Sulfonic acid group modified furan-based polyamide and preparation method and device thereof

Abstract

The invention discloses sulfonic acid modified furanyl polyamide and its preparation method and device, and relates to the field of heat treatment processing medium. It uses 2,5-furandicarboxylic acid chloride, 4,4'-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid derived from biomass resources as polymerization monomers to generate environmentally friendly new semi-bio-based polyamide through polymerization reaction, and comprises the following steps: under the protection of inert gas, dissolving 4,4'-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid in an organic solvent to form a diamine solution; adding 2,5-furandicarboxylic acid chloride to the diamine solution in batches at a temperature in the range of -10°C to 30°C to react; continuing the reaction until the furanyl polyamide of the desired molecular weight is obtained. The bio-based raw materials used are widely available, abundant in reserves and renewable, and can be used as a supplement and partial substitute for non-renewable fossil raw material monomers, reducing the emission intensity of greenhouse gases and mitigating the greenhouse effect, thereby synthesizing high-performance environmentally friendly electrode materials.

Description

Technical Field

[0001] The invention relates to the field of heat treatment processing media, in particular to sulfonic acid group-modified furan-based polyamide and a preparation method and device thereof. Background Art

[0002] Polyamide (PA), commonly known as nylon, is a type of polymer that contains repeating amide groups (-NHCO-) ​​in the main chain of the polymer synthesized mainly from dibasic acids and diamines, amino acids or lactams. It is one of the five general engineering plastics together with polycarbonate (PC), polybutylene terephthalate (PBT), polyoxymethylene (POM) and polyphenylene ether (PPO). Polyamide is the basic resin with the most varieties, the largest output, the widest application and the best comprehensive performance among the five general engineering plastics. The main chain of semi-aromatic polyamide is mainly composed of alternating alkylene, aromatic rings and amide groups. This structural characteristic determines that it has the advantages of both aliphatic polyamide and fully aromatic polyamide. It has good heat resistance and dimensional stability, good processing performance, and high cost performance, which makes it have a higher application prospect. The market demand continues to increase and it is widely used in the automotive, electronic and electrical industries.

[0003] On the other hand, lithium-ion batteries have dominated the global portable electronics and grid storage battery markets, and these applications also place the most stringent requirements on the performance of lithium-ion batteries, including duty cycle (i.e., operating temperature and charge and discharge rate) and durability (expected service life). Therefore, steady and significant progress has been made in the development of various positive and negative active materials, making electrode materials with various crystal structures and chemical properties promising candidates for large-scale commercial battery development. In order to meet the demand for better lithium batteries, considerable improvements are still needed in the performance and durability of its electrode materials.

[0004] The bio-based semi-aromatic polyamide synthesized by the high molecular weight furan-based aromatic polyamide synthesis method published by the patent publication number "CN110256668A" has excellent thermodynamic and mechanical properties and can be used to prepare fibers, membrane materials, and nanoparticle / polymer composite materials. And the raw materials used are biomass resources, which have the advantages of wide sources, abundant reserves and degradability. Thereby reducing the use of petrochemical resources and the discharge of toxic wastes, achieving green environmental protection, reducing the emission intensity of greenhouse gases, and mitigating the greenhouse effect. It has important environmental significance. On this basis, by introducing sulfonic acid groups into the aramid molecular chain, the manganese ion adsorption capacity of aramid fiber is improved while basically maintaining the original excellent performance, so as to obtain an electrode material with excellent performance and durability. In view of the above problems, the inventors propose sulfonic acid modified furan-based polyamide and its preparation method and device to solve the above problems. Summary of the invention

[0005] In order to improve the manganese ion adsorption capacity of aramid fiber while basically maintaining the original excellent performance, so as to obtain an electrode material with excellent performance and durability, the purpose of the present invention is to provide a sulfonic acid modified furan-based polyamide and a preparation method and device thereof.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solution: the preparation method of sulfonic acid modified furan polyamide is to use 2,5-furandicarboxylic acid chloride and 4,4'-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid derived from biomass resources as polymerization monomers to generate an environmentally friendly new semi-bio-based polyamide through a polymerization reaction, comprising the following steps:

[0007] S1. Under the protection of inert gas, dissolving 4,4′-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid in an organic solvent to form a diamine solution;

[0008] S2, adding 2,5-furandicarboxylic acid chloride to the diamine solution in batches at a temperature in the range of -10°C to 30°C, and reacting under stirring;

[0009] S3. Continue the reaction until the desired molecular weight of furan-based polyamide is obtained.

[0010] The furan-based polyamide material comprises repeating units having the following formulae (I) and (II):

[0011]

[0012] The number average molecular weight of the furan-based polyamide is greater than 200,000.

[0013] The furan-based polyamide has the structure of the following formula (III) or (IV):

[0014]

[0015] In formula (III), n is 500 to 1000;

[0016]

[0017] In formula (IV), m>1, k>1 and m+k=500-1000.

[0018] The organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and acetonitrile, the mass ratio of the organic solvent to the diamine monomer is 2:1 to 10:1, and the molar ratio of the 4,4′-diaminodiphenyl ether to 2,5-diaminobenzenesulfonic acid is 5:1 to 10:1.

[0019] The molar ratio of the 2,5-furandicarboxylic acid chloride to the diamine monomer is 1:1 to 1:1.5, the inert gas is preferably one or more of nitrogen, helium or argon, and the reaction time is 2 hours.

[0020] The device used in the preparation method of sulfonic acid modified furan polyamide comprises a support frame, an operating table is fixedly installed on the upper end of the support frame, a first motor is arranged at one end of the operating table, a coating device for uniformly coating slurry is arranged on the upper surface of the operating table, and a collecting device for collecting slurry is arranged at one end of the operating table away from the first motor.

[0021] Preferably, the coating device comprises a fixed plate, the first motor is fixedly mounted on the upper surface of the fixed plate, symmetrical slide grooves are provided on both sides of the operating table, threaded rods are rotatably mounted inside the two slide grooves, the outer wall of the threaded rod is threadedly connected with a slider, the slider is T-shaped, the slider matches the slide groove, the outer wall of the same end of the two threaded rods is fixedly mounted with a pulley, the outer wall of the two pulleys is sleeved with a belt, and the power output shaft of the first motor is fixedly connected with one end of one of the threaded rods. A baffle is fixedly mounted on the outer wall of the slider, buckling plates are fixedly mounted on both sides of the upper surface of the operating table, buckling grooves are provided on the outer wall of the buckling plate, and a limit plate is fixedly mounted on the outer wall of the baffle, and a second motor is fixedly mounted on the upper surface of the limit plate, and a coating cylinder is fixedly mounted on the power output shaft of the second motor, the power output shaft of the second motor passes through the buckling groove, and a plurality of coating holes arranged equidistantly in a ring are provided on the outer wall of the coating cylinder. A connecting rod is rotatably installed at one end of the coating cylinder away from the second motor, a transmission plate is fixedly installed on the outer wall of one end of the connecting rod located inside the coating cylinder, a transmission groove is provided on the upper surface of the transmission plate, one end of the connecting rod away from the transmission plate is fixedly connected to the outer wall of the baffle, a through hole is provided on the upper surface of the baffle near one end of the connecting rod, and a feed hopper is inserted into the through hole.

[0022] Preferably, the collecting device includes a fixed sleeve, two of which are symmetrically installed at the bottom of the operating table, a buckle plate passes through the interior of the fixed sleeve, the buckle plate is L-shaped, the outer wall of the fixed sleeve is threaded with bolts, storage plates are placed on the upper surfaces of the two buckle plates, liquid flow grooves are opened on both sides of the upper surface of the operating table, and the storage plate is located below one end of the liquid flow groove.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention uses a sulfonic acid group-modified furan-based polyamide, and uses 2,5-furandicarboxylic acid chloride, 4,4′-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid as raw materials. The furan-based polyamide provided by the present invention has excellent thermodynamic properties and mechanical properties, and is outstanding in manganese ion adsorption capacity, and can be used as an electrode material with excellent performance and durability. The used bio-based raw materials are widely available, abundant in reserves and renewable, and can be used as a supplement and partial replacement for non-renewable fossil raw material monomers, thereby reducing the emission intensity of greenhouse gases and mitigating the greenhouse effect, thereby synthesizing a high-performance environmentally friendly electrode material. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0026] Figure 1 It is an overall schematic diagram of the present invention.

[0027] Figure 2 It is a schematic diagram of the structure of the operating table of the present invention.

[0028] Figure 3 It is a schematic diagram of the threaded rod structure of the present invention.

[0029] Figure 4 For the present invention Figure 2 A magnified view of the structure at A.

[0030] Figure 5 It is a schematic diagram of the coating tube structure of the present invention.

[0031] Figure 6 It is a schematic diagram of the transmission plate structure of the present invention.

[0032] In the figure: 1. support frame; 2. collecting device; 21. storage plate; 22. buckle plate; 23. bolt; 24. fixing sleeve; 3. coating device; 31. feed hopper; 32. baffle; 33. coating hole; 34. coating cylinder; 35. snap-fit ​​plate; 36. snap-fit ​​groove; 37. fixing plate; 38. threaded rod; 39. slide groove; 310. second motor; 311. limit plate; 312. slider; 313. pulley; 314. belt; 315. through hole; 316. connecting rod; 317. transmission plate; 318. transmission groove; 4. liquid flow trough; 5. operating table; 6. first motor. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Embodiment 1: Figure 1-6 As shown, the present invention provides a method for preparing sulfonic acid group-modified furan-based polyamide, comprising the following steps:

[0035] The preparation method of sulfonic acid modified furan polyamide is to use 2,5-furandicarboxylic acid chloride, 4,4'-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid derived from biomass resources as polymerization monomers to generate an environmentally friendly new semi-bio-based polyamide through a polymerization reaction, comprising the following steps:

[0036] S1. Under the protection of inert gas, dissolving 4,4′-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid in an organic solvent to form a diamine solution;

[0037] S2, adding 2,5-furandicarboxylic acid chloride to the diamine solution in batches at a temperature in the range of -10°C to 30°C, and reacting under stirring;

[0038] S3. Continue the reaction until the desired molecular weight of furan-based polyamide is obtained.

[0039] The furan-based polyamide material comprises repeating units having the following formulae (I) and (II):

[0040]

[0041] The number average molecular weight of the furan-based polyamide is greater than 200,000.

[0042] The furan-based polyamide has the structure of the following formula (III) or (IV):

[0043]

[0044] In formula (III), n is 500 to 1000;

[0045]

[0046] In formula (IV), m>1, k>1 and m+k=500-1000.

[0047] The organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and acetonitrile, the mass ratio of the organic solvent to the diamine monomer is 2:1 to 10:1, and the molar ratio of the 4,4′-diaminodiphenyl ether to 2,5-diaminobenzenesulfonic acid is 5:1 to 10:1.

[0048] The molar ratio of the 2,5-furandicarboxylic acid chloride to the diamine monomer is 1:1 to 1:1.5, the inert gas is preferably one or more of nitrogen, helium or argon, and the reaction time is 2 hours.

[0049] 20 liters of N,N-dimethylacetamide, 1.88 kg of 4,4'-diaminodiphenyl ether, and 177 g of 2,5-diaminobenzenesulfonic acid were added to the reaction kettle in sequence, and the temperature was cooled to 0°C with stirring, and 2 kg of 2,5-furandicarboxylic acid chloride was added in batches at 0 to 10°C. After stirring and reacting for 2 hours, a sulfonic acid group-modified furan-based polyamide slurry was obtained; the obtained slurry was then coated on a base film, extracted with water, and dried at 75°C.

[0050] The device for preparing sulfonic acid modified furan polyamide comprises a support frame 1, an operating table 5 is fixedly mounted on the upper end of the support frame 1, a first motor 6 is arranged at one end of the operating table 5, a coating device 3 for uniformly coating slurry is arranged on the upper surface of the operating table 5, and a collecting device 2 for collecting slurry is arranged at one end of the operating table 5 away from the first motor 6.

[0051] By adopting the above technical solution, the support frame 1 is used to support the operating table 5, the operating table 5 is used to lay the base film, the coating device 3 can evenly coat the base film with slurry, thereby changing the traditional method of manually coating the base film, and the collecting device 2 is used to collect excess slurry, which saves resources and reduces the waste of slurry.

[0052] The coating device 3 includes a fixed plate 37, the first motor 6 is fixedly installed on the upper surface of the fixed plate 37, and symmetrical slide grooves 39 are opened on both sides of the operating table 5. Threaded rods 38 are rotatably installed inside the two slide grooves 39, and the outer wall of the threaded rod 38 is threadedly connected with a slider 312. The slider 312 is T-shaped and matches the slide groove 39. A pulley 313 is fixedly installed on the outer wall of the same end of the two threaded rods 38, and a belt 314 is sleeved on the outer wall of the two pulleys 313. The power output shaft of the first motor 6 is fixedly connected to one end of one of the threaded rods 38.

[0053] By adopting the above technical solution, the slide groove 39 provides a sliding space for the slider 312, and the T-shaped slider 312 can slide inside the slide groove 39 without being disengaged. The pulley 313 can facilitate the rotation of the belt 314. When the first motor 6 rotates, the cooperation between the pulley 313 and the belt 314 will drive the two threaded rods 38 to rotate together. When the two threaded rods 38 rotate together, the two threaded rods 38 will drive the slider 312 to slide inside the slide groove 39.

[0054] A baffle 32 is fixedly installed on the outer wall of the slider 312, and buckling plates 35 are fixedly installed on both sides of the upper surface of the operating table 5. The outer wall of the buckling plate 35 is provided with a buckling groove 36. A limiting plate 311 is fixedly installed on the outer wall of the baffle 32. A second motor 310 is fixedly installed on the upper surface of the limiting plate 311. A coating cylinder 34 is fixedly installed on the power output shaft of the second motor 310. The power output shaft of the second motor 310 passes through the buckling groove 36. The outer wall of the coating cylinder 34 is provided with a plurality of coating holes 33 arranged equidistantly in a ring shape.

[0055] By adopting the above technical solution, the snap-fit ​​groove 36 can keep the coating cylinder 34 horizontal during movement, the snap-fit ​​plate 35 can shield the slurry to prevent it from running around, and the limit plate 311 is used to support the second motor 310. The second motor 310 can drive the coating cylinder 34 to rotate, and the rotation of the coating cylinder 34 can drive the coating hole 33 to drive the slurry to evenly coat the base film.

[0056] A connecting rod 316 is rotatably mounted on one end of the coating cylinder 34 away from the second motor 310, and a transmission plate 317 is fixedly mounted on the outer wall of one end of the connecting rod 316 located inside the coating cylinder 34, and a transmission groove 318 is provided on the upper surface of the transmission plate 317. The end of the connecting rod 316 away from the transmission plate 317 is fixedly connected to the outer wall of the baffle 32, and a through hole 315 is provided on the upper surface of the baffle 32 near the end of the connecting rod 316, and a feed hopper 31 is inserted into the through hole 315.

[0057] By adopting the above technical solution, the connecting rod 316 is a hollow shell tubular structure, the transmission plate 317 can transfer the slurry to one end of the connecting rod 316, and the transmission groove 318 is used for temporary storage of the slurry. When the slurry passes through the transmission groove 318, it will drive the slurry to be transferred from the coating hole 33 on the outer wall of the coating cylinder 34, so that the slurry will not flow out directly from one end of the coating cylinder 34, thereby achieving uniform coating of the slurry.

[0058] The collecting device 2 includes a fixing sleeve 24, two of which are symmetrically installed at the bottom of the operating table 5. A buckle plate 22 runs through the interior of the fixing sleeve 24, and the buckle plate 22 is L-shaped. The outer wall of the fixing sleeve 24 is threadedly connected with a bolt 23. Storage plates 21 are placed on the upper surfaces of the two buckle plates 22. Liquid flow grooves 4 are opened on both sides of the upper surface of the operating table 5, and the storage plate 21 is located below one end of the liquid flow groove 4.

[0059] By adopting the above technical solution, the fixing sleeve 24 plays a limiting role, which can make the buckle plate 22 slide in a fixed direction. The buckle plate 22 is used to support the storage plate 21. Turning the bolt 23 can conveniently adjust the length of the buckle plate 22 and fix it, so that the buckle plate 22 can fix storage plates 21 of different sizes. When the base film is coated with slurry, the slurry will flow out from the flow trough 4, and the flow trough 4 will transfer the slurry to the inside of the storage plate 21, so as to collect excess slurry and save resources.

[0060] Example 2 is different from Example 1 in that 20 liters of N,N-dimethylacetamide, 1.867 kilograms of 4,4'-diaminodiphenyl ether, and 195 grams of 2,5-diaminobenzenesulfonic acid are added to the reaction kettle in sequence, stirred and cooled to 0°C, and 2 kilograms of 2,5-furandicarboxylic acid chloride are added in batches at 0 to 10°C. After stirring and reacting for 2 hours, a sulfonic acid group-modified furan-based polyamide slurry is obtained; the obtained slurry is then coated on a base film, extracted with water, and dried at 75°C.

[0061] Example 3 is different from Example 1 in that 20 liters of N,N-dimethylacetamide, 1.659 kilograms of 4,4'-diaminodiphenyl ether, and 390 grams of 2,5-diaminobenzenesulfonic acid are added to the reaction kettle in sequence, and the temperature is cooled to 0°C with stirring, and 2 kilograms of 2,5-furandicarboxylic acid chloride is added in batches at 0 to 10°C. After stirring and reacting for 2 hours, a sulfonic acid group-modified furan-based polyamide slurry is obtained; the obtained slurry is then coated on a base film, extracted with water, and dried at 75°C.

[0062] Example 4 is different from Example 1 in that the three membrane materials are cut and weighed, and then immersed in a manganese ion solution with a concentration of 20 g / L for 24 hours, taken out, rinsed with clean water and wiped dry, and placed in an electric furnace for burning. 3 to 5 drops of dilute nitric acid are added to the residue to dissolve the fixed volume in a 10 mL volumetric flask, and the manganese ion content is determined by atomic absorption spectrometer. The data are included in Table 1.

[0063] The tensile strength and thermal shrinkage of the above three membrane materials were measured at the same time, and the data are included in Table 1.

[0064] From the test data described in Table 1, it can be concluded that in addition to having high tensile and temperature resistance properties, it also has good manganese ion absorption capacity.

[0065]

[0066] Table 1 Test data of sulfonic acid modified furan polyamide coated diaphragm

[0067] The above examples show that the higher the ratio of sulfonic acid groups, the worse the temperature resistance and the higher the manganese ion absorption capacity.

[0068] Working principle: When the first motor 6 rotates, the cooperation between the pulley 313 and the belt 314 will drive the two threaded rods 38 to rotate together. When the two threaded rods 38 rotate together, the two threaded rods 38 will drive the slider 312 to slide inside the slide groove 39, wherein the limit plate 311 is used to support the second motor 310. The second motor 310 can drive the rotation of the coating cylinder 34. The rotation of the coating cylinder 34 can drive the coating hole 33 to drive the slurry to evenly coat the base film. Among them, the connecting rod 316 is a hollow shell tubular structure, the transmission plate 317 can transfer the slurry to one end of the connecting rod 316, and the transmission groove 318 is used for temporary storage of the slurry. When the slurry passes through the transmission groove 318, it will drive the slurry to be transferred from the coating hole 33 on the outer wall of the coating cylinder 34, so that the slurry will not flow out directly from one end of the coating cylinder 34, thereby achieving uniform coating of the slurry. The coating device 3 can evenly coat the base film with the slurry, thereby changing the traditional method of manually coating the base film and achieving a better coating effect.

[0069] Finally, by turning the bolt 23, the length of the buckle plate 22 can be easily adjusted and fixed, so that the buckle plate 22 can fix the storage plates 21 of different sizes. When the base film is coated with slurry, the slurry will flow out from the flow trough 4, and the flow trough 4 will transfer the slurry to the interior of the storage plate 21, so as to collect excess slurry and save resources.

[0070] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. The preparation method of sulfonic acid modified furan polyamide is to use 2,5-furandicarboxylic acid chloride, 4,4'-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid derived from biomass resources as polymerization monomers to generate environmentally friendly semi-bio-based polyamide through polymerization reaction, comprising the following steps: S1. Under the protection of inert gas, dissolving 4,4′-diaminodiphenyl ether and 2,5-diaminobenzenesulfonic acid in an organic solvent to form a diamine solution; S2, adding 2,5-furandicarboxylic acid chloride to the diamine solution in batches at a temperature in the range of -10°C to 30°C, and reacting under stirring; S3, continuing the reaction until a furan-based polyamide with a desired molecular weight is obtained; The organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and acetonitrile, the mass ratio of the organic solvent to the diamine monomer is 2:1 to 10:1, and the molar ratio of the 4,4′-diaminodiphenyl ether to 2,5-diaminobenzenesulfonic acid is 5:1 to 10:1; The molar ratio of the 2,5-furandicarboxylic acid chloride to the diamine monomer is 1:1 to 1:1.5, the inert gas is one or more of nitrogen, helium or argon, and the reaction time is 2 hours.

2. The method for preparing the sulfonic acid group-modified furan-based polyamide according to claim 1, It is characterized in that The furan-based polyamide material comprises repeating units having the following formulae (I) and (II): The number average molecular weight of the furan-based polyamide is greater than 200,000.

3. The method for preparing the sulfonic acid group-modified furan-based polyamide according to claim 2, It is characterized in that The furan-based polyamide has the structure of the following formula (III) or (IV): In formula (III), n is 500 to 1000; In formula (IV), m>1, k>1 and m+k=500-1000.

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