CN115010612A - Crystallization process of 4,4' -diaminodiphenyl ether - Google Patents
Crystallization process of 4,4' -diaminodiphenyl ether Download PDFInfo
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Abstract
The invention provides a crystallization process of 4,4' -diaminodiphenyl ether, which comprises the following steps: adding the 4,4' -diaminodiphenyl ether crude product into a crystallization solvent, adding a crystallizing agent and a protective agent, heating to 80-90 ℃ for dissolving, then cooling to 1-3 ℃ above the crystallization point, adding 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 30-40 min, cooling in a gradient manner, stopping cooling when the temperature is reduced to 5-15 ℃, and preserving heat for 0.5-1 h to obtain the 4,4' -diaminodiphenyl ether product. The method adopts a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water as a crystallization solvent, adds a specific mordant and a protective agent, and prepares the 4,4' -diaminodiphenyl ether crystal product with the particle size of 1-2mm and uniform particle size distribution by controlling the conditions of the crystallization process, such as the adding temperature of seed crystals, the temperature-controlled cooling rate, the crystal growing temperature and the like.
Description
Technical Field
The invention relates to the technical field of fine chemical production, in particular to a crystallization process of 4,4' -diaminodiphenyl ether.
Background
4,4 '-diaminodiphenyl ether (4, 4' -oxybisbenzenamine) with molecular formula C 12 H 12 N 2 O, molecular weight of 200.24, is a medical intermediate, is used for preparing heat-resistant plastics such as polyimide resin, polymaleimide resin, polyamideimide resin, polyesterimide resin and the like, and can also be used for producing a cross-linking agent. Polyimide is used as a special engineering material, has the advantages of high temperature resistance, radiation resistance, high mechanical strength and the like, and is widely applied to the fields of films, coatings, fibers, aerospace, electronic and electrical industry, foamed plastics, photoresist and the like. Polyimide is a polymer material with good development prospect, and the application of the polyimide in various fields is expanding in recent years, and 4,4 '-diaminodiphenyl ether is an important raw material for synthesizing polyimide, so the demand of 4,4' -diaminodiphenyl ether will increase in the future.
At present, 4,4' -diaminodiphenyl ether commercial products mainly have sublimates and crystallisates, and sublimate material particles are bigger (diameter 5-10cm), are not convenient for later stage material to dissolve, cause to throw and need long-time stirring after the material and dissolve, influence production efficiency, and if the material dissolves inadequately, still can cause the product yield to be lower. The crystallized product has the advantages of easy dissolution, convenient transportation and storage and the like, so the market application range of the 4,4' -diaminodiphenyl ether crystallized product is wider at present.
The 4,4 '-diaminodiphenyl ether crystallization process mainly comprises a cooling crystallization method and a dissolution crystallization method, wherein the cooling crystallization method mainly takes anhydrous dimethylformamide or anhydrous methanol as a solvent, and the purpose of separating out 4,4' -diaminodiphenyl ether crystals is achieved by cooling to form a supersaturated solution. The elution crystallization method mainly uses anhydrous dimethylformamide as a solvent and water as an elution agent, and water is dripped into the system to quickly reduce the solubility of 4,4' -diaminodiphenyl ether in the dimethylformamide-water mixed solvent to form a supersaturated solution so as to precipitate crystals. The yield of the 4,4' -diaminodiphenyl ether product obtained by the elution crystallization method is high, but the mother liquor of the elution crystallization method is a mixture of water and dimethylformamide, and the recovery of the dimethylformamide is difficult to realize by the common rectification method. At present, the cooling crystallization method has the main problems that: the yield of the 4,4' -diaminodiphenyl ether product obtained by the cooling crystallization method is low, the grain size of the prepared 4,4' -diaminodiphenyl ether product is small, the grain size distribution width is small, the 4,4' -diaminodiphenyl ether product is difficult to filter, wash and dry, the subsequent processing and use are inconvenient, the wall adhesion phenomenon is easy to occur in the crystallization process, the crystallization process is difficult to control, the crystal habit of the product is poor, and the product is easy to agglomerate after being stored for a long time. Therefore, it is very important to find a crystallization method of 4,4' -diaminodiphenyl ether which has moderate particle size, uniform distribution, easy dissolution and high storage stability.
Disclosure of Invention
Aiming at the problems of low yield, small grain size, wide grain size distribution and inconvenience in subsequent processing and use of 4,4 '-diaminodiphenyl ether products prepared by the existing cooling crystallization method, the invention provides a crystallization process of 4,4' -diaminodiphenyl ether.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a crystallization process of 4,4' -diaminodiphenyl ether comprises the following steps:
adding a crude 4,4 '-diaminodiphenyl ether product into a crystallization solvent, uniformly mixing, adding a mordant and a protective agent, heating to 80-90 ℃, and dissolving to obtain a crude 4,4' -diaminodiphenyl ether solution;
the crystallization solvent is a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water; the mordant is a Tween compound;
step two, cooling the crude 4,4' -diaminodiphenyl ether solution to 1-3 ℃ above the crystallization point under the stirring condition, adding 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 30-40 min, cooling in a gradient manner, stopping cooling when the temperature is reduced to 5-15 ℃, preserving heat and growing crystals for 0.5-1 h, filtering, washing and drying to obtain a 4,4' -diaminodiphenyl ether product;
the specific procedures of gradient cooling are as follows: and adjusting the temperature every 10-20 min, wherein n is the temperature adjustment frequency in the temperature control process, the temperature reduction degree of the nth time is (2n-0.5) - (2n +0.5) DEG C, and n is a natural number greater than 1.
Compared with the prior art, the crystallization process of 4,4 '-diaminodiphenyl ether provided by the invention adopts a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water as a crystallization solvent, adds a specific crystal habit modifier and a protective agent, and regulates and controls the crystal growth process by controlling the conditions of the crystallization process, such as the conditions of the adding temperature of seed crystals, the temperature-controlled cooling rate, the crystal growing temperature and the like, so that the 4,4' -diaminodiphenyl ether crystal product with the particle size of 1-2mm, uniform particle size distribution and higher purity and yield is prepared.
The crystallization method of 4,4' -diaminodiphenyl ether products provided by the invention realizes effective control of the growth process of 4,4' -diaminodiphenyl ether crystals by controlling crystallization conditions, solves the problem that the crystals are easy to stick to the wall in the crystallization process, can prepare the 4,4' -diaminodiphenyl ether products with higher purity and yield by one-time crystallization, has complete crystal habit, moderate granularity, easy filtration, washing and drying of crystal slurry, can effectively improve the efficiency of the crystallization process, has good product fluidity, can effectively avoid the caking problem in the transportation and storage processes, can greatly improve the production efficiency and product quality of the 4,4' -diaminodiphenyl ether products by using the 4,4' -diaminodiphenyl ether products obtained by the preparation process as raw materials for preparing polyimide, is favorable for improving the market competitiveness of the products, has higher popularization and application value.
In the second step, the crystallization point temperature of 4,4' -diaminodiphenyl ether is: the temperature corresponding to the mixed solution of the 4,4' -diaminodiphenyl ether, the mordant and the protective agent is changed from turbidity to clarification.
Because the crude 4,4' -diaminodiphenyl ether is less dissolved in the crystallization solvent, a turbid liquid is formed by the initial crude 4,4' -diaminodiphenyl ether, the mordant, the protective agent and the crystallization solvent, and the temperature of the turbid liquid changed into a clear solution in the heating and dissolving process is the crystallization point temperature of the 4,4' -diaminodiphenyl ether. Heating to 80-90 ℃ to dissolve, so as to ensure that the crude 4,4' -diaminodiphenyl ether is fully dissolved.
And further, the crystallization point temperature of the 4,4' -diaminodiphenyl ether is recorded as a, in the second step, the crude 4,4' -diaminodiphenyl ether solution is cooled to a + (1-3) DEG C, and then the seed crystal of the 4,4' -diaminodiphenyl ether is added.
Preferably, the crystallization solvent is a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water in a mass ratio of 10-20: 100: 1-10.
Preferably, the mass ratio of the 4,4' -diaminodiphenyl ether crude product to the crystallization solvent is 20-70: 100.
Further preferably, the mass ratio of the crude 4,4' -diaminodiphenyl ether to the crystallization solvent is 30-40: 100.
The preferable addition amount of the crystallization solvent and the crystallization solvent can reduce impurity occlusion in crystals, improve the purity of products and facilitate the concentration and more uniform distribution of the particle size of the prepared 4,4' -diaminodiphenyl ether crystals on the premise of ensuring the product yield.
Preferably, the mordant is tween 60.
Preferably, the addition amount of the habit modifier is 0.1-0.5 per mill of the mass of the crystallization solvent.
More preferably, the addition amount of the habit modifier is 0.1 to 0.2 per mill of the mass of the crystallization solvent.
The preferable addition amount of the mordant and the mordant can effectively control the supersaturation degree of the system, avoid further promoting the continuous growth of crystals under the condition that fine crystals are generated, and effectively regulate and control the crystal nucleation and the crystal growth rate of the 4,4' -diaminodiphenyl ether, so that the crystal habit growth is good, and the particle size distribution is relatively concentrated.
Preferably, the protective agent is hydrazine hydrate with the mass concentration of 75-85%.
Preferably, the addition amount of the protective agent is 0.1-0.5 per mill of the mass of the crystallization solvent.
Further preferably, the addition amount of the protective agent is 0.2 to 0.3 per mill of the mass of the crystallization solvent.
The preferable addition amount of the protective agent and the protective agent can effectively protect the occurrence of the color change problem of the 4,4' -diaminodiphenyl ether in the crystallization process, avoid the occurrence of black spots in the 4,4' -diaminodiphenyl ether product and improve the quality of the 4,4' -diaminodiphenyl ether product.
Preferably, the granularity of the 4,4' -diaminodiphenyl ether seed crystal is 80-200 meshes.
Preferably, the adding amount of the 4,4' -diaminodiphenyl ether seed crystal is 0.2-0.7 per mill of the mass of the crystallization solvent.
More preferably, the adding amount of the 4,4' -diaminodiphenyl ether seed crystal is 0.3-0.6 per mill of the mass of the crystallization solvent.
The optimized grain size and the addition amount of the seed crystal are matched with the addition temperature of the seed crystal, so that explosive nucleation can be avoided, the supersaturation degree of a system can be consumed, and the generation of new nuclei is inhibited, so that the preparation of the 4,4' -diaminodiphenyl ether crystal with moderate grain size and uniform grain size distribution is facilitated; simultaneously, the method is favorable for improving the purity and the yield of the 4,4' -diaminodiphenyl ether product.
Preferably, in the second step, the temperature is adjusted every 15min, the temperature reduction rate of the nth time is (2n-0.5) DEG C/15 min to (2n +0.5) DEG C/15 min, and n is a natural number larger than 1.
By controlling a specific cooling program, a crystallization system can be in a proper supersaturation degree, the nucleation and growth of crystals are controlled, the explosive nucleation is avoided, the impurity occlusion in the crystals is reduced, the generation of new nuclei is inhibited, the wall sticking problem in the crystallization process is avoided, the 4,4 '-diaminodiphenyl ether crystals with moderate particle size and uniform particle size distribution are obtained, and meanwhile, the yield and the purity of the 4,4' -diaminodiphenyl ether product can be improved.
The crystallization process of 4,4 '-diaminodiphenyl ether provided by the invention realizes the control of the grain diameter and the crystal habit of the 4,4' -diaminodiphenyl ether product in the crystallization process by selecting a specific crystallization solvent, adding a mordant and a protective agent, adding a seed crystal at a specific temperature to control nucleation and control cooling rate, obtains the high-quality 4,4 '-diaminodiphenyl ether product with moderate grain diameter and concentrated grain diameter distribution, has the purity of the product of over 99.8 percent and the yield of over 91 percent, has clean and no black spots, has the grain diameter of the prepared 4,4' -diaminodiphenyl ether crystal of 1-2mm in concentrated distribution, has good product fluidity, is not easy to agglomerate when stored, is easy to dissolve in subsequent application, can obviously improve the production efficiency and the product quality of downstream products, and has extremely high popularization and application values.
Drawings
FIG. 1 is a photograph of a macro camera of the 4,4' -diaminodiphenyl ether product prepared in example 1;
FIG. 2 is a photograph of a macro camera of the 4,4' -diaminodiphenyl ether product prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A crystallization process of 4,4' -diaminodiphenyl ether comprises the following steps:
step one, weighing 100g of dry crude 4,4' -diaminodiphenyl ether (the content is 99.2%) and adding the crude 4,4' -diaminodiphenyl ether into a crystallizer, adding a crystallization solvent (45 g of dicyclohexylamine, 350g of propylene glycol dimethyl ether and 5g of water), uniformly mixing, adding 0.12g of hydrazine hydrate with the mass concentration of 80% and 600.08 g of tween, stirring and heating to 72 ℃, wherein the system is changed from turbid to clear, continuously heating to 83 ℃, and keeping the temperature for 0.5h to fully dissolve to obtain a crude 4,4' -diaminodiphenyl ether solution;
step two, cooling the crude 4,4' -diaminodiphenyl ether solution to 73 ℃ under the stirring condition, adding 0.12g of 150-mesh 4,4' -diaminodiphenyl ether seed crystal, growing the crystal for 0.5h, then carrying out temperature control cooling, adjusting the temperature once every 15min, wherein the cooling rate of the nth time is 2n ℃/15min, n is the temperature control adjustment frequency, adjusting the temperature for 8 times, reducing the temperature to 10 ℃ within about 110min, stopping cooling, growing the crystal for 1h, filtering, washing and drying to obtain 90.3g of 4,4' -diaminodiphenyl ether product, 86% of 10-50 meshes and 99.85% of HPLC content.
The photograph of the 4,4 '-diaminodiphenyl ether product prepared in this example with a macro camera is shown in fig. 1, and it can be seen from the photograph that the 4,4' -diaminodiphenyl ether product prepared in this example is white long rod-like crystals, no black spots are present on the crystals, the particle size is 1-2mm, the crystal habit is complete, and no coalescence is present.
Example 2
A crystallization process of 4,4' -diaminodiphenyl ether comprises the following steps:
step one, weighing 100g of dried crude 4,4' -diaminodiphenyl ether (the content is 99.2%) and adding the crude 4,4' -diaminodiphenyl ether into a crystallizer, adding a crystallization solvent (48 g of dicyclohexylamine, 245g of propylene glycol dimethyl ether and 8g of water), uniformly mixing, adding 0.1g of hydrazine hydrate with the mass concentration of 80% and 600.1 g of tween, stirring and heating to 77 ℃, wherein the system is changed from turbid to clear, continuously heating to 85 ℃, and keeping the temperature for 0.5h to fully dissolve to obtain a crude 4,4' -diaminodiphenyl ether solution;
step two, under the stirring condition, cooling the crude 4,4' -diaminodiphenyl ether solution to 78 ℃, adding 0.18g of 80-mesh 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 0.5h, then carrying out temperature-controlled cooling, carrying out temperature-controlled adjustment once every 15min, wherein the cooling rate of the nth time is (2n-0.5) ° C/15 min, n is the number of temperature-controlled adjustment times, adjusting the temperature for 8 times, cooling to 10 ℃ for 2.0h, stopping cooling, growing crystals for 1h, filtering, washing, drying, and obtaining 92g of 4,4' -diaminodiphenyl ether product, 88.4% of 10-50 meshes and 99.87% of HPLC content.
Example 3
A crystallization process of 4,4' -diaminodiphenyl ether comprises the following steps:
step one, weighing 100g of dry crude 4,4' -diaminodiphenyl ether (the content is 99.2 percent), adding the crude 4,4' -diaminodiphenyl ether into a crystallizer, adding a crystallization solvent (41 g of dicyclohexylamine, 205g of propylene glycol dimethyl ether and 4g of water), uniformly mixing, adding 0.12g of hydrazine hydrate with the mass concentration of 80 percent and 600.05 g of tween, stirring and heating the mixture to 84 ℃, wherein the system is changed from turbid to clear, continuously heating the mixture to 903 ℃, and keeping the temperature for 0.5h to fully dissolve the mixture to obtain a crude 4,4' -diaminodiphenyl ether solution;
and step two, cooling the crude 4,4' -diaminodiphenyl ether solution to 85 ℃ under the stirring condition, adding 0.12g of 200-mesh 4,4' -diaminodiphenyl ether seed crystal, growing the crystal for 0.5h, then cooling at controlled temperature, adjusting the temperature once every 15min, wherein the cooling rate at the nth time is (2n +0.5) ° c/15 min, n is the number of times of temperature adjustment, adjusting the temperature for 8 times, cooling at 9 ℃ for 2h, stopping cooling, growing the crystal for 1h, filtering, washing and drying to obtain 94.7g of 4,4' -diaminodiphenyl ether product, 80.29% of 10-50 meshes and 99.85% of HPLC content.
Example 4
A crystallization process of 4,4' -diaminodiphenyl ether comprises the following steps:
step one, weighing 100g of dry crude 4,4' -diaminodiphenyl ether (the content is 99.2%) and adding the crude 4,4' -diaminodiphenyl ether into a crystallizer, adding a crystallization solvent (68 g of dicyclohexylamine, 393g of propylene glycol dimethyl ether and 39g of water), uniformly mixing, adding 0.12g of hydrazine hydrate with the mass concentration of 80% and 600.1 g of tween, stirring and heating to 70 ℃, wherein the system is changed from turbid to clear, continuously heating to 83 ℃, and keeping the temperature for 0.5h to fully dissolve to obtain a crude 4,4' -diaminodiphenyl ether solution;
step two, cooling the crude 4,4' -diaminodiphenyl ether solution to 72 ℃ under the stirring condition, adding 0.15g of 100-mesh 4,4' -diaminodiphenyl ether seed crystal, growing the crystal for 0.5h, then carrying out temperature control cooling, adjusting the temperature once every 20min, wherein the cooling rate of the nth time is 2n ℃/20min, n is the number of temperature control adjustment times, adjusting the temperature for 8 times, reducing the temperature for 110min to 9 ℃, stopping cooling, growing the crystal for 45min, filtering, washing and drying to obtain 91.3g of 4,4' -diaminodiphenyl ether product, the content of 10-50 meshes is 78.3%, and the HPLC content is 99.91%.
Comparative example 1
A crystallization process of 4,4' -diaminodiphenyl ether comprises the following steps:
step one, weighing 100g of dry crude 4,4' -diaminodiphenyl ether (the content is 99.2%) and adding the crude 4,4' -diaminodiphenyl ether into a crystallizer, adding 400g of N, N-dimethylformamide crystallization solvent, uniformly mixing, adding 0.12g of hydrazine hydrate with the mass concentration of 80%, stirring and heating to 68 ℃, wherein the system is changed from turbid to clear, continuously heating to 75 ℃, and preserving heat for 0.5h to fully dissolve the crude 4,4' -diaminodiphenyl ether;
step two, cooling the crude 4,4' -diaminodiphenyl ether solution to 69 ℃ under the stirring condition, adding 0.12g of 150-mesh 4,4' -diaminodiphenyl ether seed crystal, growing crystal for 0.5h, then cooling at controlled temperature, adjusting the temperature once every 15min, wherein the cooling rate of the nth time is 2n ℃/15min, n is the number of times of temperature adjustment, adjusting the temperature for 8 times, cooling to 10 ℃ after 108min, stopping cooling, growing crystal for 1h, filtering, washing and drying to obtain 63.5g of 4,4' -diaminodiphenyl ether product, 38.56% of 10-50 meshes, 52.8% of 50-100 meshes and 99.45% of HPLC content.
The optical micrograph of the 4,4 '-diaminodiphenyl ether crystals prepared in this comparative example is shown in FIG. 2, and it can be seen from the figure that the 4,4' -diaminodiphenyl ether product prepared by the above-mentioned method has an uneven particle size distribution, has agglomerates, and is yellowish in color.
Comparative example 2
This comparative example provides a process for the crystallization of 4,4' -diaminodiphenyl ether which is identical to example 1 except that propylene glycol dimethyl ether in example 1 is replaced with an equal amount of butyl vinyl ether and the remaining conditions are identical to example 1.
The comparative example prepares 87.3g of 4,4' -diaminodiphenyl ether crystal product, 42 percent of 10-50 meshes and 99.75 percent of HPLC content.
Comparative example 3
The comparative example provides a crystallization process of 4,4' -diaminodiphenyl ether, which is completely the same as that in example 1, except that the gradient temperature-controlled cooling in the second step in example 1 is replaced by constant temperature cooling, the cooling rate is 10 ℃/15min, the temperature is reduced to 10 ℃ at the rate of 10 ℃/15min, and the rest conditions are completely the same as those in example 1.
89.8g of 4,4' -diaminodiphenyl ether crystal product, 34% of 10-50 meshes and 99.84% of HPLC content are prepared in the comparative example.
Comparative example 4
This comparative example provides a crystallization process of 4,4' -diaminodiphenyl ether, which is identical to example 1 except that sodium citrate is substituted for tween 60, the vehicle in example 1, and the other conditions are identical to example 1.
The comparative example prepares 90.1g of 4,4' -diaminodiphenyl ether crystal product, 55.3 percent of 10-50 meshes and 99.86 percent of HPLC content.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A crystallization process of 4,4' -diaminodiphenyl ether is characterized by comprising the following steps:
step one, adding a 4,4 '-diaminodiphenyl ether crude product into a crystallization solvent, uniformly mixing, adding a mordant and a protective agent, heating to 80-90 ℃ for dissolution, and obtaining a 4,4' -diaminodiphenyl ether crude product solution;
the crystallization solvent is a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water; the mordant is a Tween compound;
step two, under the stirring condition, cooling the crude 4,4' -diaminodiphenyl ether solution to 1-3 ℃ above the crystallization point, adding 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 30-40 min, cooling in a gradient manner, stopping cooling when the temperature is reduced to 5-15 ℃, preserving heat and growing crystals for 0.5-1 h, filtering, washing and drying to obtain a 4,4' -diaminodiphenyl ether product;
the specific procedures of gradient cooling are as follows: the temperature is controlled and adjusted once every 10-20 min, the temperature reduction degree of the nth time is (2n-0.5) - (2n +0.5) DEG C, and n is a natural number larger than 1.
2. The process for crystallizing 4,4' -diaminodiphenyl ether according to claim 1, wherein the crystallization solvent is a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water in a mass ratio of 10-20: 100: 1-10.
3. The crystallization process of 4,4 '-diaminodiphenyl ether as claimed in claim 1 or 2, wherein the mass ratio of the crude 4,4' -diaminodiphenyl ether to the crystallization solvent is 20-70: 100.
4. The process for the crystallization of 4,4' -diaminodiphenyl ether according to claim 1, wherein the mordant is tween 60.
5. The process for crystallizing 4,4' -diaminodiphenyl ether as claimed in claim 1 or 4, wherein the amount of the habit modifier added is 0.1 to 0.5% by mass of the crystallization solvent.
6. A process for the crystallization of 4,4' -diaminodiphenyl ether as claimed in claim 1, characterized in that the protecting agent is hydrazine hydrate with a mass concentration of 75% to 85%.
7. The crystallization process of 4,4' -diaminodiphenyl ether according to claim 1 or 6, characterized in that the addition amount of the protecting agent is 0.1 to 0.5 per mill of the mass of the crystallization solvent.
8. The process for crystallizing 4,4 '-diaminodiphenyl ether as claimed in claim 1, wherein the grain size of the 4,4' -diaminodiphenyl ether seed crystal is 80 to 200 mesh.
9. The process for crystallizing 4,4 '-diaminodiphenyl ether as claimed in claim 1 or 8, wherein the amount of the 4,4' -diaminodiphenyl ether seed crystal added is 0.2 to 0.7% by mass of the crystallization solvent.
10. The process for crystallizing 4,4' -diaminodiphenyl ether as claimed in claim 1, wherein in step two, the temperature is controlled every 15min, the cooling rate at the nth time is (2n-0.5) ° c/15 min to (2n +0.5) ° c/15 min, and n is a natural number greater than 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353214A (en) * | 2017-07-13 | 2017-11-17 | 山东冠森高分子材料科技股份有限公司 | With the directly refined 4,4 ＇ diaminodiphenyl ether techniques of mixed solvent recrystallization |
| CN108752222A (en) * | 2018-08-20 | 2018-11-06 | 万达集团股份有限公司 | A kind of the crystallization and purification technique and crystallization and purification system of 4,4 '-diaminodiphenyl ethers |
| CN110015965A (en) * | 2019-04-26 | 2019-07-16 | 山东欧亚化工有限公司 | A method of 4,4 '-diaminodiphenyl ether secondary crystallizations of production |
-
2022
- 2022-06-24 CN CN202210730115.0A patent/CN115010612B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353214A (en) * | 2017-07-13 | 2017-11-17 | 山东冠森高分子材料科技股份有限公司 | With the directly refined 4,4 ＇ diaminodiphenyl ether techniques of mixed solvent recrystallization |
| CN108752222A (en) * | 2018-08-20 | 2018-11-06 | 万达集团股份有限公司 | A kind of the crystallization and purification technique and crystallization and purification system of 4,4 '-diaminodiphenyl ethers |
| CN110015965A (en) * | 2019-04-26 | 2019-07-16 | 山东欧亚化工有限公司 | A method of 4,4 '-diaminodiphenyl ether secondary crystallizations of production |
Non-Patent Citations (1)
| Title |
|---|
| 信庆民 等: "4,4′-二氨基二苯醚的合成与精制", 《河北化工》, no. 1, pages 41 * |
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