Preparation method of nanoscale bio-based semi-aromatic polyamide particles

Abstract

The present invention discloses a method for preparing nanoscale bio-based semi-aromatic polyamide particles, which comprises the following steps: adding a first solvent to dilute the bio-based semi-aromatic polyamide into a solution, and then adding a second solvent and stirring evenly to form a first mixed solution; dropping the first mixed solution into a second mixed solution formed by mixing the second solvent and a third solvent to obtain a turbid third mixed solution containing nanoscale bio-based semi-aromatic polyamide particles; filtering, washing, and drying the third mixed solution to obtain the nanoscale bio-based semi-aromatic polyamide. The present invention prepares nanoscale bio-based semi-aromatic polyamide. The method is simple and low in cost, and can prepare nanoscale bio-based semi-aromatic polyamide particles with required particle sizes according to needs. The nanoscale particles can be used in any coating aspect with a water-based solvent system, and can effectively improve the heat resistance and thermal breakdown temperature of the coated product, having the value of popularization and use.

Description

Technical Field

[0001] The present invention relates to the technical field of aqueous coating processes, and specifically to a method for preparing nano-scale bio-based semi-aromatic polyamide particles. Background Art

[0002] In the current industry of aqueous coating processes, most of the materials used to pursue heat shrinkage performance in the coating slurry are large proportions of inorganic particles as the main substances, mixed with some polymer materials used as binders. For example, in the aqueous-coated lithium battery separator, ceramics are used as the main substance in the coating slurry, and some polyacrylates or modified polyacrylates are added as binders. At this time, the lithium battery separator after water coating has good heat shrinkage performance, but there is not much improvement in the film-breaking temperature. At the same time, most of the polymer materials applicable to water coating are presented in the form of solvents or viscous emulsions, and it is difficult to improve the heat film-breaking temperature in the coated structure like inorganic substances. And it is very difficult for polymer materials that can improve the heat film-breaking temperature to achieve nano-scale particles, which cannot meet the coating requirements of a few micrometers. In view of the above problems, the inventor proposes a method for preparing nano-scale bio-based semi-aromatic polyamide particles to solve the above problems. Summary of the Invention

[0003] In order to solve the problem that most of the polymer materials applicable to water coating are presented in the form of solvents or viscous emulsions, and it is difficult to improve the heat film-breaking temperature in the coated structure like inorganic substances, and it is very difficult for polymer materials that can improve the heat film-breaking temperature to achieve nano-scale particles, which cannot meet the coating requirements of a few micrometers; the purpose of the present invention is to provide a method for preparing nano-scale bio-based semi-aromatic polyamide particles.

[0004] To solve the above technical problems, the present invention adopts the following technical solutions: A method for preparing nano-scale bio-based semi-aromatic polyamide particles, comprising the following steps:

[0005] S1. Add a first solvent to dilute the bio-based semi-aromatic polyamide into a solution, and then add a second solvent and stir evenly to form a first mixed solution;

[0006] S2. Drop the first mixed solution into a second mixed solution formed by mixing the second solvent and a third solvent to obtain a turbid third mixed solution containing nano-scale bio-based semi-aromatic polyamide particles;

[0007] S3. Filter, wash, and dry the third mixed solution to obtain nano-scale bio-based semi-aromatic polyamide.

[0008] In a preferred embodiment, in step S1, the first solvent is one or more of N-methylpyrrolidone, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, and dimethyl sebacate.

[0009] In a preferred embodiment, in step S1, the bio-based semi-aromatic polyamide is a polymer formed from a diacid monomer derived from substituted or unsubstituted furandicarboxylic acid or its derivatives and a diamine monomer derived from substituted or unsubstituted 4,4'-diaminodiphenyl ether or its derivatives.

[0010] In a preferred embodiment, the degree of polymerization n of the bio-based semi-aromatic polyamide is 700 - 2000, and the number average molecular weight of the bio-based semi-aromatic polyamide is greater than 200000.

[0011] In a preferred embodiment, in step S1, the solid content of the bio-based semi-aromatic polyamide diluted into a solution by the first solvent is 0.5% - 10%.

[0012] In a preferred embodiment, in step S1, the second solvent is water, and the addition amount of the second solvent is 15 - 28 times that of the bio-based semi-aromatic polyamide solid.

[0013] In a preferred embodiment, in step S2, the third solvent is one or several of methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, tripropylene glycol, and glycerol.

[0014] In a preferred embodiment, in step S2, the mass fraction of the second solvent in the second mixture is 50% - 100%.

[0015] In a preferred embodiment, in step S3, the solvent used in the washing process is water, the temperature in the drying process is 35°C - 100°C, and the drying time is 15 - 30 min.

[0016] In a preferred embodiment, add 25 grams of bio-based semi-aromatic polyamide to beaker one, then add 475 grams of dimethylformamide and stir evenly until it becomes clear. Then add 625 grams of water to beaker one and stir evenly to obtain the first mixture. Add 700 grams of water and 300 grams of isopropanol to beaker two and stir evenly to form the second mixture. Then drop the first mixture into the second mixture. After the first mixture is completely dropped into the second mixture, turn off the stirrer to obtain the third mixture. Filter the third mixture to obtain a solid, then wash the solid three times with water and dry it at 55°C to obtain the nano bio-based semi-aromatic polyamide solid.

[0017] Preferably, in one implementation case, 10 g of bio-based semi-aromatic polyamide is added to beaker 1, and then 490 g of dimethylformamide is added and stirred evenly until it becomes clear. Then, 200 g of water is added to beaker 1 and stirred evenly to obtain mixture 1. 425 g of water and 75 g of isopropanol are added to beaker 2 and stirred evenly to obtain mixture 2. Then, mixture 1 is added dropwise to the stirring mixture 2. After mixture 1 is completely added dropwise to mixture 2, the stirring is stopped to obtain mixture 3. Mixture 3 is filtered to obtain a solid, and then the solid is rinsed three times with water and dried at 55 °C to obtain nano bio-based semi-aromatic polyamide powder.

[0018] Preferably, in one implementation case, 2.5 g of bio-based semi-aromatic polyamide is added to beaker 1, and then 497.5 g of dimethylformamide is added and stirred evenly until it becomes clear. Then, 37.5 g of water is added to beaker 1 and stirred evenly to obtain clear mixture 1 as Figure 1 shown. 450 g of water and 50 g of isopropanol are added to beaker 2 and stirred evenly to obtain mixture 2 as Figure 2 shown. Then, mixture 1 is added dropwise to the stirring mixture 2. After mixture 1 is completely added dropwise to mixture 2, the stirring is stopped to obtain mixture 3 as Figure 3 shown. Mixture 3 is filtered to obtain the upper-layer solid as Figure 4 shown. The upper-layer solid is rinsed three times with water and dried at 55 °C to obtain nano bio-based semi-aromatic polyamide.

[0019] Preferably, in one implementation case, 25 g of bio-based semi-aromatic polyamide is added to beaker 1, and then 475 g of dimethylsulfonamide is added and stirred evenly. Then, 625 g of water is added and stirred until it becomes clear. 700 g of water and 300 g of isopropanol are added to beaker 2 and stirred to obtain mixture 2. Mixture 1 is added dropwise to the stirring mixture 2. After mixture 1 is completely added dropwise to mixture 2, the stirring is stopped to obtain mixture 3. Mixture 3 is filtered to obtain a solid, and then the solid is rinsed three times with water and dried at 55 °C to obtain nano bio-based semi-aromatic polyamide.

[0020] Preferably, in one implementation case, 25 g of bio-based semi-aromatic polyamide is added to beaker 1, and then 475 g of N-methylpyrrolidone is added and stirred evenly. Then, 625 g of water is added and stirred until it becomes clear. 700 g of water and 300 g of isopropanol are added to beaker 2 and stirred to obtain mixture 2. Mixture 1 is added dropwise to the stirring mixture 2. After mixture 1 is completely added dropwise to mixture 2, the stirring is stopped to obtain mixture 3. Mixture 3 is filtered to obtain a solid, and then the solid is rinsed three times with water and dried at 55 °C to obtain nano bio-based semi-aromatic polyamide.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The present invention prepares nano bio-based semi-aromatic polyamide, with a simple method and low cost. From the particle size detection data of the above embodiments, it can be obtained that the more the proportion of bio-based semi-aromatic polyamide in the first mixed solution, the larger the particle size of the prepared particles; under the same solid content, the particles prepared with dimethylformamide have the smallest particle size, and the particles prepared with N-methylpyrrolidone have the largest particle size. Thus, nano bio-based semi-aromatic polyamide particles with the required particle size can be prepared as needed. The nano-sized particles can be used in any coating aspect with water as the solvent system, which can effectively improve the heat resistance of the coated product and the thermal breakage temperature, and has the value of popularization and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0024] Figure 1 It is a schematic diagram of the method of the present invention.

[0025] Figure 2 It is the structural formula of the bio-based semi-aromatic polyamide of the present invention.

[0026] Figure 3 It is a schematic diagram of the first mixed solution of the present invention.

[0027] Figure 4 It is a schematic diagram of the second mixed solution of the present invention.

[0028] Figure 5 It is a schematic diagram of the third mixed solution of the present invention.

[0029] Figure 6 It is a schematic diagram of the nano bio-based semi-aromatic polyimide after suction filtration of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0030] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0031] As Figures 1-6 shown, the present invention provides a method for preparing nano bio-based semi-aromatic polyamide particles, including the following steps:

[0032] S1. Add Solvent 1 to dilute the bio-based semi-aromatic polyamide into a solution, and then add Solvent 2 and stir evenly to form a first mixed solution;

[0033] S2. Dropwise add the first mixed solution into the second mixed solution which is a mixture of Solvent 2 and Solvent 3 to obtain a third mixed solution which is a suspension containing nano-scale bio-based semi-aromatic polyamide particles;

[0034] S3. Filter, wash, and dry the third mixed solution to obtain nano-scale bio-based semi-aromatic polyamide.

[0035] Further, in step S1, Solvent 1 is one or more of N-methylpyrrolidone, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, and dimethyl sebacate.

[0036] Further, in step S1, the bio-based semi-aromatic polyamide is derived from a polymer formed by a diacid monomer substituted or unsubstituted furan dicarboxylic acid or its derivative and a diamine monomer substituted or unsubstituted 4,4'-diaminodiphenyl ether or its derivative.

[0037] Further, the degree of polymerization n of the bio-based semi-aromatic polyamide is 700 - 2000, and the number average molecular weight of the bio-based semi-aromatic polyamide is greater than 200000.

[0038] Further, in step S1, the solid content after diluting the bio-based semi-aromatic polyamide into a solution by Solvent 1 is 0.5% - 10%.

[0039] Further, in step S1, Solvent 2 is water, and the addition amount of Solvent 2 is 15 - 28 times that of the bio-based semi-aromatic polyamide solid.

[0040] Further, in step S2, Solvent 3 is one or several of methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, tripropylene glycol, and glycerol.

[0041] Further, in step S2, the mass fraction of Solvent 2 in the second mixed solution is 50% - 100%.

[0042] Further, in step S3, the solvent used in the washing process is water, the temperature in the drying process is 35°C - 100°C, and the drying time is 15 - 30 min.

[0043] Now, specific embodiments prepared by the method of the present invention are provided:

[0044] Example 1: A method for preparing nano-scale bio-based semi-aromatic polyamide particles, comprising the following steps: Add 25 grams of bio-based semi-aromatic polyamide to Beaker 1, then add 475 grams of dimethylformamide and stir evenly until it becomes clear. Then add 625 grams of water to Beaker 1 and stir evenly to obtain Mixture 1. Add 700 grams of water and 300 grams of isopropanol to Beaker 2 and stir evenly to form Mixture 2. Then drip Mixture 1 into Mixture 2. After Mixture 1 is completely dripped into Mixture 2, turn off the stirring to obtain Mixture 3. Filter Mixture 3 to obtain a solid, and then wash the solid with water three times and dry it at 55 °C to obtain nano bio-based semi-aromatic polyamide solid.

[0045] Example 2: A method for preparing nano-scale bio-based semi-aromatic polyamide particles, comprising the following steps: Add 10 grams of bio-based semi-aromatic polyamide to Beaker 1, then add 490 grams of dimethylformamide and stir evenly until it becomes clear. Then add 200 grams of water to Beaker 1 and stir evenly to obtain Mixture 1. Add 425 grams of water and 75 grams of isopropanol to Beaker 2 and stir evenly to obtain Mixture 2. Then drip Mixture 1 into the stirring Mixture 2. After Mixture 1 is completely dripped into Mixture 2, turn off the stirring to obtain Mixture 3. Filter Mixture 3 to obtain a solid, and then wash the solid with water three times and dry it at 55 °C to obtain nano bio-based semi-aromatic polyamide powder.

[0046] Example 3: A method for preparing nano-scale bio-based semi-aromatic polyamide particles, comprising the following steps: Add 2.5 grams of bio-based semi-aromatic polyamide to Beaker 1, then add 497.5 grams of dimethylformamide and stir evenly until it becomes clear. Then add 37.5 grams of water to Beaker 1 and stir evenly to obtain a clear Mixture 1 as Figure 1 shown. Add 450 grams of water and 50 grams of isopropanol to Beaker 2 and stir evenly to obtain Mixture 2 as Figure 2 shown. Then drip Mixture 1 into the stirring Mixture 2. After Mixture 1 is completely dripped into Mixture 2, turn off the stirring to obtain Mixture 3 as Figure 3 shown. Filter Mixture 3 to obtain the upper-layer solid as Figure 4 shown. Wash the upper-layer solid with water three times and dry it at 55 °C to obtain nano bio-based semi-aromatic polyamide.

[0047] Example 4: A method for preparing nano-scale bio-based semi-aromatic polyamide particles, comprising the following steps: Add 25 grams of bio-based semi-aromatic polyamide to beaker one, then add 475 grams of dimethylsulfoximine and stir evenly, then add 625 grams of water and stir until it becomes clear. Add 700 grams of water and 300 grams of isopropanol to beaker two and stir to obtain mixture two. Drop mixture one into the stirring mixture two. After mixture one is completely dropped into mixture two, stop stirring to obtain mixture three. Filter mixture three to obtain a solid, then rinse the solid with water three times and dry it at 55 °C to obtain nano bio-based semi-aromatic polyamide.

[0048] Example 5: A method for preparing nano-scale bio-based semi-aromatic polyamide particles, comprising the following steps: Add 25 grams of bio-based semi-aromatic polyamide to beaker one, then add 475 grams of N-methylpyrrolidone and stir evenly, then add 625 grams of water and stir until it becomes clear. Add 700 grams of water and 300 grams of isopropanol to beaker two and stir to obtain mixture two. Drop mixture one into the stirring mixture two. After mixture one is completely dropped into mixture two, stop stirring to obtain mixture three. Filter mixture three to obtain a solid, then rinse the solid with water three times and dry it at 55 °C to obtain nano bio-based semi-aromatic polyamide.

[0049] The obtained nano bio-based semi-aromatic polyamide was detected by a nano particle size analyzer to obtain particle size detection data, and the detection results are shown in the following table:

[0050] Example 1 Example 2 Example 3 Example 4 Example 5 Particle size (nm) 223.73 187.24 102.13 243.64 266.72

[0051] In summary, the nano bio-based semi-aromatic polyamide is prepared by the present invention. The method is simple and has low cost. And from the particle size detection data of the above examples, it can be obtained that the more the proportion of bio-based semi-aromatic polyamide in mixture one, the larger the particle size of the prepared particles; under the same solid content, the particles prepared with dimethylformamide have the smallest particle size, and the particles prepared with N-methylpyrrolidone have the largest particle size. Thus, nano-scale bio-based semi-aromatic polyamide particles with the required particle size can be prepared according to needs. The nano-scale particles can be used in any coating aspect with a water-based solvent system, and can effectively improve the heat resistance performance and thermal breakdown temperature of the coated product, having the value of popularization and use.

[0052] 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 equivalent technologies, the present invention also intends to include these changes and modifications.

Claims

1. A preparation method of nano-scale bio-based semi-aromatic polyamide particles, characterized in that, It includes the following steps: S1. Add Solvent 1 to dilute the bio-based semi-aromatic polyamide into a solution, and then add Solvent 2 and stir evenly to form Mixture 1; S2. Dropwise add Mixture 1 into Mixture 2 which is a mixture of Solvent 2 and Solvent 3 to obtain Suspended Mixture 3 containing nano-scale bio-based semi-aromatic polyamide particles; S3. Filter, wash and dry Mixture 3 to obtain nano-scale bio-based semi-aromatic polyamide; In step S1, the Solvent 1 is one or more of N-methylpyrrolidone, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide and dimethyl sebacate; In step S1, the solid content after diluting the bio-based semi-aromatic polyamide into a solution by the Solvent 1 is 0.5%-10%; In step S1, the Solvent 2 is water, and the addition amount of the Solvent 2 is 15-28 times that of the bio-based semi-aromatic polyamide solid; In step S2, the Solvent 3 is one or several of methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, tripropylene glycol and glycerol; In step S2, the mass fraction of the Solvent 2 in Mixture 2 is 50%-100%, and 100% is not included.

2. The preparation method of a nano-scale bio-based semi-aromatic polyamide particle according to claim 1, characterized in that, In step S1, the bio-based semi-aromatic polyamide is a polymer formed by substituted or unsubstituted furandicarboxylic acid and substituted or unsubstituted 4,4'-diaminodiphenyl ether.

3. The preparation method of a nano-level bio-based semi-aromatic polyamide particle according to claim 2, characterized in that, The degree of polymerization n of the bio-based semi-aromatic polyamide is 700-2000, and the number-average molecular weight of the bio-based semi-aromatic polyamide is greater than 200000.

4. The preparation method of a nano-scale bio-based semi-aromatic polyamide particle according to claim 1, wherein, In step S3, the solvent used in the washing process is water, the temperature in the drying process is 35℃-100℃, and the drying time is 15-30 min.

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