and a diamine in a solvent at a lower temperature, so that the thermal stability of the aliphatic dibasic acid in the nylon salt is significantly improved, and then gradually Polymerization at elevated temperature, thereby reducing the decomposition of aliphatic dibasic acids and improving product quality. This process requires the preparation of a nylon salt solution in a solvent in advance, which consumes a large amount of water or organic solvents, and the solvent in the nylon salt solution will also be evaporated in the subsequent polymerization, which consumes a lot
  • CN112062950B has reported a kind of continuous nylon polymerization process, utilizes the nylon polymer of melting as reactive dispersion system, makes dibasic acid and dibasic amine react therein to form a salt, then polymerization takes place, as the nylon of dispersion system can become Part of the product, thereby avoiding the consumption of small molecule solvents and the energy consumption of evaporating small molecule solvents.
  • This method is more suitable for nylon with a high content of aromatic dibasic acid monomers, because usually nylon as a reactive dispersion system has a higher melting point, which makes the temperature for starting the reaction higher, which is not conducive to the stability of aliphatic dibasic acids , while aromatic dibasic acids have better thermal stability.
  • the present invention proposes a continuous process for preparing aliphatic dibasic acid nylon, which is an energy-saving, environment-friendly, green process with high production efficiency.
  • a continuous process for preparing aliphatic dibasic acid nylon The raw materials include polymerized monomers and polyamides.
  • the polymerized monomers include dibasic acids and dibasic amines.
  • the mass of aliphatic dibasic acids in the dibasic acids is The proportion accounts for 80-100%; the dibasic acid and polyamide raw materials are continuously put into a continuous mixing device with shear dispersion and conveying functions, the system temperature is lower than the melting point of polyamide raw materials, and polyamide raw materials are dispersed to the melting In the aliphatic dibasic acid, mix evenly to form a continuous flowing melt, then continuously add diamine, mix evenly, and then continuously enter the follow-up polymerization device for reaction until the nylon polymerization reaches the required molecular weight.
  • Dibasic acids and diamines are commonly used raw materials for nylon polymerization, but if only these two raw materials are used for polymerization in a continuous melting system, since neither of them has sufficient melt strength after melting, it cannot withstand the continuous mixing device.
  • the diamine and the dibasic acid meet at high temperature to polymerize and dehydrate to generate water vapor pressure, it will cause the leakage of water vapor, and will also bring out part of the polymerized monomer, making the ratio of acid and amine in the system unbalanced, so A certain amount of polyamide needs to be added to the raw material.
  • Polyamide is dispersed into molten aliphatic dibasic acid under the action of temperature and shear, which can provide sufficient melt strength to the melt.
  • Polyamide is a polymer product, which can undergo a reversible chemical reaction with a dibasic acid, has outstanding compatibility, and does not affect the performance of the polymer product.
  • the present invention utilizes the lower melting point of the aliphatic dibasic acid itself to control the mixing temperature of the dibasic acid and polyamide to be higher than the melting point of the aliphatic dibasic acid and lower than the melting point of the polyamide raw material.
  • the amide raw material is dispersed into the molten aliphatic dibasic acid during transportation, and mixed uniformly to form a continuously flowing melt.
  • the molecular weight of polyamide decreases sharply, and the melting and flowable temperature of low molecular weight nylon oligomers also decreases, thereby reducing the temperature at which the entire system can flow, satisfying the aliphatic
  • the stability of the dibasic acid monomer enables it to be transported stably in the continuous mixing device, ensuring the stability of the product.
  • the amount of polyamide in the final product is equal to the amount of polyamide in the raw material plus the amount of polyamide produced by the polymerization of the polymerized monomers. Therefore, the difference between the amount of polyamide in the product minus the amount of polyamide raw material is the actual output of the process.
  • the polymerization reaction time is the time for the material to flow through the effective volume of the entire device, so the total output of the device is inversely proportional to the polymerization reaction time. In order to ensure the stability of the final product, it is necessary to control a certain polymerization time.
  • the total amount of the final product is also constant.
  • the amount of polyamide used in the raw material should be as small as possible, so as to increase the proportion of the polymer produced by the actual monomer polymerization in the total product.
  • the molten aliphatic dibasic acid has a relatively high polarity, which enables the polyamide to dissolve in it. Since the polymerization of amide is a reversible reaction, the dissolved polyamide will undergo acidolysis reaction, the molecular weight will decrease, the solubility will be further increased, and the melt softening temperature will also decrease. However, if the degree of acid hydrolysis is too large, the strength after melting and softening will be too low, or it will be completely liquefied.
  • the temperature of the melting and dispersing section of the present invention can be lower than the melting point of the polyamide raw material, thereby reducing the degree of acidolysis of the polyamide raw material, so that the melt after melting and mixing of dibasic acid and polyamide has a certain polyamide ratio in the raw material. Greater melt strength.
  • the melt strength after mixing is the key factor to withstand the vapor pressure generated by dehydration during the polymerization of diamines and dibasic acids.
  • the completely liquefied mixture cannot withstand the pressure of high-temperature water vapor, so the cylinder of the mixture must have sufficient strength. Therefore, the relatively low temperature of the melting and dispersing section can better maintain the strength of the melt after mixing, and can reduce the proportion of polyamide in the raw material and increase the proportion of polymerized monomers.
  • the actual production efficiency of the device can be lower than the melting point of the polyamide raw material, thereby reducing the degree of acidolysis of the polyamide raw material, so that the melt after melting and mixing of dibasic acid and polyamide
  • the mass ratio of the aliphatic dibasic acid to the polyamide raw material in the present invention is 0.5-50:1. If the amount of polyamide raw material is too small, it cannot enhance the melt strength; if the amount is too large, the utilization rate of the equipment will be lost.
  • the ratio of 0.5-50:1 can ensure the actual production efficiency of the device, and can also provide enough strength for the melt to withstand the pressure of water vapor generated by dehydration. When the weight of the required polyamide raw material exceeds 50% of the total weight of the raw material to have sufficient melt strength to achieve the sealing effect, the actual output of the process is too low. Compared with the traditional nylon polymerization process, the advantage is not obvious, so this method is not recommended Invention method.
  • the mixing temperature of the dibasic acid and the polyamide raw material of the present invention is higher than the melting point of at least one aliphatic dibasic acid raw material, so as to ensure that at least one aliphatic dibasic acid raw material can form a melt in the device, so that other materials can be processed in the device. Uniformly dispersed in the melt under the action of shear.
  • the dibasic acid and polyamide raw materials of the present invention are evenly mixed to obtain a mixed melt, and at least one section of the device before the diamine is added is filled with the mixed melt to form a sealing section.
  • the subsequent addition of diamine and dibasic acid will dehydrate when they meet, and there will be high-temperature water vapor in the system. Therefore, it is necessary to fill a period of time with the melt of the mixture formed by dibasic acid and polyamide in the raw material before adding dibasic amine.
  • the material mixing and conveying device can avoid the leakage of water vapor, and also avoid the leakage of oxygen into the subsequent polymerization process and the leakage of diamine monomer, resulting in quality problems.
  • the melting temperature of the sealing section is lower than the mixing temperature of dibasic acid and polyamide raw materials.
  • the melt strength increases under the action of polyamide, which can achieve the effect of sealing and form a sealing section. Due to the presence of amide oligomers in the melt mixture formed by the dibasic acid and polyamide, the melting point of the dibasic acid in the melt will be further reduced, so that the softening temperature of the entire melt is lower than the melting point of the dibasic acid in the raw material. At this time, when the sealing section lowers the system temperature to below the melting point of the aliphatic dibasic acid raw material, the melt can still have proper fluidity. At the same time, lowering the system temperature is beneficial to further increase the strength of the melt. Therefore, it is further preferred that the sealing section has a melt temperature lower than the melting point of at least one aliphatic dibasic acid in molten state.
  • the aliphatic dibasic acid in the present invention is at least one selected from dibasic acids with 6-18 carbon atoms.
  • the aliphatic dibasic acid in the raw material contains adipic acid.
  • adipic acid has the highest melting point, about 155°C. The melt formed by adipic acid can maintain sufficient strength at higher temperatures, and the operating window is wider.
  • adipic acid is also the most polar among these dibasic acids, and has the best compatibility with the most commonly used nylons, such as PA6 and PA66, and has the best compatibility with other monomers used to prepare high-temperature-resistant nylon. , its melt can better melt nylon products with relatively high melting point, and it is more convenient to prepare copolymerized nylon with higher temperature resistance.
  • the nylon produced by the polymerization of adipic acid has the best temperature resistance and the widest application space.
  • the continuous mixing device of the present invention is a screw extrusion device. All continuous mixing devices with shear dispersion conveying function can be used as appropriate, preferably screw extrusion devices.
  • the most commonly used screw extrusion device is a twin-screw extrusion device.
  • the thread combination design of the screw extrusion device is flexible, and different conveying and shearing dispersion capabilities can be designed in different stages according to needs.
  • the screw extrusion device has a material dispersing ability and an interface renewal ability far exceeding that of a general mixing device, which can quickly mix the polymer raw material and the molten dibasic acid evenly, and make the heat generated when the diamine and the dibasic acid form a salt It can disperse quickly, so that the temperature of the material will not be too high, and it can better avoid the problems of yellowing color caused by local high temperature, low polymer melt strength and other problems that affect production stability and quality.
  • the diamine of the present invention is preferably fed into the continuous mixing device in liquid form.
  • the diamine can be melted into a liquid state, or dissolved in a small molecule solvent, and added to the material mixing device in liquid form, which makes it easier to ensure the sealing performance of the mixing device and prevent the loss of volatile raw materials.
  • the materials are preferably provided with a section of upward flow, so that the melt formed by the materials can form a sealing section when flowing upward even at a lower viscosity, and the upper space of the device will not be blocked due to low viscosity. Being full causes a large amount of gaseous diamine to overflow.
  • the molar ratio of dibasic acid and dibasic amine in the polymerized monomer of the present invention is 1:0.8-1.2.
  • the molar ratio of the diamine and the dibasic acid involved in the polymerization is close to 1 to obtain a higher molecular weight polymer, and the volatility of the dibasic amine is usually higher than that of the dibasic acid.
  • Nylon oligomers with unbalanced amine value and acid value or polymer raw materials with unequal carboxyl and amino functional groups will affect the final polymer molecular weight.
  • the binary monomer of the raw material repolymerization
  • the molar ratio of acid and diamine is 1:0.8-1.2.
  • the polyamides in the raw materials of the present invention are selected from PA66, PA56, PA610, PA612, PA1010, PA1212, PAMXD6, or copolymers based on these polyamide structures, preferably PA66, PA56, PAMXD6, among these three polyamides All dibasic acid monomers are adipic acid, and the whole device has a larger operating space.
  • the subsequent polymerization device in the present invention is at least one of a screw extrusion device, a tubular reaction device and a tank reaction device.
  • Subsequent polymerization units may be sequentially connected continuous flow reactors or screw extrusion units.
  • the continuous flow reactor is a type of continuous polymerization reactor, which can be in the form of a pipeline, a reactor or a tower. It mainly ensures that the material in and out is continuously flowing. Ideally, there is no backflow, and all materials are in it. The residence time is equal.
  • the continuous flow reactor can control the time of material polymerization, so as to obtain polymers with different molecular weights.
  • the device is also preferably a polymerization device with continuous flow and discharge of the material, which is most beneficial to realize continuous production.
  • the screw extruder is devolatilized, extruded and granulated.
  • the polyamide polymerization process there will be small molecules released, and the production can be completely continuous through the devolatilization of the screw extrusion device.
  • a screw extrusion device can be added directly behind to continue polymerization and remove volatilized small molecules, so that the materials can be further homogenized.
  • the method of adding various raw materials in the present invention is very flexible. It can be added to the feed section at the same time at the machine head, or part of the raw materials can be added in the middle of the equipment through side feeding or liquid pumping. Even the same raw material can also be added at the same time. Add in batches at different positions to further make the mixing more uniform.
  • the total average residence time of the material in the material mixing device and subsequent polymerization device from feeding to discharging in the present invention is 10-120 min.
  • the rate of the polymerization reaction is related to the temperature.
  • the high temperature polymerizes quickly and the efficiency is high, but too high temperature will cause a series of problems such as yellowing and degradation, so it is necessary to balance the relationship between reaction temperature and time.
  • the average residence time of the material in the present invention from feeding to discharging in the material mixing device and subsequent polymerization device is preferably 10-120min. It can be estimated by the time for the volume of the mixed material to fill the effective volume of all mixing and polymerization devices under a certain output.
  • the average residence time of the material in the device is theoretically the same, which can avoid the discontinuous process due to the different residence time of the material caused by the feeding and discharging sequence, resulting in molecular weight loss. uneven.
  • the polymerization time can be adjusted by adjusting the total feed amount, so as to prepare polymers with different molecular weights to meet the needs of different applications.
  • changing the output of the device can change the polymerization reaction time, thereby controlling the molecular weight of the product; controlling the feeding ratio of different materials can conveniently control the composition of the copolymerization unit, thereby obtaining products with different physical properties.
  • the same set of equipment can realize the production of products with different performances and improve the flexibility of production. All adjustments can be done online to avoid waste caused by intermittent process switching and product downtime.
  • the polymerization method of the present invention utilizes the relatively low melting point of the aliphatic dibasic acid itself, and the polyamide raw material is dispersed into the molten aliphatic dibasic acid during the transportation process, and mixed uniformly to form a melt that can flow continuously. Due to the reversible reaction between polyamide and liquid dibasic acid, the molecular weight of polyamide decreases sharply, and the melting and flowable temperature of low molecular weight nylon oligomers also decreases, thereby reducing the temperature at which the entire system can flow, satisfying the aliphatic The stability of the dibasic acid monomer enables it to be transported stably in the continuous mixing device, ensuring the stability of the product.
  • polyamide is dispersed into the molten aliphatic dibasic acid under the action of temperature and shear, which can provide sufficient melt strength to the melt, so that the material can be continuously conveyed forward, and realizes feeding, reaction and discharging.
  • the continuity of the process overcomes the intermittent production shortcomings of the traditional reactor process.
  • the present invention omits the step of preparing nylon salt in aqueous solution, avoids the generation of waste liquid in the preparation process of nylon salt, and is a green and environment-friendly nylon synthesis method. It has the characteristics of high production efficiency, low energy consumption, energy saving and environmental protection, and is easy to be popularized and applied on a large scale in actual production. No small molecule solvent is used in the process of forming the nylon salt, which saves water and energy.
  • the temperature of the system in the sealing section is lowered to below the melting point of the molten aliphatic dibasic acid, which can still make the melt have proper fluidity, and is conducive to further improving the strength of the melt and ensuring the sealing sex.
  • the continuous nylon polymerization method of the present invention avoids the problem of unstable product quality caused by batch production, and is not affected by factors such as temperature and pH value in the preparation process of nylon salt in aqueous solution, and the obtained nylon product has uniform Good performance and stable quality.
  • a continuous process for preparing aliphatic dibasic acid nylon the raw materials include polymerized monomers and polyamides, and the polymerized monomers include aliphatic dibasic acids and diamines; aliphatic dibasic acids and polyamide raw materials are continuously
  • a continuous mixing device with shear dispersion and conveying functions is put into operation. The temperature of the system is lower than the melting point of the polyamide raw material.
  • the polyamide raw material is dispersed into the molten aliphatic dibasic acid during the conveying process and mixed evenly to form a continuous flowing melt. , and then continuously add diamine, mix evenly and then continuously enter the follow-up polymerization device for reaction until the nylon polymerization reaches the required molecular weight.
  • a continuous process for preparing aliphatic dibasic acid nylon The raw materials include polymerized monomers and polyamides.
  • the polymerized monomers include dibasic acids and dibasic amines.
  • the mass of aliphatic dibasic acids in the dibasic acids is The proportion accounts for 80%; the dibasic acid and polyamide raw materials are continuously put into a continuous mixing device with shear dispersion and conveying functions, the system temperature is lower than the melting point of polyamide raw materials, and polyamide raw materials are dispersed into molten fat during conveying In the dibasic acid, mix evenly to form a continuous flowing melt, then continuously add diamine, mix evenly, and then continuously enter the subsequent polymerization device for reaction until the nylon polymerization reaches the required molecular weight.
  • the mass ratio of the aliphatic dibasic acid to the polyamide raw material is 50:1, and the effective yield is about 45%.
  • the dibasic acid and polyamide raw materials are mixed at a temperature above the melting point of at least one aliphatic dibasic acid raw material.
  • Dibasic acid and polyamide raw materials are evenly mixed to obtain a mixed melt, and at least one section of the device before the diamine is added is filled with the mixed melt to form a sealed section.
  • the melting temperature of the sealing section is lower than the mixing temperature of dibasic acid and polyamide raw materials.
  • the subsequent polymerization device is a screw extrusion device.
  • a continuous process for preparing aliphatic dibasic acid nylon The raw materials include polymerized monomers and polyamides.
  • the polymerized monomers include dibasic acids and dibasic amines.
  • the mass of aliphatic dibasic acids in the dibasic acids is The ratio accounts for 90%; the dibasic acid and polyamide raw materials are continuously put into a continuous mixing device with shear dispersion and conveying functions, the system temperature is lower than the melting point of polyamide raw materials, and polyamide raw materials are dispersed into molten fat during conveying In the dibasic acid, mix evenly to form a continuous flowing melt, then continuously add diamine, mix evenly, and then continuously enter the subsequent polymerization device for reaction until the nylon polymerization reaches the required molecular weight.
  • the mass ratio of the aliphatic dibasic acid to the polyamide raw material is 40:1.
  • the dibasic acid and polyamide raw materials are mixed at a temperature above the melting point of at least one aliphatic dibasic acid raw material.
  • Dibasic acid and polyamide raw materials are evenly mixed to obtain a mixed melt, and at least one section of the device before the diamine is added is filled with the mixed melt to form a sealed section.
  • the melting temperature of the sealing section is lower than the mixing temperature of dibasic acid and polyamide raw materials.
  • the aliphatic dibasic acid is at least one selected from dibasic acids with 6-18 carbon atoms.
  • the diamine is fed into the continuous mixing device in liquid form.
  • the subsequent polymerization device is a screw extrusion device and a tank reaction device.
  • the total average residence time of the material in the material mixing device and subsequent polymerization device is 10-120min.
  • a continuous process for preparing aliphatic dibasic acid nylon The raw materials include polymerized monomers and polyamides.
  • the polymerized monomers include dibasic acids and dibasic amines.
  • the mass of aliphatic dibasic acids in the dibasic acids is The ratio accounts for 95%; the dibasic acid and polyamide raw materials are continuously put into a continuous mixing device with shear dispersion and conveying functions.
  • the temperature of the system is lower than the melting point of the polyamide raw materials, and the polyamide raw materials are dispersed into the molten fat In the dibasic acid, mix evenly to form a continuous flowing melt, then continuously add diamine, mix evenly, and then continuously enter the subsequent polymerization device for reaction until the nylon polymerization reaches the required molecular weight.
  • the mass ratio of the aliphatic dibasic acid to the polyamide raw material is 30:1.
  • the dibasic acid and polyamide raw materials are mixed at a temperature above the melting point of at least one aliphatic dibasic acid raw material.
  • Dibasic acid and polyamide raw materials are evenly mixed to obtain a mixed melt, and at least one section of the device before the diamine is added is filled with the mixed melt to form a sealed section.
  • the melt temperature of the sealing segment is lower than the melting point of the molten aliphatic dibasic acid.
  • the diamine is preferably fed into the continuous mixing device in liquid form.
  • the molar ratio of dibasic acid and dibasic amine in the polymerized monomer is 1:0.8-1.2.
  • the polyamide in the raw material is selected from PA66, PA56, PA610, PA612, PA1010, PA1212, PAMXD6, or copolymers mainly based on these polyamide structures.
  • the subsequent polymerization device is a screw extrusion device and a tubular reaction device.
  • the total average residence time of the material in the material mixing device and subsequent polymerization device is 10-120min.
  • a continuous process for preparing aliphatic dibasic acid nylon The raw materials include polymerized monomers and polyamides.
  • the polymerized monomers include dibasic acids and dibasic amines.
  • the mass of aliphatic dibasic acids in the dibasic acids is The ratio accounts for 95%; the dibasic acid and polyamide raw materials are continuously put into a continuous mixing device with shear dispersion and conveying functions.
  • the temperature of the system is lower than the melting point of the polyamide raw materials, and the polyamide raw materials are dispersed into the molten fat In the dibasic acid, mix evenly to form a continuous flowing melt, then continuously add diamine, mix evenly, and then continuously enter the subsequent polymerization device for reaction until the nylon polymerization reaches the required molecular weight.
  • the mass ratio of the aliphatic dibasic acid to the polyamide raw material is 25:1.
  • the dibasic acid and polyamide raw materials are mixed at a temperature above the melting point of at least one aliphatic dibasic acid raw material.
  • Dibasic acid and polyamide raw materials are evenly mixed to obtain a mixed melt, and at least one section of the device before the diamine is added is filled with the mixed melt to form a sealed section.
  • the melt temperature of the sealing segment is lower than the melting point of the molten aliphatic dibasic acid.
  • the aliphatic dibasic acid is adipic acid.
  • the diamine is preferably fed into the continuous mixing device in liquid form.
  • the molar ratio of dibasic acid and dibasic amine in the polymerized monomer is 1:0.8-1.2.
  • the polyamides in the raw materials are selected from PA66, PA56, PAMXD6 or copolymers based on these polyamide structures.
  • the subsequent polymerization device is a tubular reaction device.
  • the method of adding various raw materials in the present invention is very flexible. It can be added to the feed section at the same time at the machine head, or part of the raw materials can be added in the middle of the equipment through side feeding or liquid pumping. Even the same raw material can also be added at the same time. Add in batches at different positions to further make the mixing more uniform.
  • the total average residence time of the material in the material mixing device and subsequent polymerization device from feeding to discharging in the present invention is 10-120 min.
  • the temperature of the three-section cylinder where the diamine has just been added is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 248°C, continuous extrusion and granulation to obtain PAMXD6 resin, the average residence time of the material in the device is 30 minutes, the melting point is 243°C, the viscosity is 2.3, the color is white, and the effective yield is about 85%.
  • the power consumption of the device is about 197 degrees per hour.
  • the weight ratio of 4:1 mix adipic acid, PAMXD6 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst, and send it from the front end through the weight loss metering device to a series co-direction double
  • the screw extruder unit set the temperature of the screw feeding section to 100-120°C, the temperature of the melting and dispersing section to 160-220°C, and set the temperature of the melt sealing section to 145°C after the material is dispersed, and then add m-xylylenediamine through weight loss control , so that the molar ratio of m-xylylenediamine to adipic acid is 1.01:1, the temperature of the three-section cylinder just after m-xylylenediamine is added is set to 180°C, a slight air leakage occurs at the screw packing, and then the temperature is gradually raised , and then enter the continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the head temperature is set at 248°C, and the material is continuously extruded and cooled in water to obtain PAMXD6 resin, which cannot be pelletized.
  • the average residence time of the material in the device is 30 minutes, the melting point is 239°C, the viscosity is 1.6, the color is yellow, the effective yield is about 85%, and the power consumption of the device is 205 degrees per hour.
  • the ratio of PAMXD6 in the raw material is increased to a ratio of adipic acid to PAMXD6 resin of 2:1, and the temperature of the melting and dispersing section is 160-220°C. Without air leakage, PAMXD6 resin was obtained with an effective yield of about 75%.
  • the power consumption of the device is 215 degrees per hour.
  • the raw materials and consumption of embodiment 7 and embodiment 6 are all the same, and the mixing temperature of melting and dispersing section is higher than embodiment 6, and under the same equipment condition, at this moment, slight air leakage occurred at the screw packing place of the melting mixing extruder, indicating As the temperature of the mixing process increases, the molecular weight of the polymer in the raw material decreases more, resulting in lower melt strength and poor sealing effect. The quality of the product produced by polymerization under this condition is obviously not as good as that of Example 6, and the energy consumption is higher.
  • Example 8 After increasing the proportion of polyamide raw materials on the basis of Example 6, the melt strength increases, and the mixing uniformity and system tightness can also be satisfied at a higher mixing temperature, without air leakage, but the effective output Reduced, loss of equipment utilization. At the same time, more energy is consumed because more polymer needs to be melted initially, resulting in an increase of about 8% in energy consumption. Therefore, although the equipment has not been optimally optimized, comparisons under the same conditions have shown that the lower mixing temperature is more conducive to reducing the proportion of polymer in the raw material, thereby improving the effective mixing process. output, improve device utilization, and increase production efficiency.
  • the temperature of the three-section cylinder just added with hexamethylenediamine is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 260°C, continuous extrusion granulation, to obtain PA66 resin, the average residence time of the material in the device is 30 minutes, the melting point is 268°C, the viscosity is 2.3, and the color is white.
  • the effective yield is 82%, and the average power consumption of the whole set of equipment is about 202 degrees per hour.
  • the weight ratio of 3:1 mix adipic acid, PA66 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst, and send it from the front end through the weight loss metering device to a series co-direction bidirectional with a total length to diameter ratio of 100:1
  • the screw extruder unit set the temperature of the screw feeding section to 100-150°C, the temperature of the melting and dispersing section to 160-280°C, and set the temperature of the melt sealing section to 130°C after the material is dispersed, and then control the added hexamethylenediamine through weight loss,
  • the molar ratio of hexamethylenediamine and adipic acid is 1.01:1.
  • the temperature of the three-section barrel just after hexamethylenediamine was added was set at 180°C, and the packing of the screw extrusion device was seriously leaked, making it impossible to form a seal.
  • the temperature of the three-section cylinder just added with hexamethylenediamine is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 268°C, continuous extrusion and granulation to obtain PA66 resin, the average residence time of the material in the device is 30 minutes, the melting point is 263°C, the viscosity is 2.1, and the color is yellow.
  • the effective yield is 68%, and the average power consumption of the whole set of equipment is 245 degrees per hour.
  • the added hexamethylenediamine was controlled by weight loss, so that the molar ratio of hexamethylenediamine and adipic acid was 1.01:1.
  • the temperature of the three-section cylinder just added with hexamethylenediamine is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 260°C, continuous extrusion and granulation, to obtain PA66 resin, the average residence time of the material in the device is 30 minutes, the melting point is 261°C, the viscosity is 2.1, the color is yellow, the effective yield is 82%, and the device operation consumes The electricity is 223 degrees per hour.
  • the temperature of the three-section cylinder just added with hexamethylenediamine is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 260°C, continuous extrusion and granulation to obtain PA66 resin, the average residence time of the material in the device is 60 minutes, the melting point is 269°C, the viscosity is 2.8, and the color is slightly yellow.
  • the effective yield is 82%, the average power consumption of the whole device is about 174 degrees per hour, and the total output of the device is about 149kg/h.
  • Example 10 on the basis of Example 9, the mixing temperature of the melting and dispersing section was increased to 280°C, which exceeded the melting point of PA66 resin, and the molecular weight of PA66 resin decreased more sharply, so that the melt strength was significantly reduced, and the seal could not be formed, and the process could not Continue;
  • Example 11 improves the weight ratio of PA66 resin and adipic acid in the raw material to 1:1.5 on the basis of Example 9 to increase the melt strength. Under the amount of raw material, the actual effective yield of the device is reduced by about 14 %, energy consumption increases by about 20%, this adjustment scheme is not recommended.
  • Example 12 On the basis of Example 9, the mixing temperature of the melting and dispersing section is also increased to 280°C, but the seal cannot be formed. On the premise of not increasing the amount of PA66 resin, Example 12 is lowered to a lower temperature in the sealing section To 95 °C to increase the melt strength, which requires a longer transmission distance to achieve cooling. Therefore, the position of adding hexamethylenediamine in Example 12 is two sections later than in Example 9, which in fact increases the requirements for the device, and the melting point of the obtained product is on the low side, the color is also more difficult to control, and the energy consumption has also increased by 10%. .
  • Example 13 reduces the total output, prolongs the polymerization reaction time, and obtains a polymer with a larger molecular weight. It shows that the method of the present invention can prepare products with different molecular weights by controlling the polymerization reaction time to meet different demands. Due to the doubling of the reaction time, the total output is reduced by about half from 305 kg/h in Example 9 to 149 kg/h, the actual effective output ratio of the device remains unchanged, and the energy consumption is reduced by about 14%.
  • the effective volume is 150 liters
  • the total output corresponding to the polymerization time of 30 minutes is about 300 kg/h
  • the total output corresponding to the polymerization time of 60 minutes is about 150 kg/h.
  • the temperature of the three-section cylinder just after pentamethylenediamine is added is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-280°C, and then enters the
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 250°C, continuous extrusion and granulation to obtain PA56 resin, the average residence time of the material in the device is 30 minutes, the melting point is 252°C, the viscosity is 2.2, and the color is white.
  • the weight ratio of 8:1 mix sebacic acid, PA610 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst, and send it from the front end through the weight loss metering device to a series co-direction bidirectional with a total length to diameter ratio of 100:1
  • the screw extruder unit set the temperature of the screw feeding section to 100-120°C, and the temperature of the melting and dispersing section to 120-190°C. After the material is dispersed, the temperature of the melt sealing section is maintained at 155°C at the end of the dispersion.
  • the packing of the screw extrusion device has a slight air leakage, and then the temperature is gradually raised, and then enters the continuous flow reaction with an effective volume of 150L equipped with an active stirring device
  • the temperature of the polymerization section is 220-285°C, and then it enters a co-rotating twin-screw extruder with a length-to-diameter ratio of 48:1.
  • the head temperature was set at 220°C, continuous extrusion, strand granulation was not possible, and the obtained PA610 resin was collected in water.
  • the average residence time of the material in the device is 30 minutes, the melting point is 218°C, the viscosity is 1.6, and the color is light yellow.
  • the weight ratio of 8:1 mix sebacic acid, PA610 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst, and send it from the front end through the weight loss metering device to a series co-direction bidirectional with a total length to diameter ratio of 100:1
  • the screw extruder unit set the temperature of the screw feed section to 100-120°C, the temperature of the melting and dispersing section to 120-190°C, and set the temperature of the melt sealing section to 95°C after the material is dispersed, and then control the added hexamethylenediamine through weight loss,
  • the molar ratio of hexamethylenediamine and sebacic acid is 1.02:1.
  • the temperature of the three-section cylinder just added with hexamethylenediamine is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 220°C, continuous extrusion granulation, to obtain PA610 resin, the average residence time of the material in the device is 30 minutes, the melting point is 224°C, the viscosity is 2.3, and the color is white.
  • Example 16 The temperature of the melt sealing section of Example 15 is not lowered, and remains above the melting point of sebacic acid. Under continuous transportation at this temperature, the melt strength is not enough, and there is a slight air leakage phenomenon, resulting in a serious decline in the quality of the polymerized product; implementation In Example 16, the temperature of the sealing section of the melt is lowered below the melting point of sebacic acid, the melt can still maintain fluidity, and the melt strength is improved without air leakage.
  • dodecanedioic acid, PA612 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst are mixed, and the weight loss metering equipment is sent from the front end to a series with a total length-to-diameter ratio of 100:1.
  • the twin-screw extruder unit set the temperature of the screw feeding section to 90-105°C, the temperature of the melting and dispersing section to 120-190°C, and set the temperature of the melt sealing section to 85°C after the material is dispersed.
  • Amines such that the molar ratio of hexamethylenediamine to dodecanedioic acid is 1.02:1.
  • the temperature of the three-section cylinder just added with hexamethylenediamine is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 220°C, continuous extrusion and granulation to obtain PA612 resin, the average residence time of the material in the device is 30 minutes, the melting point is 205°C, the viscosity is 2.1, and the color is white.
  • dodecanedioic acid, PA1212 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst are mixed, and the weight loss metering equipment is sent from the front end to a series with a total length-to-diameter ratio of 100:1.
  • the twin-screw extruder unit set the temperature of the screw feeding section to 90-95°C, the temperature of the melting and dispersing section to 120-160°C, and set the temperature of the melt sealing section to 75°C after the material is dispersed, and then add twelve alkanediamine, so that the molar ratio of dodecanediamine and dodecanedioic acid is 1.01:1.
  • the temperature of the three-section cylinder where the diamine has just been added is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 180°C, continuous extrusion granulation, to obtain PA1212 resin, the average residence time of the material in the device is 30 minutes, the melting point is 178°C, the viscosity is 2.1, the color is white, and the effective yield is 97%.
  • the temperature of the three-section cylinder where the diamine has just been added is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 220°C, continuous extrusion granulation, to obtain PA1010 resin, the average residence time of the material in the device is 30 minutes, the melting point is 192°C, the viscosity is 2.1, the color is white, the effective yield is 95%, and the average The electricity consumption is 194 degrees per hour.
  • the weight ratio of 9:1 mix sebacic acid, PA1010 resin, 0.5% of the total weight of antioxidant, and 0.2% of the catalyst, and send it from the front end through the weight loss metering device to a series co-directional double
  • the screw extruder unit set the temperature of the screw feed section to 100-120°C, the temperature of the melting and dispersing section to 120-230°C, and set the temperature of the melt sealing section to 95°C after the material is dispersed, and then control the added hexamethylenediamine through weight loss,
  • the molar ratio of hexamethylenediamine and sebacic acid is 1.01:1.
  • the temperature of the three-section cylinder just after decanediamine was added was set to 180°C, and at this time, the screw packing of the mixing device began to leak air.
  • the temperature is gradually raised, and then it enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device. There are three vents, and the last two vents are vacuumed.
  • the head temperature is set at 220°C, continuous extrusion granulation, to obtain PA1010 resin, the average residence time of the material in the device is 30 minutes, the melting point is 193°C, the viscosity is 2.2, the color is white, the effective yield is 75%, and the average The electricity consumption is 213 degrees per hour.
  • Example 20 has the same raw materials and dosage as Example 19, and the mixing temperature of the melting and dispersing section is higher than that of Example 19, exceeding the melting point of the PA1010 resin, which reduces the molecular weight of the polymer more, resulting in a decrease in the strength of the melt, requiring more Therefore, increasing the ratio of PA1010 to 3:1, the energy consumption and total output remain unchanged, the actual production efficiency is reduced, the effective yield is reduced from 95% to 75%, and due to the need for remelting The increase in the amount of polymer increases the energy consumption of the entire device by 10%.
  • the composition of the dibasic acid in the raw material is adipic acid and terephthalic acid in a weight ratio of 5:1.
  • the temperature of the screw feeding section is set at 100-150°C, and the temperature of the melting and dispersing section is 160-200°C. After the material is dispersed, it is melted.
  • the temperature of the sealing section of the body is set to 110°C, and then the added hexamethylenediamine is controlled through weight loss, so that the molar ratio of hexamethylenediamine to adipic acid is 1.01:1.
  • the temperature of the three-section cylinder where the diamine has just been added is set at 180°C, and then the temperature is gradually raised, and then enters a continuous flow reactor with an effective volume of 150L equipped with an active stirring device.
  • the temperature of the polymerization section is 220-285°C, and then enters the long diameter
  • the co-rotating twin-screw extruder with a ratio of 48:1 has three vent holes, and the last two vent holes are vacuumed.
  • the head temperature is set at 260°C, continuous extrusion granulation, to obtain PA66/6T copolymer resin, the average residence time of the material in the device is 30 minutes, the melting point is 272°C, the viscosity is 2.2, and the color is white.
  • the composition of the dibasic acid in the raw material is sebacic acid and terephthalic acid in a weight ratio of 5:1.
  • the temperature of the screw feeding section is set at 100-150°C, and the temperature of the melting and dispersing section is 160-245°C.
  • the material cannot be well dispersed. , continue to heat up to 275 ° C to be well dispersed, and the packing of the screw extrusion device has serious air leakage and cannot form a seal.
  • the composition of the dibasic acid in the raw material is dodecanedioic acid and terephthalic acid in a weight ratio of 5:1.
  • the temperature of the screw feeding section is set at 100-150°C, and the temperature of the melting and dispersing section is 160-245°C.
  • the material cannot be well dispersed. , continue to heat up to 275 ° C to be well dispersed, and the packing of the screw extrusion device has serious air leakage and cannot form a seal.
  • the method of the present invention can also be used for synthesizing the copolymerized nylon that has aromatic dibasic acid monomer, but because aromatic dibasic acid has higher fusing point, must guarantee that the ratio of aromatic dibasic acid is no more than 20%, just can be in raw material
  • the dibasic acid and polyamide are mixed evenly below the melting point of the polymer.
  • the mixed dibasic acid in Example 21 uses adipic acid and terephthalic acid, and a uniformly dispersed melt can be obtained at a mixing temperature of 160-200°C, and the polyamide product can be obtained smoothly by continuing the polymerization reaction.
  • Examples 22 and 23 respectively use sebacic acid and dodecanedioic acid to replace the adipic acid in Example 21, and a uniformly dispersed melt can be obtained at a mixing temperature of 275°C under the same amount of polymer, because the mixing temperature exceeds If the melting point of PA66 resin is lowered, the PA66 resin will also melt, and the molecular weight of the polymer will decrease more violently, so that the melt strength will be significantly reduced, so that the sealing cannot be completed, and the process cannot continue.
  • adipic acid is the most polar among 6-18 carbon aliphatic dibasic acids, and has the best compatibility with the most common nylon products PA6 and PA66, and better compatibility with common monomers. It is easier to get a homogeneous melt, so it is more flexible in the preparation of copolymerized nylon.
  • the finished nylon product produced by the continuous process of the present invention has good uniformity, and conventional melt conveying and die discharge can be used. Stable, high product pass rate.
  • the preparation method of the present invention can add one or several auxiliary agents such as conventional antioxidants, catalysts, toughening agents, molecular weight regulators and lubricants for polyamide synthesis according to needs, and can also directly complete the polymerization reaction without adding auxiliary agents.
  • This preparation method is suitable for the synthesis of polyamide resins whose dibasic acid monomers are mainly aliphatic dibasic acids, and is not limited to the types listed in the examples, and has a wide range of applications.

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Abstract

本发明提供了一种制备脂肪族二元酸尼龙的连续化工艺。原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占80-100％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。是一种节能环保，且生产效率高的绿色工艺。

Description

一种制备脂肪族二元酸尼龙的连续化工艺 技术领域
本发明涉及工程塑料技术领域，具体涉及一种制备脂肪族二元酸尼龙的连续化工艺。
背景技术
尼龙(Nylon)是聚酰胺的俗称，英文名称为polyamide，其分子链上含有重复的酰胺官能团。尼龙在机械性能、耐候性、耐腐蚀性、耐高温等性能和成本方面的综合优势，使得其被广泛应用于电子电气、机械、纤维、汽车等各个领域。
用于合成尼龙的原料包括二元胺和二元酸，二元酸又包括了脂肪族和芳香族的单体。其中的脂肪族二元酸的热稳定性较差，在高温下容易分解，影响聚合反应的发生，从而造成聚合物的质量缺陷，例如颜色变化、性能变化等等。最常用的尼龙的聚合工艺是将二元酸和二元胺在较低温度下，在溶剂中先制备得到尼龙盐，使尼龙盐中脂肪族二元酸的热稳定性显著提高，然后再逐步升温聚合，从而减少脂肪族二元酸的分解，提高产品的质量。这套工艺需要提前在溶剂中制备尼龙盐溶液，期间消耗大量的水或者有机溶剂，并且尼龙盐溶液中的溶剂也要在后续的聚合中蒸发掉，又要消耗大量的能源。
CN112062950B报道了一种连续化的尼龙聚合工艺，利用熔融的尼龙聚合物作为反应性分散体系，使得二元酸和二元胺在其中反应成盐，继而发生聚合反应，作为分散体系的尼龙可以成为产品的一部分，从而避免了消耗小分子溶剂以及蒸发小分子溶剂的耗能。这个方法更适合芳香族二元酸单体含量高的尼龙，因为通常作为反应性分散体系的尼龙均具有较高的熔点，从而使得开始反应的温度较高，不利于脂肪族二元酸的稳定，而芳香族二元酸则具有更好的热稳定性。
发明内容
本发明针对上述技术问题，提出了一种制备脂肪族二元酸尼龙的连续化工艺，是一种节能环保，且生产效率高的绿色工艺。
为了实现上述发明目的，本发明采用的技术方案是：
一种制备脂肪族二元酸尼龙的连续化工艺，原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占80-100％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
二元酸和二元胺是尼龙聚合常用的原料，但是如果仅使用这两种原料在连续熔融体系中进行聚合，由于二者熔融后都不具有足够的熔体强度，无法承受连续混料装置中二元胺和二元酸在高温下相遇聚合脱水产生水蒸气的压力，会导致水蒸气的泄露，也会随之带出部分聚合单体，使得体系中酸和胺的配比失衡，因此在原料中需要加入一定量的聚酰胺。聚酰胺在温度和剪切的作用下分散到熔融的脂肪族二元酸中，能够给熔体提供足够的熔体强度。聚酰胺是聚合的产物，其能够和二元酸发生可逆的化学反应，具有突出的相容性，并且可以不影响聚合产物的性能。
本发明利用脂肪族二元酸本身较低的熔点，控制二元酸和聚酰胺的混合温度高于脂肪族二元酸的熔点，且低于聚酰胺原料的熔点，在该温度条件下，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成可以连续流动的熔融体。由于聚酰胺能与液态的二元酸发生可逆反应，使得聚酰胺的分子量急剧降低，低分子量的尼龙寡聚物的熔融可流动温度也降低，从而降低整个体系可以流动的温度，满足了脂肪族二元酸单体的稳定性，使其能在连续混料装置中稳定输送，保证了产品的稳定性。
由本发明的原理可知，最终产物聚酰胺的量等于原料中聚酰胺的量加上聚合单体聚合产生的聚酰胺的量。因此产物中的聚酰胺的量减去聚酰胺原料量的差才是工艺实际的产量。对于本发明的连续聚合装置，在其有效体积一定的情况下，理想状态下，聚合反应时间就是物料流过整套装置有效体积的时间，因此装置的总产量和聚合反应时间成反比。为了保证最终产物的稳定性，需要控制一定的聚合时间。在聚合时间一定的情况下，最终产物的总量也是一定的。为了提高聚合装置的利用率和生产效率，原料中聚酰胺的用量应当尽可能的少，以增加总产物中实际单体聚合产生的聚合物的比例。
熔融的脂肪族二元酸具有较大的极性，能够使得聚酰胺溶解在其中。由于酰胺的聚合是一个可逆反应，因此溶解后的聚酰胺会发生酸解反应，分子量降低，进一步增加溶解性，熔融软化的温度也随之降低。但是酸解程度过大，会导致熔融软化后强度过低，或者完全液化。本发明熔融分散段的温度可以低于聚酰胺原料的熔点，从而减少聚酰胺原料酸解的程度，使得二元酸和聚酰胺熔融混合后的熔体在原料中聚酰胺比例一定的情况下具有更大的熔体强度。混合后的熔体强度是承受二元胺和二元酸聚合过程中脱水产生蒸气压力的关键因素，完全液化的混合物无法承受高温水蒸气的压力，必须使得混合物筒体具备足够的强度。因此，相对较低的熔融分散段温度可以更好保持混合后熔体的强度，就可以减少原料中聚酰胺的比例而提高聚合单体所占的比例，在总产量一定的情况下下，提高装置的实际生产效率。
本发明所述脂肪族二元酸与聚酰胺原料的质量比例为0.5-50：1。聚酰胺原料用量过少，不能起到增强熔体强度的作用；用量过多，会损失设备的利用率。0.5-50：1的比例能保证 装置的实际生产效率，也能够提供给熔体足够的强度来承受脱水产生水蒸气的压力。当所需聚酰胺原料的重量超过原料总重的50％才能具备足够的熔体强度来达到密封效果时，工艺的实际产量过低，相对于传统的尼龙聚合工艺，优势不明显，不推荐本发明方法。
本发明二元酸和聚酰胺原料的混合温度高于至少一种脂肪族二元酸原料的熔点，保证至少一种脂肪族二元酸原料能在装置中形成熔体，使其它物料在装置的剪切作用下均匀分散到该熔体中。
本发明二元酸和聚酰胺原料混合均匀后得到混合熔体，在二元胺加入前的装置内至少有一段被该混合熔体充满，形成密封段。
后续加入的二元胺和二元酸相遇会脱水，体系中会有高温的水蒸汽存在，所以需要在二元胺加入之前，由原料中二元酸和聚酰胺所形成混合物的熔体充满一段物料混合输送的装置，这样才能避免水蒸气的泄露，也避免了氧气进入到后面的聚合过程和二元胺单体的泄露，造成质量问题。
优选地，所述密封段的熔体温度低于二元酸和聚酰胺原料的混合温度。
当物料分散均匀后，在聚酰胺的作用下熔体强度增加，能达到密封的效果，形成密封段。由于二元酸和聚酰胺形成的熔体混合物中存在酰胺寡聚物，会导致熔体中二元酸的熔点进一步降低，使得整个熔体的软化温度低于原料中二元酸的熔点。此时，在密封段降低体系温度至脂肪族二元酸原料的熔点之下，依然能使熔体具有合适的流动性。同时，体系温度降低后有利于进一步提高熔体的强度。因此，进一步优选地，所述密封段的熔体温度低于至少一种熔融态脂肪族二元酸的熔点。
本发明所述脂肪族二元酸选自6-18个碳原子的二元酸中的至少一种。
优选地，所述原料中的脂肪族二元酸含己二酸。6-18个碳原子的二元酸中熔点最高的是己二酸，大约在155℃，由己二酸形成的熔体可以在更高的温度下保持足够的强度，可操作窗口更宽。另外，己二酸也是这些二元酸中极性最大的，和最常用的尼龙，如PA6，PA66相容性最好，和用于制备耐高温尼龙的其他单体的相容性也最好，其熔体可以更好的熔化熔点相对较高的尼龙产品，更方便用来制备具有更高耐温性能的共聚尼龙。同时，6-18个碳原子的二元酸中，和同样的二元胺聚合生成尼龙时，己二酸聚合生成的尼龙具有最佳的耐温性能，具有最广泛的适用空间。
本发明所述连续混料装置为螺杆挤出装置。所有具有剪切分散输送功能的连续混料装置可以酌情使用，优选螺杆挤出装置。最常用的螺杆挤出装置是双螺杆挤出装置，螺杆挤出装置的螺纹组合设计灵活，可以根据需要在不同的阶段设计不同的输送和剪切分散能力。并且螺杆挤出装置具有远超一般混合装置的物料分散能力和界面更新能力，能够让聚合物原料和 熔融的二元酸迅速混合均匀，并且使得二元胺和二元酸成盐时产生的热量能够迅速散开，不至于使得料温过高，能够更好的避免因为局部高温导致的颜色发黄，聚合物熔体强度过低等影响生产稳定和质量的问题。
本发明所述二元胺优选以液态形式加入连续混料装置。二元胺可熔化为液态，或者溶解在小分子溶剂中，以液态形式加入物料混合装置，这样更容易保证混合装置的密封性能，防止挥发性原料的损失。
优选地，在二元胺加入后，至少有一段物料的流动方向向上。
所有物料混合后，物料优选设置一段向上的流动，从而使得物料形成的熔融体即使在较低的粘度下，也在向上的流动时形成密封段，不会因为粘度低而使装置的上部空间无法被充满造成气态二元胺大量溢出。
本发明所述聚合单体中二元酸和二元胺的摩尔比例为1：0.8-1.2。通常情况下，参与聚合的二元胺和二元酸摩尔比例接近于1才能都得到较高分子量的聚合物，二元胺的挥发性通常高于二元酸。胺值和酸值不平衡的尼龙寡聚物或者聚合物原料上本身带有不等的羧基和氨基官能团时，会影响最终的聚合物分子量，为了平衡这些因素，原料重聚合单体的二元酸和二元胺的摩尔比例为1：0.8-1.2。
本发明所述原料中的聚酰胺选自PA66，PA56，PA610，PA612，PA1010，PA1212，PAMXD6，或者以这些聚酰胺结构为主体的共聚物，优选PA66，PA56，PAMXD6，这三种聚酰胺中的二元酸单体均为己二酸，整个装置具有更大的操作空间。
本发明所述后续聚合装置为螺杆挤出装置、管式反应装置和釜式反应装置中的至少一种。
为了能够达到足够大的分子量，需要足够的反应时间，从而需要螺杆挤出装置具有特别长的长径比，通常需要多级螺杆挤出装置串联实现，增加了固定投资，设备占地也会加大。可以通过串联其他聚合装置来减小设备的体积。管道式反应器、反应釜式聚合装置和具备更大直径的螺杆混合装置均可用于本发明中。
后续聚合装置可以为依次连接的连续流反应器或者螺杆挤出装置。连续流反应器是一类连续化聚合的反应器，可以是管道式，也可以是反应釜、塔的形式，主要保证物料进出都是连续流动的，理想状态下没有返流，所有物料在其中的停留时间相等。连续流反应器可以控制物料聚合的时间，从而得到不同分子量的聚合物。物料在通过连续流反应器后，装置也优选物料连续流动出料的聚合装置，实现连续化生产最为有利。
聚合过程经螺杆挤出装置脱挥，挤出造粒。在聚酰胺聚合过程中，会有小分子脱出，通过螺杆挤出装置脱挥可以实现生产完全连续化。各种原料在后续聚合装置中聚合完成后，可以直接在后面加螺杆挤出装置继续聚合并脱除挥发的小分子，使得物料进一步均化。
本发明各种原料的加入方式非常灵活，可以在机头同时加入进料段，也可以把部分的原料在设备的中段通过侧喂料或者液体泵入的方式加入，甚至同一种原料也可在不同位置分批加入从而进一步使得混合更加均匀。
本发明物料从进料到出料，在物料混合装置和后续聚合装置中总的平均停留时间为10-120min。
聚合反应的速率和温度相关，温度高聚合快，效率高，但是过高的温度会引起黄变、降解等一系列的问题，因此需要平衡反应温度和时间的关系。本发明物料从进料到出料在物料混合装置和后续聚合装置中的平均停留时间优选10-120min。可以通过在一定产量下，混合物料的体积充满所有混合和聚合装置的有效容积的时间来估算。在物料连续流动时，固定产量的条件下，物料的在装置中平均停留时间理论上是相同的，这样可以避免非连续过程因为进料、出料先后造成的物料停留时间不同，从而引起的分子量不均。在装置固定的情况下，可以通过调节总进料量来调节聚合反应的时间，从而制备分子量不同的聚合物，满足不同应用的需求。通常情况下，改变装置的产量，可以改变聚合反应的时间，从而控制产品的分子量；控制不同物料的投料比例则可以方便的控制共聚单元的组成，从而得到物性不同的产品。同一套装置可以实现不同性能产品的生产，提高生产的灵活性。所有的调整可以在线完成，避免间歇性工艺切换产品停机造成的浪费。
本发明的有益效果在于：
1、本发明的聚合方法利用脂肪族二元酸本身较低的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成可以连续流动的熔融体。由于聚酰胺能与液态的二元酸发生可逆反应，使得聚酰胺的分子量急剧降低，低分子量的尼龙寡聚物的熔融可流动温度也降低，从而降低整个体系可以流动的温度，满足了脂肪族二元酸单体的稳定性，使其能在连续混料装置中稳定输送，保证了产品的稳定性。同时聚酰胺在温度和剪切的作用下分散到熔融的脂肪族二元酸中，能够给熔体提供足够的熔体强度，使物料的连续向前输送，实现了进料、反应和出料的连续性，克服了传统反应釜工艺的间歇性生产缺点。
2、本发明省去了水溶液中制备尼龙盐的步骤，避免了尼龙盐制备过程中废液的产生，是一种绿色环保的尼龙合成方法。具备生产效率高、能耗低、节能、环保的特点，易于在实际生产中大规模推广应用。形成尼龙盐的过程中不用到小分子溶剂，节约了水和能源。
3、控制二元胺加入前的物料温度在聚酰胺原料熔点之下，较低的温度使得聚酰胺原料具有更好的稳定性，能够提高熔体的强度，从而减少聚酰胺原料的用量，提高聚合 装置的利用率和生产效率。
4、当物料分散均匀后，在密封段降低体系温度至熔融态脂肪族二元酸的熔点之下，依然能使熔体具有合适的流动性，且有利于进一步提高熔体的强度，保证密封性。
5、本发明的连续化尼龙聚合方法避免了分批次生产造成的产品质量不稳定的问题，且不受水溶液中尼龙盐制备过程中温度、pH值等因素的影响，得到的尼龙产品具有均匀性好、质量稳定的特点。
具体实施方式
为了更加清楚、详细地说明本发明的目的技术方案，下面通过相关实施例对本发明进行进一步描述。以下实施例仅为具体说明本发明的实施方法，并不限定本发明的保护范围。
实施例1
一种制备脂肪族二元酸尼龙的连续化工艺，原料包括聚合单体和聚酰胺，所述聚合单体包括脂肪族二元酸和二元胺；将脂肪族二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
实施例2
一种制备脂肪族二元酸尼龙的连续化工艺，原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占80％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
所述脂肪族二元酸与聚酰胺原料的质量比例为50：1，有效产率约45％。
二元酸和聚酰胺原料的混合温度高于至少一种脂肪族二元酸原料的熔点。
二元酸和聚酰胺原料混合均匀后得到混合熔体，在二元胺加入前的装置内至少有一段被该混合熔体充满，形成密封段。所述密封段的熔体温度低于二元酸和聚酰胺原料的混合温度。
所述后续聚合装置为螺杆挤出装置。
实施例3
一种制备脂肪族二元酸尼龙的连续化工艺，原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占90％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再 连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
所述脂肪族二元酸与聚酰胺原料的质量比例为40：1。
二元酸和聚酰胺原料的混合温度高于至少一种脂肪族二元酸原料的熔点。
二元酸和聚酰胺原料混合均匀后得到混合熔体，在二元胺加入前的装置内至少有一段被该混合熔体充满，形成密封段。所述密封段的熔体温度低于二元酸和聚酰胺原料的混合温度。
所述脂肪族二元酸选自6-18个碳原子的二元酸中的至少一种。
所述二元胺以液态形式加入连续混料装置。
所述后续聚合装置为螺杆挤出装置和釜式反应装置。
物料从进料到出料，在物料混合装置和后续聚合装置中总的平均停留时间为10-120min。
实施例4
一种制备脂肪族二元酸尼龙的连续化工艺，原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占95％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
所述脂肪族二元酸与聚酰胺原料的质量比例为30：1。
二元酸和聚酰胺原料的混合温度高于至少一种脂肪族二元酸原料的熔点。
二元酸和聚酰胺原料混合均匀后得到混合熔体，在二元胺加入前的装置内至少有一段被该混合熔体充满，形成密封段。所述密封段的熔体温度低于熔融态脂肪族二元酸的熔点。
所述二元胺优选以液态形式加入连续混料装置。
在二元胺加入后，至少有一段物料的流动方向向上。
所述聚合单体中二元酸和二元胺的摩尔比例为1：0.8-1.2。
所述原料中的聚酰胺选自PA66，PA56，PA610，PA612，PA1010，PA1212，PAMXD6，或者以这些聚酰胺结构为主体的共聚物。
所述后续聚合装置为螺杆挤出装置和管式反应装置。
物料从进料到出料，在物料混合装置和后续聚合装置中总的平均停留时间为10-120min。
实施例5
一种制备脂肪族二元酸尼龙的连续化工艺，原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占95％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再 连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
所述脂肪族二元酸与聚酰胺原料的质量比例为25：1。
二元酸和聚酰胺原料的混合温度高于至少一种脂肪族二元酸原料的熔点。
二元酸和聚酰胺原料混合均匀后得到混合熔体，在二元胺加入前的装置内至少有一段被该混合熔体充满，形成密封段。所述密封段的熔体温度低于熔融态脂肪族二元酸的熔点。
所述脂肪族二元酸为己二酸。
所述二元胺优选以液态形式加入连续混料装置。
在二元胺加入后，至少有一段物料的流动方向向上。
所述聚合单体中二元酸和二元胺的摩尔比例为1：0.8-1.2。
所述原料中的聚酰胺选自PA66，PA56，PAMXD6或者以这些聚酰胺结构为主体的共聚物。
所述后续聚合装置为管式反应装置。
本发明各种原料的加入方式非常灵活，可以在机头同时加入进料段，也可以把部分的原料在设备的中段通过侧喂料或者液体泵入的方式加入，甚至同一种原料也可在不同位置分批加入从而进一步使得混合更加均匀。
本发明物料从进料到出料，在物料混合装置和后续聚合装置中总的平均停留时间为10-120min。
实施例6
按照4：1的重量比混合己二酸、PAMXD6树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-120℃，熔融分散段温度120-195℃，物料分散后熔体密封段的温度设为145℃，之后通过失重控制加入间苯二甲胺，使得间苯二甲胺和己二酸的摩尔比例为1.01：1。二元胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为248℃，连续挤出造粒，得到PAMXD6树脂，物料在装置重平均停留时间为30分钟，熔点为243℃，粘度2.3，颜色白，有效产率约85％。装置耗电每小时大约197度。
实施例7
按照4：1的重量比混合己二酸、PAMXD6树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-120℃，熔融分散段温度160-220℃，物料分散后熔体密封段的温度设为145℃，之后通过失重控制加入间苯二甲胺，使得间苯二甲胺和己二酸的摩尔比例为1.01：1，间苯 二甲胺刚加入的三节筒体温度设为180℃，螺杆盘根处出现了轻微漏气现象，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为248℃，连续挤出物料到水中冷却，得到PAMXD6树脂，无法拉条造粒。物料在装置重平均停留时间为30分钟，熔点为239℃，粘度1.6，颜色黄，有效产率约85％，装置耗电每小时205度。
实施例8
本实施例在实施例7的基础上，增加原料中PAMXD6的比例至己二酸和PAMXD6树脂比例为2：1，熔融分散段温度160-220℃。无漏气现象，得到PAMXD6树脂，有效产率约75％。装置耗电每小时215度。
实施例7与实施例6的原料和用量均相同，熔融分散段的混合温度高于实施例6，同样的设备条件下，此时熔融混合挤出机螺杆盘根处出现了轻微漏气，说明由于混合过程温度提高以后，原料中聚合物的分子量降低更多，导致熔体强度更低，密封效果欠佳。在此条件下聚合生产的产物明显质量不如实施例6中的产物，并且能耗要更高。
实施例8在实施例6的基础上提高聚酰胺原料比例后，熔体强度增大，在较高的混合温度下也能满足混合均匀性和体系的密封性，无漏气现象，但有效产量降低，损失了设备的利用率。同时，因为初始需要熔融更多的聚合物，消耗了更多的能量，使得能耗提高了约8％。因此，虽然设备没有经过最佳的优化，但是同样条件下的比较已经可以发现混合过程在满足混合均匀性的前提下，较低的混合温度更有利于减少原料中聚合物的比例，从而提高有效产量，提高装置的利用率，提高生产效率。
实施例9
按照3：1的重量比混合己二酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-190℃，物料分散后熔体密封段的温度设为130℃，之后通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。己二胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为260℃，连续挤出造粒，得到PA66树脂，物料在装置重平均停留时间为30分钟，熔点为268℃，粘度2.3，颜色白。有效产率82％，整套装置运行的平均耗电每小时约202度。
实施例10
按照3：1的重量比混合己二酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-280℃，物料分散后熔体密封段的温度设为130℃，之后通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。己二胺刚加入的三节筒体温度设为180℃，螺杆挤出装置盘根严重漏气，无法形成密封。
实施例11
按照1.5：1的重量比混合己二酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-280℃，物料分散后熔体密封段的温度设为130℃，之后通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。己二胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为268℃，连续挤出造粒，得到PA66树脂，物料在装置重平均停留时间为30分钟，熔点为263℃，粘度2.1，颜色发黄。有效产率68％，整套装置运行的平均耗电每小时245度。
实施例12
按照3：1的重量比混合己二酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-280℃，物料分散后熔体密封段的温度降为95℃，之后通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。此条件下也能形成密封。通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。己二胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为260℃，连续挤出造粒，得到PA66树脂，物料在装置重平均停留时间为30分钟，熔点为261℃，粘度2.1，颜色黄，有效产率82％，装置运行耗电每小时223度。
实施例13
按照3：1的重量比混合己二酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-190℃，物料分散后熔体密封段的温度设为130℃，之后通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。己二胺刚加 入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为260℃，连续挤出造粒，得到PA66树脂，物料在装置重平均停留时间为60分钟，熔点为269℃，粘度2.8，颜色微黄。有效产率82％，整套装置运行的平均耗电每小时约174度，装置总产量约为149kg/h。
实施例10在实施例9的基础上提高了熔融分散段的混合温度到280℃，超过了PA66树脂的熔点，PA66树脂的分子量降低更剧烈，使熔体强度明显降低，无法形成密封，工艺无法继续；实施例11在实施例9的基础上提高了原料中PA66树脂与己二酸的重量比至1：1.5来增加熔体强度，在该原料用量下，装置的实际有效产率降低约14％，能耗增加约20％，此调整方案不推荐。
实施例12在实施例9基础上，同样提高了熔融分散段的混合温度到280℃，而无法形成密封，在不增加PA66树脂用量的前提下，实施例12在密封段降低到更低的温度到95℃来提高熔体强度，这就要求更长的传输距离实现降温。因此，实施例12加入己二胺的位置要比实施例9晚两节，事实上提高了对装置的要求，并且所得产物的熔点偏低，颜色也更难控制，能耗也增加了10％。
实施例13和实施例9比较，减少了总产量，延长了聚合反应时间，得到了分子量更大的聚合物。说明本发明的方法可以通过对聚合反应时间的控制制备分子量不同的产品，满足不同的需求。由于增加了一倍的反应时间，总产量由实施例9的305kg/h降低约一半至149kg/h，装置的实际有效产量占比不变，能耗降低约14％。
对于本发明实际适用的这套装置，有效容积为150升，对应30分钟聚合时间的总产量约为300kg/h左右，60分钟聚合时间对应的总产量约为150kg/h。
实施例14
按照3：1的重量比混合己二酸、PA56树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-190℃，物料分散后熔体密封段的温度设为125℃，之后通过失重控制加入的戊二胺，使得戊二胺和己二酸的摩尔比例为1.02：1。戊二胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-280℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为250℃，连续挤出造粒，得到PA56树脂，物料在装置重平均停留时间为30分钟，熔点为252℃，粘度2.2，颜色白。
实施例15
按照8：1的重量比混合癸二酸、PA610树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-120℃，熔融分散段温度120-190℃，物料分散后熔体密封段的温度维持分散结束时的155℃，之后通过失重控制加入的己二胺，使得己二胺和癸二酸的摩尔比例为1.02：1，螺杆挤出装置盘根有轻微漏气，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为220℃，连续挤出，无法拉条造粒，得到的PA610树脂在水中收集。物料在装置重平均停留时间为30分钟，熔点为218℃，粘度1.6，颜色淡黄。
实施例16
按照8：1的重量比混合癸二酸、PA610树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-120℃，熔融分散段温度120-190℃，物料分散后熔体密封段的温度设为95℃，之后通过失重控制加入的己二胺，使得己二胺和癸二酸的摩尔比例为1.02：1。己二胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为220℃，连续挤出造粒，得到PA610树脂，物料在装置重平均停留时间为30分钟，熔点为224℃，粘度2.3，颜色白。
实施例15的熔体密封段温度未降低，保持在癸二酸的熔点之上，在该温度的持续输送下，熔体强度不够，有轻微的漏气现象，导致聚合产品质量严重下降；实施例16降低了熔体密封段的温度在癸二酸的熔点之下，熔体仍能保持流动性，且熔体强度提高，无漏气现象。
实施例17
按照9：1的重量比混合十二烷二酸、PA612树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为90-105℃，熔融分散段温度120-190℃，物料分散后熔体密封段的温度设为85℃，之后通过失重控制加入的己二胺，使得己二胺和十二烷二酸的摩尔比例为1.02：1。己二胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为220℃，连续挤出造粒，得到PA612树脂，物料在装置重平均停留时间为30分钟，熔点为205℃，粘度2.1，颜色白。
实施例18
按照15：1的重量比混合十二烷二酸、PA1212树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为90-95℃，熔融分散段温度120-160℃，物料分散后熔体密封段的温度设为75℃，之后通过失重控制加入的十二烷二胺，使得十二烷二胺和十二烷二酸的摩尔比例为1.01：1。二元胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为180℃，连续挤出造粒，得到PA1212树脂，物料在装置重平均停留时间为30分钟，熔点为178℃，粘度2.1，颜色白，有效产率97％。
实施例19
按照9：1的重量比混合癸二酸、PA1010树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-120℃，熔融分散段温度120-170℃，物料分散后熔体密封段的温度设为95℃，之后通过失重控制加入的己二胺，使得己二胺和癸二酸的摩尔比例为1.01：1。二元胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为220℃，连续挤出造粒，得到PA1010树脂，物料在装置重平均停留时间为30分钟，熔点为192℃，粘度2.1，颜色白，有效产率95％，装置运行平均每小时耗电194度。
实施例20
按照9：1的重量比混合癸二酸、PA1010树脂和占总重量0.5％的抗氧剂，0.2％的催化剂，通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-120℃，熔融分散段温度120-230℃，物料分散后熔体密封段的温度设为95℃，之后通过失重控制加入的己二胺，使得己二胺和癸二酸的摩尔比例为1.01：1。癸二胺刚加入的三节筒体温度设为180℃，此时混料装置螺杆盘根处开始漏气。
增加原料中PA1010的比例，使得癸二酸和PA1010的比例为3：1，漏气停止。其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为220℃，连续挤出造粒，得到PA1010树脂，物料在装置重平均停留时间为30分钟，熔点为193℃，粘度2.2，颜色白，有效产率75％，装置运行平均每小时耗 电213度。
实施例20与实施例19的原料和用量均相同，熔融分散段的混合温度高于实施例19，超过了PA1010树脂熔点，使聚合物分子量降低更多，导致熔体的强度下降，需要更多的聚合物才能实现物料的密封，因此，增加PA1010的比例至3：1，能耗和总产量保持不变，实际生产效率降低，有效产率由95％降低至75％，并且由于需要重熔的聚合物量增加，使得整套装置的能耗反而提高了10％。
实施例21
按照4：1的重量比混合二元酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂。其中原料中二元酸的组成为重量比5：1的己二酸和对苯二甲酸。通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-200℃，物料分散后熔体密封段的温度设为110℃，之后通过失重控制加入的己二胺，使得己二胺和己二酸的摩尔比例为1.01：1。二元胺刚加入的三节筒体温度设为180℃，其后逐步升温，之后进入装有主动搅拌装置的有效容积150L的连续流反应器，聚合段温度为220-285℃，之后进入长径比为48：1的同向双螺杆挤出机，设有三个排气孔，后两个排气孔抽真空。机头温度设定为260℃，连续挤出造粒，得到PA66/6T共聚树脂，物料在装置重平均停留时间为30分钟，熔点为272℃，粘度2.2，颜色白。
实施例22
按照4：1的重量比混合二元酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂。其中原料中二元酸的组成为重量比5：1的癸二酸和对苯二甲酸。通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-245℃，物料无法良好分散，继续升温至275℃才能良好分散，螺杆挤出装置盘根严重漏气，无法形成密封。
实施例23
按照4：1的重量比混合二元酸、PA66树脂和占总重量0.5％的抗氧剂，0.2％的催化剂。其中原料中二元酸的组成为重量比5：1的十二烷二酸和对苯二甲酸。通过失重计量设备从前端送入总长径比为100：1的串联同向双螺杆挤出机组，设置螺杆进料段温度为100-150℃，熔融分散段温度160-245℃，物料无法良好分散，继续升温至275℃才能良好分散，螺杆挤出装置盘根严重漏气，无法形成密封。
本发明方法也可以用于合成有芳香族二元酸单体的共聚尼龙，但是因为芳香族二元酸具有更高的熔点，必须保证芳香族二元酸的比例不超过20％，才能在原料聚合物熔点之下将二元酸和聚酰胺混合均匀。
实施例21的混合二元酸采用己二酸和对苯二甲酸，在160-200℃的混合温度下就能得到分散均匀的熔体，继续聚合反应顺利得到聚酰胺产品。实施例22和23分别采用癸二酸和十二烷二酸代替实施例21的己二酸，在相同的聚合物用量下于275℃的混合温度才能得到分散均匀的熔体，由于混合温度超过了PA66树脂的熔点，使PA66树脂也熔融，并伴随聚合物分子量降低更剧烈，使熔体强度明显降低，从而无法完成密封，工艺无法继续，只有通过增加聚合物用量才能改善熔体强度，这又会带来有效生产率的降低和能耗的增加。这是由于己二酸是6-18个碳脂肪族二元酸中极性最大的，和最常见的尼龙产品PA6，PA66相容性最好，和常见的单体相容性也更好，更容易得到混合均匀的熔体，所以在制备共聚尼龙时也更灵活。
本发明的连续化工艺制得的尼龙成品均匀性好，可使用常规的熔体输送和口模出料，料条光滑均匀，不断条，切粒后例子饱满混匀，且连续生产的产品性能稳定，产品合格率高。
本发明的制备方法可以根据需要加入聚酰胺合成的常规抗氧剂、催化剂、增韧剂、分子量调节剂和润滑剂等某种或某几种助剂，也可以不加助剂直接完成聚合反应。本制备方法适用于二元酸单体以脂肪族二元酸为主的聚酰胺树脂的合成，而不限于实施例中列举的种类，应用范围广。
以上所述实施例仅表达了本发明的具体实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (16)

  1. 一种制备脂肪族二元酸尼龙的连续化工艺，其特征在于：原料包括聚合单体和聚酰胺，所述聚合单体包括二元酸和二元胺，所述二元酸中脂肪族二元酸的质量比例占80-100％；将二元酸和聚酰胺原料连续投入具有剪切分散和输送功能的连续混料装置，体系温度低于聚酰胺原料的熔点，聚酰胺原料在输送过程中分散到熔融的脂肪族二元酸中，混合均匀形成连续流动的熔融体，再连续加入二元胺，混合均匀后连续进入到后续聚合装置反应，至尼龙聚合达到所需分子量。
  2. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述原料中的脂肪族二元酸选自6-18个碳原子的二元酸中的至少一种。
  3. 根据权利要求2所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述原料中的脂肪族二元酸含己二酸。
  4. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述脂肪族二元酸与聚酰胺原料的质量比例为0.5-50：1。
  5. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：二元酸和聚酰胺原料的混合温度高于至少一种脂肪族二元酸原料的熔点。
  6. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：二元酸和聚酰胺原料混合均匀后得到混合熔体，在二元胺加入前的装置内至少有一段被该混合熔体充满，形成密封段。
  7. 根据权利要求6所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述密封段的熔体温度低于二元酸和聚酰胺原料的混合温度。
  8. 根据权利要求7所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述密封段的熔体温度低于至少一种熔融态脂肪族二元酸的熔点。
  9. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述连续混料装置为螺杆挤出装置。
  10. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述二元胺以液态形式加入连续混料装置。
  11. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：在二元胺加入后，至少有一段物料的流动方向向上。
  12. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述聚合单体中二元酸和二元胺的摩尔比例为1：0.8-1.2。
  13. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述原料中的聚酰胺选自PA66，PA56，PA610，PA612，PA1010，PA1212，PAMXD6，或者以这些聚酰胺结构为 主体的共聚物。
  14. 根据权利要求13所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述原料中的聚酰胺选自PA66，PA56，PAMXD6或者以这些聚酰胺结构为主体的共聚物。
  15. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：所述后续聚合装置为螺杆挤出装置、管式反应装置和釜式反应装置中的至少一种。
  16. 根据权利要求1所述制备脂肪族二元酸尼龙的连续化工艺，其特征在于：物料从进料到出料，在物料混合装置和后续聚合装置中总的平均停留时间为10-120min。
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3937686A (en) * 1974-01-10 1976-02-10 C/O E. I. Du Pont De Nemours & Co. Process of preparing high molecular weight polyamide with recovery of diamine and return of same to polymerization system
US3948862A (en) * 1974-05-06 1976-04-06 E. I. Du Pont De Nemours And Company Continuous process for preparing aliphatic polycarbonamides
IN186933B (zh) * 1995-10-31 2001-12-15 Du Pont
US20020132964A1 (en) * 2001-01-18 2002-09-19 Kazumi Tanaka Process for production of polyamide
US6696544B1 (en) * 1999-06-11 2004-02-24 Rhodianyl Method for making polyamides
WO2014179064A1 (en) * 2013-05-01 2014-11-06 Invista Technologies S.À.R.L. Nylon salt solution preparation processes with trim diamine mixing
US20160068632A1 (en) * 2013-05-01 2016-03-10 Invista North America S.A R.L. Nylon salt solution production from a partially balanced acid solution
CN111363144A (zh) * 2020-04-30 2020-07-03 成都肆零壹科技有限公司 一种聚酯酰胺的聚合工艺
CN111518270A (zh) * 2019-05-17 2020-08-11 成都肆零壹科技有限公司 一种绿色环保的聚酰胺树脂的制备方法
CN112062950A (zh) * 2020-03-28 2020-12-11 成都肆零壹科技有限公司 一种连续化尼龙聚合工艺

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3738876A1 (de) * 1986-11-18 1988-05-26 Mitsubishi Monsanto Chem Geformtes amidharz-produkt und verfahren zu dessen herstellung
ES2392792T3 (es) * 2007-08-24 2012-12-13 Ems-Patent Ag Masas de moldeo de poliamida para alta temperatura reforzadas con fibras de vidrio planas
CN102702510A (zh) * 2012-05-23 2012-10-03 上海臻威复合材料有限公司 醇溶尼龙及其制备方法
CN103865057A (zh) * 2012-12-17 2014-06-18 东丽先端材料研究开发（中国）有限公司 一种聚酰胺树脂及其制备方法以及聚酰胺树脂组合物
CN104558621B (zh) * 2014-12-18 2017-07-07 中国纺织科学研究院 一种连续制备低熔点共聚酰胺的方法
CN104945274B (zh) * 2015-05-19 2017-01-11 上海化工研究院 一种新型枝化的脂肪尼龙盐及其制备方法与应用
CN107337792B (zh) * 2017-07-28 2021-07-02 湖南华曙高科技有限责任公司 一种熔点可控的共聚尼龙粉末材料及其制备方法
CN109517165B (zh) * 2017-09-18 2020-09-15 上海凯赛生物技术股份有限公司 一种半芳香族生物基聚酰胺及其制备方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3937686A (en) * 1974-01-10 1976-02-10 C/O E. I. Du Pont De Nemours & Co. Process of preparing high molecular weight polyamide with recovery of diamine and return of same to polymerization system
US3948862A (en) * 1974-05-06 1976-04-06 E. I. Du Pont De Nemours And Company Continuous process for preparing aliphatic polycarbonamides
IN186933B (zh) * 1995-10-31 2001-12-15 Du Pont
US6696544B1 (en) * 1999-06-11 2004-02-24 Rhodianyl Method for making polyamides
US20020132964A1 (en) * 2001-01-18 2002-09-19 Kazumi Tanaka Process for production of polyamide
WO2014179064A1 (en) * 2013-05-01 2014-11-06 Invista Technologies S.À.R.L. Nylon salt solution preparation processes with trim diamine mixing
US20160068632A1 (en) * 2013-05-01 2016-03-10 Invista North America S.A R.L. Nylon salt solution production from a partially balanced acid solution
CN111518270A (zh) * 2019-05-17 2020-08-11 成都肆零壹科技有限公司 一种绿色环保的聚酰胺树脂的制备方法
CN112062950A (zh) * 2020-03-28 2020-12-11 成都肆零壹科技有限公司 一种连续化尼龙聚合工艺
CN112390945A (zh) * 2020-03-28 2021-02-23 成都肆零壹科技有限公司 一种连续化尼龙聚合方法
CN113527666A (zh) * 2020-03-28 2021-10-22 成都肆零壹科技有限公司 一种连续化尼龙聚合方法
CN111363144A (zh) * 2020-04-30 2020-07-03 成都肆零壹科技有限公司 一种聚酯酰胺的聚合工艺

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