Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
• • 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
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the invention relates to the technical field of engineering plastics, in particular to a continuous nylon polymerization method.
• Nylon's comprehensive advantages in mechanical properties, durability, corrosion resistance, heat resistance and other performance and cost are widely used in various fields such as electronic and electrical, machinery, fiber, and automobiles. Due to the pursuit of lightweight and environmental protection in various industries, replacing steel with plastic and replacing wood with plastic has become a major trend in design material selection. Nylon is one of the fastest growing parts in today's plastics industry, and the improvement of production technology has always been a research hotspot.
• nylon polymerization methods include nylon salt process and melt polymerization process.
• the nylon salt process generally first prepares nylon salt in water or a strong polar organic solvent, and then melts and polycondensates at a certain temperature to obtain the final polyamide.
• polyamide 1313 was prepared by first forming a salt in an aqueous solution and then melt polycondensation. In the initial stage of melt polycondensation, a large amount of water will be added as a dispersant to ensure the stability of the final product quality.
• This process has the following problems:
• the diamine In melt polymerization, the diamine needs to be added in the state where the dibasic acid is melted. The process must first melt the dibasic acid and then perform the polymerization reaction, and the reaction efficiency is low.
• the present invention provides a continuous nylon polymerization method, that is, adding a certain amount of polyamide resin as a reactive dispersion medium to the raw material system to make each group
• the components can be uniformly and stably dispersed in the dispersion medium to ensure the uniformity of the subsequent polymerization reaction.
• the polymerization raw materials by mass include 5-60 parts of polymerized monomer dibasic acid and/or dibasic acid ester, 3-50 parts of diamine and reactive dispersion medium polyamide 10-90
• the polymerization step includes continuously adding the polymerization raw materials to the material mixing device in proportion, so that the raw materials are mixed and reacted in the material mixing device to form a continuously conveyed melt, and the uniformly dispersed melt is reacted in the subsequent polymerization device until the nylon polymerization reaches the desired value. Need molecular weight.
• the technical scheme of the present invention adds polyamide resin to the raw material as a reactive dispersion system, on the one hand, it reduces the heat of reaction per unit weight, and on the other hand, it makes the dispersion system have a certain melting point and viscosity and can adapt to continuous flow materials.
• Application of mixing device. The solution of the present invention makes the addition of the material in a continuous state, and the mixing process and the continuous conveying process are carried out simultaneously, so that the heat release process is dispersed to different parts of the device along with the continuous forward conveyance of the material.
• the raw materials of the solution of the present invention contain polymers, the materials have a certain viscosity after being evenly mixed, which solves the problem that the traditional small-molecule monomer raw materials have low viscosity and cannot withstand the vapor pressure generated by the small molecules removed after the polycondensation reaction occurs.
• Continuous feeding is not possible, and melt polymerization can only concentrate the feeding, which will release heat and reduce the feeding efficiency.
• the present invention adds a certain amount of polyamide resin to the raw material, and the molten polyamide resin as a reactive dispersion system can combine dibasic acid and/or dibasic acid ester with dibasic
• the amine is uniformly and stably dispersed in the system, avoiding the addition of a large amount of water or small molecular organic solvents, and eliminating the preparation steps of preparing nylon salts in aqueous solutions or small molecular organic solvents.
• polyamide also participates in the reaction as a raw material, stays in the final product, and becomes a part of the product polyamide. Together with the polymerized monomer, it determines the performance of the final product.
• the polyamide raw material eventually becomes part of the product, so the steps of final removal and treatment of the solvent are omitted using small molecule solvents, making the process more environmentally friendly.
• the melt mixing process can be realized very easily and continuously in a continuous flow mixing device.
• the boiling point of the system is lower than that of the dibasic acid, and the more volatile dibasic acid ester can also replace all or part of the dibasic acid as the raw material.
• the reaction speed is faster than the dibasic acid.
• the small molecules removed by the polycondensation will be Contains alcohol. Compared with water, alcohol is a molecule that is easier to detach, which makes the polymerization reaction easier to proceed, and the alcohol can be collected and processed later.
• the temperature of the material mixing process can satisfy the melting of the raw material polyamide.
• the small molecules in the system such as polymerized monomers, have a plasticizing effect on the raw polyamide, which may reduce the melting temperature of the polyamide, but the temperature of the system must be able to ensure that the polyamide can melt and play the role of a reactive dispersion medium. Since the polymerized monomer can react with the raw material polyamide at high temperature, the dispersion medium of the present invention is not limited to the raw material polyamide in a molten state, and may also be a melt formed after the raw material polyamide and the polymerized monomer react.
• Various continuous flow material mixing devices can be used in the material mixing step of the present method, preferably at least one of a screw extrusion device, a continuous internal mixing device and a tubular reaction device.
• Screw equipment, continuous mixing device, and tubular reaction device have good sealing performance and pressure resistance due to their small diameter, which can ensure that the system can still be sealed and mixed well even if the temperature in the system exceeds the boiling point of the diamine raw material. And there is almost no loss of diamine.
• the screw extrusion device and the continuous banburying device are mixing devices equipped with a rotor and a barrel with a strong dispersion effect.
• the device has outstanding heat dissipation efficiency and can quickly disperse the heat generated when the diamine and dibasic acid are combined. It causes the local temperature in the system to run out of control, which leads to the decomposition of the material and the darkening of the color. In this way, all raw materials can be added to the system more quickly and continuously, and the production efficiency is high.
• screw extrusion devices and continuous mixing devices have better mixing efficiency and heat dissipation efficiency than tubular reaction devices, and screw extrusion devices are more convenient to add liquid materials, screw extrusion devices are further preferred, especially those with mixing effects.
• Two-shaft and above screw extrusion and mixing device The most commonly used screw extruder is a co-rotating twin-screw extruder with mixing effect. Through the combination of different thread elements, a suitable mixing effect and matching conveying capacity can be achieved. Other devices with similar screw conveying and mixing functions can also be applied to the present invention.
• the material mixing device is a tubular reaction device.
• the melting point of the dibasic acid/dibasic acid ester raw material is higher than that of the polyamide raw material, it is more difficult to melt. It is better to use a screw extrusion device or a continuous banburying device with outstanding solid particle dispersion ability to mix the raw materials.
• the refractory high-melting aromatic dibasic acid can be dissolved in the polyamide dispersion system, or fine particles can be dispersed in the degraded molten polyamide, both of which can smoothly polymerize with the diamine.
• a tubular reaction device used as a mixing device, in order to avoid that the polyamide raw materials cannot be melted in time in the tubular reaction device, the polymer can be melted first and then added to the pipeline, which is beneficial to improve the mixing efficiency.
• the tubular reaction device is more suitable for the case where the melting point of the dibasic acid is lower than that of the polyamide raw material. At this time, when the dibasic acid is added to the molten polyamide raw material, the dibasic acid will quickly melt to form a liquid. Even if the shear of the tubular mixing device is weak, the molten material can be completely dispersed.
• the subsequent polymerization device of the present invention is at least one of a screw extrusion device, a tubular reaction device and a kettle-type reaction device.
• a screw extrusion device In order to achieve a sufficiently large molecular weight, sufficient reaction time is required, and the screw extruder is required to have a particularly long aspect ratio.
• multi-stage screw extruders are required to be realized in series, which increases the fixed investment and the equipment area. Big. The volume of the equipment can be reduced by connecting other polymerization devices in series. Pipeline reactors, reactor-type polymerization devices, and screw mixing devices with larger diameters can all be used in the present invention.
• the subsequent polymerization device may be a continuous flow reactor or a screw extrusion device connected in sequence.
• Continuous flow reactor is a type of continuous polymerization reactor, which can be in the form of pipeline, reactor or tower. It mainly ensures that the materials are in continuous flow in and out, and there is no backflow in the ideal state, 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 of different molecular weights.
• the device is also preferably a polymerization device in which the materials are continuously flowed and discharged, which is the most advantageous to realize continuous production.
• the polymerization process is devolatilized by a screw extrusion device, and extrusion granulation is performed.
• small molecules will be released.
• Completely continuous production can be realized by devolatilization through screw extrusion device.
• a screw extrusion device can be directly added to the back to continue polymerization and remove the volatilized small molecules, so that the materials are further homogenized.
• the method of adding various raw materials of the present invention is very flexible. It can be added to the feed section at the same time at the head of the machine, or part of the raw materials can be added in the middle section of the equipment by side feeding or liquid pumping, and even the same raw material can be added at the same time. Add in batches at different locations to further make the mixing more uniform.
• the diamine of the present invention is added to the material mixing device in liquid form.
• the diamine can be melted into a liquid or dissolved in a small molecule solvent, and added to the material mixing device as a liquid; for the diamine with a higher melting point, you can first disperse the dibasic acid or ester and the diamine to the melt It is easier to ensure the sealing performance of the mixing device and prevent the loss of volatile raw materials.
• the polymerized monomers are separately dispersed into the molten polyamide to form a melt, and then various melts are continuously added to the material mixing device and mixed uniformly.
• Dibasic acid is the most commonly used starting material for the preparation of polyamides. Compared with diamines, dibasic acid has a higher melting point and is a solid that is more difficult to disperse and is less likely to volatilize, especially when the raw material contains aromatic dibasic acid. It is more difficult to disperse, and adding in advance will not affect the ratio of materials.
• the raw material dibasic acid and the molten raw material polyamide are reacted and mixed uniformly, and then the diamine is continuously added to it, and the reaction is uniformly mixed in the material mixing device.
• Diamines are molten liquids or dissolved in small molecule solvents.
• Diamines and dibasic acids or esters will react at high temperatures to form salts or de-polymerize small molecules.
• the removed small molecules such as water or alcohol, will form high-pressure gas at high temperature. Therefore, it is further preferred that at least one section of the device before the addition of the diamine has a filling rate of 100%, so that a section of the mixing device is filled with materials before the addition of the diamine, and a sealed section can be formed.
• the material is preferably set to flow upwards under the action of the pump, so that the melt formed by the material will form a sealing section when it flows upward even at a lower viscosity, and it will not be caused by the low viscosity.
• the upper space of the device cannot be filled, causing a large amount of gaseous diamine to overflow.
• the molar ratio of the diamine and the dibasic acid and/or the dibasic acid ester of the present invention is 0.4-2.5:1.
• the raw material polyamide of the present invention can use amide oligomers with lower molecular weight as the polyamide raw materials, and the content ratio of amino groups and carboxyl groups in the oligomer raw materials can be larger.
• the ratio of carboxyl groups adjusts the ratio of acid and amine raw materials, so that the ratio of acid and amine in the final whole system is balanced, and a high molecular weight product is obtained. Therefore, in the present invention, the ratio of acid to amine in the three main raw materials can be adjusted between 0.4-2.5:1, so that the source of the raw materials of the present invention is more extensive, very primary amide oligomers, even containing only one
• the oligopolyamide of the repeating unit can also be used as the raw material polyamide.
• the end groups of such amide oligomers can be mainly amino groups, carboxyl groups, or the ratio of amino groups to carboxyl groups, or even primary polymers containing unpolymerized carboxylic acid or amine monomers.
• the amine value and acid value of the oligomer can be measured to determine the ratio of additional amine and acid to the raw material.
• the method of the present invention can also be used to prepare amino or carboxyl-terminated polyamides of various molecular weights. Low molecular weight polyamide can be used as an important component in polyurethane and epoxy resin formulations.
• the dibasic acid raw material of the present invention contains aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid accounts for at least 20% of the dibasic acid raw material, which is more advantageous than the traditional method.
• Aromatic dibasic acid is a common polymerization monomer used for high temperature resistant polyamide materials, but because of the special molecular structure, its solubility and melting performance are far worse than aliphatic dibasic acid, so it contains aromatic dibasic acid.
• the preparation of acid-based nylon is also more difficult than that of aliphatic nylon. Because the method of the present invention makes full use of the dispersion advantages of polyamide as a dispersion system, and can also take advantage of the high mixing efficiency of the screw extrusion equipment, even when a high proportion of aromatic dibasic acid cannot be completely dissolved in the polyamide , The aromatic acid has become very fine particles evenly distributed in the system.
• the dispersion of the thread element can still form a completely uniform system, and as the aromatic dibasic acid gradually reacts, the remaining fine Aromatic dibasic acid particles will continue to dissolve and disperse into the system, which can well solve a series of problems faced by aromatic dibasic acid polymerization, and is especially suitable for the preparation of semi-aromatic nylon containing aromatic dibasic acid, especially Compared with other methods, it has outstanding advantages when preparing products with a higher proportion of aromatic raw materials.
• the maximum temperature reached by the materials during the polymerization process is not less than 250°C, which ensures that the materials can better react and mix in the molten state, and improves the polymerization efficiency.
• the melting point of the polyamide product of the present invention is higher than 250°C.
• the production of high melting point polyamide requires a higher temperature to ensure the fluidity of the material, but the high temperature material is easy to oxidize, especially for intermittent reaction devices, due to the inconsistent residence time of the material at high temperature, it is easier to cause the material with a long residence time to occur Oxidation affects product performance.
• the continuous production process of the present invention is suitable for the production of polyamides whose melting point exceeds 250°C.
• the use of the process of the present invention has outstanding advantages when producing high-temperature resistant polyamides with a melting point higher than 290°C.
• the molar ratio of aromatic dibasic acid accounts for at least 20% of the molar ratio of the dibasic acid raw material.
• the polyamide of the present invention accounts for more than 10% of the mass ratio of the polymerization raw material.
• the addition of the reactive dispersion system polyamide is very critical to the realization of the mixing reaction of the screw and the tubular reactor, because the polyamide is introduced and melted as a reactive dispersion system to ensure that the materials can be uniformly mixed in the mixing device.
• Some aromatic diacids used as raw materials for polymerization monomers may have a melting point higher than the temperature in the mixing device. Even if the high melting point powdered diacids cannot be melted, they can be dispersed into the molten polyamide to form a uniform melt. The acid reacts with other raw materials and the melting point is lowered. Part of the diacid can be dissolved into the reactive dispersion system, and part of the diacid is still fine powder uniformly dispersed in the melt without causing uneven mixing of the reaction materials.
• the temperature in the mixing device may be higher than the boiling point of some diamine raw materials, and once the polymerization reaction starts after the diamine and diacid meet, small molecules will be released.
• the diamine raw material above the boiling point and the released small molecules will be in a gaseous state in the mixing device, generating a certain pressure.
• polyamide has a certain molecular weight
• the raw material dispersion system formed by its reaction forms a melt with a certain viscosity, and a certain section of the cavity is filled in the mixing device to form a seal to prevent low-boiling raw materials from leaking under pressure, so as to be more suitable for the screw And the application of tubular reactor.
• the proportion of polyamide should not be less than 10%, otherwise it will be difficult to adapt to the application of screw and tubular reactors.
• the monomer polyamide raw material added in the present invention is the same as the nylon product, and the obtained homopolymer product is obtained. If the monomer polyamide raw material is different from the nylon product, the obtained copolymer product is obtained.
• the proportion of polyamide raw materials can be adjusted as needed, but should be at least 10% or more. If the polymerized monomer itself has a low viscosity after melting, and the temperature required for the reaction is relatively high, the proportion of polyamide in the raw material is preferably greater than 30%.
• the polymerization raw material of the present invention is preferably a dry raw material.
• the invention feeds the raw materials into the material mixing device at a uniform speed to ensure the continuous and stable progress of the melt polymerization reaction and the feeding.
• the rate of polymerization reaction is related to temperature. High temperature polymerization is fast and efficient, but too high temperature will cause a series of problems such as yellowing and degradation. Therefore, it is necessary to balance the relationship between reaction temperature and time.
• the average residence time of the material of the present invention in the material mixing device and subsequent polymerization device from feeding to discharging is preferably 10-120 min.
• the residence time of the material 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. When the material flows continuously and under the condition of fixed output, the average residence time of the material in the device is theoretically the same.
• the polymerization reaction 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, so as to obtain 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 product shutdowns.
• PA66 and PA56 are currently the most widely used polycondensation polyamides, both of which can be produced by the method of the present invention, and other monomers can be added to the polymerized monomers to adjust the properties of the polymer to meet more extensive application requirements.
• the nylon polymerization method of the present invention uses polyamide as the reactive dispersion medium to melt and polymerize with dibasic acid or ester and diamine monomer in a material mixing device.
• the raw materials enter the material mixing device continuously and uninterruptedly.
• the polymerization reaction is completed during the flow process of material transfer, the continuity of feeding, reaction and discharging is realized, and the intermittent production shortcomings of traditional reactor technology are overcome, and the step of preparing nylon salt in aqueous solution is omitted, and nylon is avoided.
• the production of waste liquid in the salt preparation process is a green and environmentally 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 widely promoted and applied in actual production.
• 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 during the preparation of nylon salt in the aqueous solution, and the obtained nylon product has uniformity The characteristics of good sex and stable quality.
• the present invention is used for mixing and dispersing materials in screw and tubular reactors. Because the device has good airtight performance and rapid heat dissipation, it is suitable for diamines of various boiling points, and the material addition efficiency is high, which overcomes the conventional molten nylon polymerization and is only applicable Diamines with higher boiling points and low efficiency of addition.
• the polyamide raw materials of the present invention have a wide range of sources, which can be finished polyamides available on the market, or prepolymer oligomers of polyamides, which can be easily prepared by mixing different acids or amines. Co-polyamide, thereby adjusting the performance of the product in a wider range.
• the dispersion system Due to the addition of polyamide resin, the dispersion system has a certain melting point and viscosity, which can adapt to the application of screw extruder and tubular reaction device, fully utilize the advantages of high heat transfer and dispersion efficiency of the equipment, and realize continuous production , Greatly improve production efficiency.
• the dibasic acid usually has a higher melting point and is more difficult to disperse
• it is preferable to disperse the dibasic acid into the polyamide first, first react with the polyamide, and then add the diamine to ensure the reaction between the polyamide and the monomer.
• the rate and dispersion effect The dibasic acid and polyamide are reacted at high temperature, and the dibasic acid is uniformly dispersed into the polymer by chemical bond or physical dispersion to form an intermediate, and then polycondensed with the diamine, so that there is no need to use water or water during the synthesis process.
• the preparation of the nylon salt in the alcohol solution greatly simplifies the polymerization process and avoids the production of waste liquid during the preparation of the nylon salt.
• the by-product produced is theoretically only water produced in the polycondensation process, which is a green and environmentally friendly high-temperature polymer synthesis method.
• dibasic acid esters with lower boiling points than dibasic acids can also be used to prepare nylon by melt polymerization using the method of the present invention, and because dibasic acid esters are used When used as a raw material, the removed small-molecule alcohol is easier to be released during devolatilization than water, and the polymerization efficiency is higher than when a dibasic acid is used as a raw material.
• the polymerization reaction 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, so as to obtain 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 product shutdowns.
• the route of the present invention does not require special preparation of nylon salt in advance, but uses molten polyamide as a solvent, so that the dibasic acid and diamine directly undergo salt formation and polymerization in the polyamide dispersion system after dispersion, so it is very convenient to pass Several dibasic acids or diamines are mixed and then fed to prepare copolymerized nylon, so as to adjust the performance of the product in a larger range. It is even possible to add part of the polyacid or polyamine into the monomer to make the product have a certain degree of cross-linking, thereby improving the temperature resistance of the product.
• the present invention uses a weight metering device or a continuous volume metering device to ensure the stability and continuity of the addition of each component. Part or all of the raw materials can be mixed according to the proportions before metering.
• the weight measurement includes the use of a weightless metering device and a liquid pump metering device
• the volume measurement includes the use of a screw metering device and a liquid pump metering device.
• the polymerization raw materials by mass include 5 parts of polymerized monomer dibasic acid and dibasic acid ester, 3 parts of diamine, and 10 parts of reactive dispersion medium polyamide; the polymerization step includes the polymerization of raw materials.
• the material mixing device is continuously added in proportion, so that the raw materials are mixed and reacted in the material mixing device to form a continuously conveyed melt, and the uniformly dispersed melt is reacted in the subsequent polymerization device until the nylon polymerization reaches the required molecular weight.
• a continuous nylon polymerization method comprising 60 parts of polymerized monomer dibasic acid, 50 parts of diamine and 90 parts of reactive dispersion medium polyamide; the raw materials are continuously added to the tubular reaction in proportion by weight measurement or volume measurement
• the device enables the polymerization monomer to react and mix uniformly in the molten reactive amide dispersion medium, and the materials are uniformly mixed and then enter the subsequent polymerization device to polymerize until the nylon resin reaches the required molecular weight.
• the temperature of the material mixing process can satisfy the melting of the raw material polyamide.
• the melting point of the dibasic acid raw material is lower than that of the polyamide raw material.
• the polyamide raw material is melted first and then sent to the tubular reaction device.
• the molar ratio of the diamine to the dibasic acid and the dibasic acid ester is between 0.4-2.5:1.
• the polymerization raw materials by mass include 50 parts of polymerized monomer dibasic acid ester, 40 parts of diamine and 10 parts of reactive dispersion medium polyamide; the raw materials are measured by weight or volume.
• the screw extrusion device is continuously added in proportion to make the polymerization monomer react and mix uniformly in the molten reactive amide dispersion medium, and the materials are uniformly mixed and then enter the subsequent polymerization device to polymerize until the nylon resin reaches the desired molecular weight.
• the raw material dibasic acid and the molten raw material polyamide are reacted and mixed uniformly, and then the diamine is continuously added to it, and the reaction is uniformly mixed in the material mixing device.
• the diamine is melted into a liquid state or dissolved in a solvent and added to the screw extrusion device in a liquid state.
• the molar ratio of the diamine and the dibasic acid ester is between 0.4-2.5:1.
• the maximum temperature reached by the material during the polymerization process is not less than 250°C.
• the average residence time of the materials in the material mixing device and subsequent polymerization device from feeding to discharging is 10-120min.
• the polymerization raw materials by mass include 5 parts of polymerized monomer dibasic acid ester, 5 parts of diamine and 90 parts of reactive dispersion medium polyamide; the raw materials are measured by weight or volume.
• the screw extruder is continuously added in proportion to make the polymerization monomer react and mix uniformly in the molten reactive amide dispersion medium. After the materials are uniformly mixed, they enter the subsequent polymerization device to polymerize until the nylon resin reaches the required molecular weight, and then pass through the screw extrusion device Devolatilization, extrusion granulation.
• the reactive amide dispersion medium is a melt formed after the reaction of the raw material polyamide and the polymerized monomer.
• the raw material dibasic acid and the molten raw material polyamide are reacted and mixed uniformly, and then the diamine is continuously added to it, and the reaction is uniformly mixed in the material mixing device.
• the filling rate of at least one section of the device before the addition of the diamine is 100%.
• the diamine is added to the screw extrusion device in liquid form.
• the molar ratio of the diamine and the dibasic acid ester is between 0.4-2.5:1.
• the maximum temperature reached by the materials during the polymerization process is not less than 290°C.
• the average residence time of the materials in the material mixing device and subsequent polymerization device from feeding to discharging is 10-120min.
• the dibasic acid raw material contains aromatic dibasic acid, and the molar ratio of the aromatic dibasic acid accounts for at least 20% of the molar ratio of the dibasic acid raw material.
• the moisture content in the raw material does not exceed 5%.
• the rear end of the screw extruder is provided with three exhaust holes, and the latter two exhaust holes are vacuumed.
• the temperature of the die was set to 310°C, and continuous extrusion and granulation were performed to obtain PA6T resin with a melting point of 313°C and a relative viscosity of 1.7.
• the average residence time of the material in the polymerization device was about 10 minutes.
• terephthalic acid, PA66 resin, hexamethylene diamine and 0.5% of the total weight of antioxidants, 0.2% of the catalyst are mixed, and they are fed into the same-rotating twin-screw extruder from the front end through a weight loss metering device. Out.
• the temperature near the front end of the screw is 150-260°C
• the subsequent polymerization temperature after the materials are evenly mixed is 250-320°C
• the total length and diameter of the screw is 192:1
• three exhaust holes are provided, and the last two are exhausted to vacuum .
• the temperature of the die was set to 310°C, and continuous extrusion and granulation were performed to obtain PA6T resin with a melting point of 312°C and a relative viscosity of 1.5.
• the average residence time of the material in the polymerization device was about 12 minutes.
• Example 5 hexamethylene diamine was added at the front end of the screw. Because diamine is easily lost due to volatilization, the ratio of hexamethylene diamine in the nylon product obtained in comparison with Example 5 is reduced.
• the material of Example 5 is smooth and uniform, and the die is discharged continuously However, the product of this example is more difficult to draw and cut into pellets than Example 5.
• the materials After the materials are evenly melted and mixed, the materials enter the two reactors through the three-way valve link in turn, react at 310°C for 15 minutes, and react under -0.04MPa vacuum for another 15 minutes. Screw extrusion granulation.
• the obtained PA10T resin has a melting point of 308°C and a relative viscosity of 2.4.
• the two reactors take turns to receive the mixed raw materials, and after they are separately polymerized, the raw materials are discharged in turn to realize continuous production.
• dimethyl terephthalate was used to replace terephthalic acid in the reaction.
• the same viscosity can be reached in a shorter reaction time, the reaction speed is faster, and the methanol generated by the reaction is collected and processed.
• adipic acid and PA66 resin in a weight ratio of 14.6:10, 0.5% of the total weight of antioxidant, 0.2% of the catalyst, and feed it into the co-rotating twin-screw extruder from the front through the weight loss metering device, and set the screw temperature.
• the temperature of the feed section of the screw is 150-220°C, and the temperature of the melting and dispersing section is 220-280°C.
• hexamethylene diamine is continuously added from the melting and dispersing section. The added hexamethylene diamine is controlled by weight loss to make hexamethylene diamine and adipic acid
• the weight ratio is 11.8:14.6.
• the temperature of the screw polymerization section is set to 220-280°C, the total length and diameter of the screw are 192:1, three vent holes are provided, and the last two are exhausted to vacuum.
• the temperature of the die was set at 260°C, and continuous extrusion and granulation were performed to obtain PA66 resin with a melting point of 265°C and a relative viscosity of 1.8.
• the average residence time of the material in the polymerization device was about 25 minutes.
• the weight ratio of 14.6:10 mix adipic acid and PA66 resin, 0.5% of the total weight of the antioxidant, 0.2% of the catalyst, and feed the same-rotating twin screw with a length-to-diameter ratio of 42:1 from the front through the weight loss metering device.
• Extruder set the screw temperature, the screw feed section temperature is 150-220°C, the melt dispersion section temperature is 220-280°C, after the material is melted, hexamethylene diamine is continuously added from the melt dispersion section, and the added hexamethylene diamine is controlled by weight loss , So that the weight ratio of hexamethylene diamine and adipic acid is 11.8:14.6.
• the materials are sent to a continuous flow tubular reactor with an effective volume of 30 liters and equipped with a stirring device through a melt pump.
• the temperature is set to 260-280°C.
• To the twin screw extruder set the temperature to 260-280°C, set up three vent holes, the last two vents to vacuum, the die temperature is set to 260°C, continuous extrusion and granulation to obtain PA66 resin ,
• the melting point is 265°C
• the relative viscosity is 2.2
• the average residence time of the material in the polymerization device is about 30 minutes.
• the materials are sent to a continuous flow tubular reactor with an effective volume of 30 liters and equipped with a stirring device through a melt pump.
• the temperature is set to 260-280°C.
• To the twin-screw extruder set the temperature to 260-280°C, with three exhaust holes, and the latter two exhaust to vacuum.
• the temperature of the die was set at 260°C, and continuous extrusion and granulation were performed to obtain PA66 resin with a melting point of 265°C and a relative viscosity of 2.8.
• the average residence time of the material in the polymerization device was about 40 minutes, which was longer than that of Example 10. , The viscosity of the obtained product is different.
• PA56 resin After the PA56 resin is melted, it is continuously sent to a pipeline reactor equipped with a static mixing device, and adipic acid is continuously added.
• the ratio of PA56 resin and adipic acid is controlled by weight loss to 10:14.6, so that the molten PA56 resin and adipic acid are in the pipeline.
• the material flows continuously in a pipeline reactor equipped with a static mixing device. After 30 minutes of reaction at 250-280°C, the continuously flowing material is drained and extruded through a screw extruder with a length-to-diameter ratio of 20:1.
• a PA56 resin was obtained with a melting point of 252°C and a relative viscosity of 2.2.
• Two polymerizers are used for feeding and discharging alternately.
• the polymerization time for vacuuming in the polymerizer is 30 minutes, and then through a twin-screw extruder with a length-to-diameter ratio of 30 for devolatilization and granulation, PA56 is obtained with a melting point of 255. , The viscosity is 2.5.
• the temperature of the screw polymerization section is set to 220-275°C, the total length and diameter of the screw are 192:1, three exhaust holes are set, and the last two exhaust holes are vacuumed.
• the temperature of the die was set at 250°C, and continuous extrusion and granulation were performed to obtain PA56 resin with a melting point of 252°C and a relative viscosity of 2.2.
• the average residence time of the material in the polymerization device was about 25 minutes.
• Example 12 uses the pipeline reactor mixture material, which can easily increase the effective volume, so that the device has a greater production capacity, but it is necessary to melt the polyamide raw material first and use a melt pump Generate a large thrust to push the material to flow in the pipeline.
• Examples 13 and 14 use screw device mixtures, which can be directly and continuously produced using granular nylon raw materials. However, because the effective volume of the screw extrusion device is small, in order to ensure the reaction time, a long length-to-diameter ratio screw ( In Example 14, the total length to diameter ratio of the screw device reached 192, which required three stages in series, so that the device occupies a large area on the ground).
• Example 13 uses a reactor to extend the reaction time, which can achieve greater viscosity and higher productivity, but makes the entire process a semi-continuous process.
• the product is in the reactor due to the problem of the order of feeding and discharging, and the materials are reacting.
• the time distribution in the kettle will be wider than that in the continuous device, so that the stability of the product performance is not as good as in Example 14.
• PA56 resin is continuously fed into a pipeline reactor equipped with a static mixing device in solid form.
• the temperature is set to 300°C to melt the resin.
• Adipic acid is continuously added.
• the ratio of PA56 resin and adipic acid is controlled by weight loss to be 10:14.6.
• the material flows continuously in a pipeline reactor equipped with a static mixing device, and reacts for 60 minutes at 250-280°C.
• the continuously flowing material is drained and extruded through a screw extruder with a length-to-diameter ratio of 20:1.
• the obtained PA56 resin has a melting point of 243°C and a relative viscosity of 1.6.
• Example 12 The results show that because the PA56 resin is added in solid form, the heating efficiency of the static mixer is limited, the output is reduced by half, and the reaction time is doubled. It is still difficult to achieve the same polymerization effect as in Example 12.
• the relative viscosity of Example 12 can reach 2.2, and the relative viscosity of Example 15 can only reach 1.6 when the reaction time is doubled.
• PA56 resin After PA56 resin is melted, it is continuously sent to a pipeline reactor equipped with a static mixing device, and terephthalic acid is continuously added.
• the ratio of PA56 resin and terephthalic acid is controlled to be 10:16.6 by weight loss, so that the molten PA56 resin and terephthalic acid can be melted.
• the dicarboxylic acid is mixed in the pipeline, and then liquid pentane diamine is continuously added to control the weight ratio of pentane diamine and PA56 to 10.5:5.
• the material flows continuously in a pipeline reactor equipped with a static mixing device, and reacts for 30 minutes at 250-300°C.
• the continuously flowing material is drained and extruded through a screw extruder with a length-to-diameter ratio of 20:1.
• the set temperature is 200-220°C
• the set temperature is 200-270°C
• the head temperature is set to 200°C
• Obtained PA1010 resin the melting point is 208°C
• the relative viscosity is 2.4
• the average residence time of the material in the polymerization device is about 115 minutes.
• the screw temperature the temperature of the feed section is 100-210°C
• the temperature of the melt dispersion section is 220-280°C
• the length of the screw The ratio is 42, and then the uniformly mixed materials are continuously fed into a plug flow pipeline reactor with an effective volume of 30 liters to continue polymerization, set the temperature to 220-280°C, and then pass through the same-rotating twin-screw with a length-to-diameter ratio of 32
• the extruder is extruded and granulated.
• the whole set of equipment is equipped with 3 vent holes. The last two vent holes are vacuumed to obtain PA66 resin.
• the melting point is 265 degrees Celsius and the relative viscosity is 2.6.
• the average residence time of the material in the polymerization device is about 35 minutes.
• the ratio of dibasic acid in the raw material is correspondingly reduced, and the molar ratio of dibasic acid to diamine is 0.67:1.
• the amount of 25 parts of prepolymer unchanged and reduce the amount of adipic acid to 3.5 parts, then the amount of hexamethylene diamine needs to be 6 parts.
• the molar ratio of adipic acid to hexamethylene diamine is approximately 0.5:1. If the proportion of adipic acid in the polymerization raw material is further reduced, the molar ratio of diacid and amine will be further reduced. If a prepolymer with amino-based end groups is selected, the molar ratio of dibasic acid and diamine will be reversed, with acid surpassing amine.
• the filling rate of at least one section is 100% to ensure that there is at least one sealing section before the addition of the diamine to prevent the gasification of hexamethylene diamine.
• the amine ran out from the entrance.
• the weight ratio of 19.4:6 mix dimethyl terephthalate and PA10T resin, 0.5% of the total weight of antioxidant, 0.2% of the catalyst, and input the single screw extruder from the feed section through the weight loss metering device.
• Screw temperature the temperature of the feed section is 100-220°C
• the temperature of the melt-dispersion section is 250-310°C.
• the set temperature is 280-320°C. Then through screw extrusion and granulation, PA10T resin is obtained, the melting point is 308°C, the relative viscosity is 2.2, and the average residence time of the material in the polymerization device is about 25 minutes.
• the co-rotating twin-screw extruder has a set temperature of 280-320°C, and is equipped with three exhaust holes, and the latter two are exhausted to vacuum.
• the temperature of the die was set to 310°C, and continuous extrusion and granulation were performed to obtain PA6T/66 resin with a melting point of 316°C and a relative viscosity of 2.8.
• the average residence time of the material in the polymerization device was about 25 minutes.
• the terephthalic acid and PA6 resin, 0.5% of the total weight of the antioxidant, 0.2% of the catalyst are mixed in a weight ratio of 18:12, and the same-rotating twin-screw extruder with a length-to-diameter ratio of 42 is fed from the front end through a weight loss metering device. Out. Set the screw temperature, the temperature of the feeding section is 150-220°C, and the temperature of the melting and dispersing section is 200-310°C. After the material is melted, hexamethylene diamine is continuously added from the melting and dispersing section, and the added hexamethylene diamine is controlled by weight loss to make the hexamethylene diamine and The molar ratio of terephthalic acid is 1.01:1.
• the materials are sent to a plug flow tubular reactor with an effective volume of 30 liters and equipped with a stirring device through a melt pump.
• a plug flow tubular reactor with an effective volume of 30 liters and equipped with a stirring device through a melt pump.
• To the twin screw extruder set the temperature to 280-305°C, with three vent holes, and the last two vents to vacuum.
• the temperature of the die is set at 310°C, and continuous extrusion and granulation are performed to obtain PA6T/6 resin, with a melting point of 290°C, a relative viscosity of 2.5, and the average residence time of the material in the polymerization device is about 25 minutes.
• the terephthalic acid and PA6 resin, 0.5% of the total weight of the antioxidant, and 0.2% of the catalyst are continuously fed into the double-rotor continuous banburying device, so that the terephthalic acid is uniformly dispersed into the PA6 In the resin.
• hexamethylene diamine is continuously added from the screw conveying section, and the added hexamethylene diamine is controlled by weight loss, so that the molar ratio of hexamethylene diamine and terephthalic acid is 1.01:1.
• the materials are evenly mixed, they are sent to a plug flow tubular reactor with an effective volume of 30 liters and equipped with a stirring device through a melt pump.
• the twin screw extruder To the twin screw extruder, set the temperature to 280-305°C, with three vent holes, and the last two vents to vacuum. The temperature of the die was set to 310°C, and continuous extrusion and granulation were performed to obtain PA6T/6 resin with a melting point of 290°C and a relative viscosity of 2.6. The average residence time of the material in the polymerization device was about 25 minutes.
• Example 22 Since the continuous internal mixing device has a better dispersion effect, a more compact device can be used to achieve the same effect as the screw extrusion device used in Example 21.
• Example 22 compared with Example 21, the diameter of the device in the material mixing stage was reduced by 1/3.
• the monomer diacid and PA6T/66 resin are mixed with 0.5% antioxidant and 0.2% catalyst.
• the monomeric diacid contains adipic acid and terephthalic acid in a molar ratio of 8:2. It is fed into a co-rotating twin-screw extruder with a length-to-diameter ratio of 42 from the front end through a weightless metering device. Set the screw temperature, the temperature of the feeding section is 150-260°C, and the temperature of the melting and dispersing section is 200-310°C. After the material is melted, hexamethylene diamine is continuously added from the melting and dispersing section.
• the molar ratio of terephthalic acid is 1.01:1.
• the co-rotating twin-screw extruder has a set temperature of 280-320°C, and is equipped with three exhaust holes, and the latter two are exhausted to vacuum.
• the temperature of the die was set to 310°C, and continuous extrusion and granulation were performed to obtain PA6T/66 resin with a melting point of 298°C and a relative viscosity of 2.7.
• the average residence time of the material in the polymerization device was about 25 minutes.
• the main screw extruder has 10 sections, and then it enters into a continuous flow reactor equipped with stirring with an effective volume of 30 liters.
• the set temperature is 280-320°C. After exiting the pipe, it enters the same-rotating twin-screw with a length-to-diameter ratio of 32:1.
• the extruder is set to a temperature of 280-320°C, and is provided with three exhaust holes, and the latter two exhaust air to vacuum.
• the temperature of the die was set to 310°C, and continuous extrusion and granulation were performed to obtain PA10T resin with a melting point of 310°C and a relative viscosity of 2.2.
• the average residence time of the material in the polymerization device was about 25 minutes.
• the nylon finished product obtained by the continuous polymerization process of the present invention has good uniformity and can be used for conventional melt conveying and die discharge.
• the material strips are smooth and uniform, continuous strips, full mixing after cutting, and continuous production performance. Stable and high product qualification rate.
• the preparation method of the present invention can add some or several additives such as conventional antioxidants, catalysts, tougheners, molecular weight regulators and lubricants for polyamide synthesis as required, or directly complete the polymerization reaction without additives. .
• the preparation method is suitable for the synthesis of various polyamide resins, and is not limited to the types listed in the examples, and has a wide range of applications.

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