CN115010612B - 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 crude product of the 4,4' -diaminodiphenyl ether into a crystallization solvent, adding a crystallization agent and a protective agent, heating to 80-90 ℃ for dissolution, then cooling to 1-3 ℃ above the crystallization point temperature, adding 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 30-40 min, cooling in a gradient way, stopping cooling when cooling to 5-15 ℃, and preserving heat for 0.5-1 h to obtain the 4,4' -diaminodiphenyl ether product. The invention adopts the mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water as crystallization solvent, adds specific crystallization agent and protective agent, and prepares the 4,4' -diaminodiphenyl ether crystal product with uniform particle size distribution and 1-2mm by controlling the conditions of crystallization process, such as the adding temperature of seed crystal, 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' -oxybisbenzenimine) of formula C 12 H 12 N 2 O, molecular weight 200.24, belongs to pharmaceutical intermediates, and can be used for preparing heat-resistant plastics such as polyimide resin, polymaleimide resin, polyamide imide resin, polyester imide resin and the like, and can also be used for producing cross-linking agents. Polyimide as one kind of special engineering material has the advantages of high temperature resistance, high radiation resistance, high mechanical strength, etc. and may be used widely in film, paint, fiber, aviation, electronic and electric industry, foamed plastic, photoresist, etc. Polyimide is a polymer material with good development prospect, and the application in various fields is expanding in recent years, while 4,4' -diaminodiphenyl ether is synthesized polyimideThe demand for 4,4' -diaminodiphenyl ether will therefore continue to increase in the future as an important raw material for amines.
At present, commercial products of 4,4' -diaminodiphenyl ether mainly comprise sublimates and crystalline products, sublimates have larger material particles (with the diameter of 5-10 cm), are inconvenient for dissolving later-stage materials, need to be stirred and dissolved for a long time after feeding, influence the production efficiency, and also can cause lower product yield if the materials are insufficiently dissolved. The crystal has the advantages of easy dissolution, convenient transportation and storage, and the like, so the current market application range of the 4,4' -diaminodiphenyl ether crystal is wider.
The crystallization process of 4,4 '-diaminodiphenyl ether mainly comprises a cooling crystallization method and a dissolving crystallization method, wherein the cooling crystallization method mainly uses anhydrous dimethylformamide or anhydrous methanol as a solvent, and the purpose of precipitating 4,4' -diaminodiphenyl ether crystals is achieved by forming supersaturated solution through cooling. The solvent-out crystallization method mainly uses anhydrous dimethylformamide as a solvent and water as a solvent-out agent, and water is dripped into the system to quickly reduce the solubility of 4,4' -diaminodiphenyl ether in the dimethylformamide-water mixed solvent, so that supersaturated solution is formed to separate out crystals. The yield of the 4,4' -diaminodiphenyl ether product obtained by the solvent-out crystallization method is higher, but the mother liquor of the solvent-out crystallization method is a mixture of water and dimethylformamide, and the recovery of the dimethylformamide is difficult to realize by a 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 prepared 4,4' -diaminodiphenyl ether product has small grain size and wide grain size distribution, is difficult to filter, wash and dry, is inconvenient for subsequent processing and use, and is easy to cause wall sticking phenomenon in the crystallization process, so that the crystallization process is difficult to control, and the product has poor crystal habit and is easy to agglomerate after long-term storage. Therefore, it is of great importance to find a crystallization method of 4,4' -diaminodiphenyl ether which has a moderate particle diameter, is uniformly distributed, is easy to dissolve and has high storage stability.
Disclosure of Invention
Aiming at the problems that the existing cooling crystallization method is low in yield of 4,4 '-diaminodiphenyl ether products, small in grain size, wide in grain size distribution and inconvenient to use in subsequent processing, 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 process for crystallizing 4,4' -diaminodiphenyl ether, comprising the steps of:
step one, adding a crude 4,4 '-diaminodiphenyl ether product into a crystallization solvent, uniformly mixing, adding a crystallization agent and a protective agent, heating to 80-90 ℃ for dissolution, and obtaining a crude 4,4' -diaminodiphenyl ether solution;
the crystallization solvent is a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water; the medium crystal agent 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 temperature, adding 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 30-40 min, cooling in a gradient way, 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: every 10-20 min of temperature control and regulation, n is the temperature regulation times in the temperature control process, the degree of temperature reduction in the nth time is (2 n-0.5) to (2n+0.5) DEG C, and n is a natural number greater than 1.
Compared with the prior art, the crystallization process of the 4,4 '-diaminodiphenyl ether provided by the invention adopts the mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water as a crystallization solvent, adds a specific crystallization agent and a protective agent, and regulates and controls the crystal growth process by controlling the conditions of the crystallization process, such as the adding temperature of a seed crystal, the temperature-controlled cooling rate, the crystal growth 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.
According to the crystallization method of the 4,4' -diaminodiphenyl ether product, provided by the invention, the crystallization condition is controlled, the effective control of the growth process of the 4,4' -diaminodiphenyl ether crystal is realized, the problem that wall sticking is easy to occur in the crystallization process is solved, the 4,4' -diaminodiphenyl ether product with higher purity and yield can be prepared by one-time crystallization, the crystal habit of the product is complete, the granularity is moderate, the crystal slurry is easy to filter, wash and dry, the efficiency of the crystallization process can be effectively improved, the flowability of the product is good, the caking problem in the transportation and storage process can be effectively avoided, and the production efficiency and the product quality of the 4,4' -diaminodiphenyl ether product can be greatly improved by using the 4,4' -diaminodiphenyl ether product as a raw material for preparing polyimide, so that the market competitiveness of the product can be improved, and the popularization and application value are higher.
In the second step, the crystallization point temperature of the 4,4' -diaminodiphenyl ether is as follows: the temperature corresponding to the time when the mixed solution of the 4,4' -diaminodiphenyl ether, the seeding agent and the protective agent changes from turbidity to clarification.
Because the crude 4,4' -diaminodiphenyl ether is less dissolved in the crystallization solvent, turbid liquid is formed by the crude 4,4' -diaminodiphenyl ether, the crystallization agent, the protective agent and the crystallization solvent, and the temperature at which the turbid liquid becomes clear solution in the process of heating and dissolving is the crystallization point temperature of the 4,4' -diaminodiphenyl ether. Heating to 80-90 deg.c for dissolving to ensure the complete dissolving of the coarse 4,4' -diaminodiphenyl ether product.
Further, in the second step, after the temperature of the crystal outlet point of the 4,4' -diaminodiphenyl ether is recorded as a, the crude solution of the 4,4' -diaminodiphenyl ether 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 crude 4,4' -diaminodiphenyl ether 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 preferred crystallization solvent and the addition amount of the crystallization solvent can reduce the occlusion of impurities in the crystals on the premise of ensuring the yield of the product, improve the purity of the product, and are beneficial to centralizing the particle size of the prepared 4,4' -diaminodiphenyl ether crystals and ensuring more uniform distribution.
Preferably, the preferred vehicle is tween 60.
Preferably, the addition amount of the crystallization agent is 0.1 to 0.5 per mill of the mass of the crystallization solvent.
Further preferably, the addition amount of the crystallization agent is 0.1 to 0.2 per mill of the mass of the crystallization solvent.
The preferred addition of the habit modifier and the habit modifier can effectively control the supersaturation degree of the system, avoid further promoting the continuous growth of crystals under the condition of generating fine crystals, and effectively regulate and control the crystal nucleation of the 4,4' -diaminodiphenyl ether and the growth rate of the crystals, so that the crystal habit is well grown 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 to 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 based on the mass of the crystallization solvent.
The preferable addition amount of the protective agent can effectively protect the 4,4' -diaminodiphenyl ether from color change in the crystallization process, avoid black spots in the 4,4' -diaminodiphenyl ether product and improve the quality of the 4,4' -diaminodiphenyl ether product.
Preferably, the particle size of the 4,4' -diaminodiphenyl ether seed crystal is 80-200 meshes.
Preferably, the addition amount of the 4,4' -diaminodiphenyl ether seed crystal is 0.2 to 0.7 per mill of the mass of the crystallization solvent.
Further preferably, the addition amount of the 4,4' -diaminodiphenyl ether seed crystal is 0.3 to 0.6 per mill of the mass of the crystallization solvent.
The preferred grain diameter and the addition amount of the seed crystal are matched with the addition temperature of the seed crystal, so that on one hand, explosive nucleation can be avoided, on the other hand, the supersaturation degree of the system is also favorably consumed, and the generation of new nuclei is restrained, thereby being favorable for preparing the 4,4' -diaminodiphenyl ether crystal with moderate grain diameter and uniform grain diameter distribution; meanwhile, the purity and the yield of the 4,4' -diaminodiphenyl ether product are improved.
Preferably, in the second step, the temperature is regulated and controlled once every 15min, the temperature reduction rate of the nth time is (2 n-0.5) DEG C/15 min to (2n+0.5) DEG C/15 min, and n is a natural number greater than 1.
By controlling a specific cooling program, the crystallization system can be in proper supersaturation degree, nucleation and growth of crystals are controlled, burst nucleation is avoided, impurity occlusion in the crystals is reduced, new nuclei are restrained, the problem of wall sticking 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 purity of the 4,4' -diaminodiphenyl ether products can be improved.
According to the crystallization process of 4,4 '-diaminodiphenyl ether, provided by the invention, the combination strategies of nucleation control and cooling rate control are realized by selecting a specific crystallization solvent, adding a crystallization medium and a protective agent and adding seed crystals at a specific temperature, so that the particle size and crystal habit of a 4,4' -diaminodiphenyl ether product in the crystallization process are controlled, a high-quality 4,4 '-diaminodiphenyl ether product with moderate particle size and concentrated particle size distribution is obtained, the purity of the product can reach more than 99.8%, the yield can reach more than 91%, the product is clean and has no black spots, the particle size of the prepared 4,4' -diaminodiphenyl ether crystal is intensively distributed at 1-2mm, the product has good fluidity, is not easy to agglomerate in storage, is easy to dissolve in subsequent application, the production efficiency and the product quality of downstream products can be obviously improved, and the popularization and application value is extremely high.
Drawings
FIG. 1 is a macro camera photograph of a 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
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A crystallization process of 4,4' -diaminodiphenyl ether:
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 (dicyclohexylamine 45g, propylene glycol dimethyl ether 350g and water 5 g), uniformly mixing, adding hydrazine hydrate with the mass concentration of 80% 0.12g and tween 60.08 g, stirring and heating to 72 ℃, changing the system 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 stirring, adding 0.12g of 150-mesh 4,4' -diaminodiphenyl ether seed crystal, growing the crystal for 0.5h, then performing temperature control cooling, performing temperature control adjustment once every 15min, wherein the nth cooling rate is 2n ℃/15min, n is the temperature control adjustment times, performing temperature adjustment for 8 times, cooling to 10 ℃ for about 110min, stopping cooling, growing the crystal for 1h, filtering, washing and drying to obtain 90.3g of 4,4' -diaminodiphenyl ether product, wherein the 10-50 mesh accounts for 86%, and the HPLC content is 99.85%.
The micro-distance camera photograph of the 4,4 '-diaminodiphenyl ether product prepared in the embodiment is shown in fig. 1, and it can be seen from the figure that the 4,4' -diaminodiphenyl ether product prepared in the embodiment is a white long rod crystal, no black spots exist on the crystal, the particle size is 1-2mm, the crystal habit is complete, and no coalescence exists.
Example 2
A crystallization process of 4,4' -diaminodiphenyl ether:
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 (dicyclohexylamine 48g, propylene glycol dimethyl ether 245g and water 8 g), uniformly mixing, adding hydrazine hydrate with the mass concentration of 80% 0.1g and tween 60.1 g, stirring and heating to 77 ℃, changing the system 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, cooling the 4,4' -diaminodiphenyl ether crude product solution to 78 ℃ under stirring, adding 0.18g of 4,4' -diaminodiphenyl ether seed crystal with 80 meshes, growing the crystal for 0.5h, then performing temperature control cooling, performing temperature control adjustment once every 15min, wherein the cooling rate of the nth time is (2 n-0.5) DEG C/15 min, the number of times of temperature control adjustment is n, the temperature adjustment is 8 times, cooling to 10 ℃ for 2.0h, stopping cooling, growing the crystal for 1h, filtering, washing and drying to obtain 92g of 4,4' -diaminodiphenyl ether product with the 10-50 meshes accounting for 88.4%, and the HPLC content of 99.87%.
Example 3
A crystallization process of 4,4' -diaminodiphenyl ether:
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 (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% and 0.05g of tween, stirring and heating to 84 ℃, changing the system from turbid to clear, continuously heating to 903 ℃, 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 85 ℃ under stirring, adding 0.12g of 4,4' -diaminodiphenyl ether seed crystal with 200 meshes, crystallizing for 0.5h, then performing temperature control cooling, performing temperature control adjustment once every 15min, wherein the cooling rate of the nth time is (2n+0.5) DEG C/15 min, the number of times of temperature control adjustment is n, the temperature is 8 times, cooling to 9 ℃ for 2h, stopping cooling, crystallizing for 1h, filtering, washing and drying to obtain 94.7g of 4,4' -diaminodiphenyl ether product, wherein the 10-50 meshes account for 80.29%, and the HPLC content is 99.85%.
Example 4
A crystallization process of 4,4' -diaminodiphenyl ether:
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 (dicyclohexylamine 68g, propylene glycol dimethyl ether 393g and water 39 g), uniformly mixing, adding hydrazine hydrate with the mass concentration of 80% 0.12g and tween 60.1 g, stirring and heating to 70 ℃, changing the system 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 stirring, adding 0.15g of 100-mesh 4,4' -diaminodiphenyl ether seed crystal, growing the crystal for 0.5h, then performing temperature control cooling, performing temperature control adjustment once every 20min, wherein the nth cooling rate is 2n ℃/20min, n is the temperature control adjustment times, performing temperature adjustment 8 times, cooling to 9 ℃ for 110min, stopping cooling, growing the crystal for 45min, filtering, washing and drying to obtain 91.3g of 4,4' -diaminodiphenyl ether product, wherein the 10-50 mesh accounts for 78.3%, and the HPLC content is 99.91%.
Comparative example 1
A crystallization process of 4,4' -diaminodiphenyl ether:
weighing 100g of dried crude 4,4 '-diaminodiphenyl ether (the content is 99.2%) and adding 400g of N, N-dimethylformamide crystallization solvent into a crystallizer, uniformly mixing, adding 0.12g of hydrazine hydrate with the mass concentration of 80%, stirring and heating to 68 ℃, changing the system from turbid to clear, continuously heating to 75 ℃, and preserving heat for 0.5h to fully dissolve to obtain a crude solution of the 4,4' -diaminodiphenyl ether;
step two, cooling the 4,4' -diaminodiphenyl ether crude product solution to 69 ℃ under stirring, adding 0.12g of 150-mesh 4,4' -diaminodiphenyl ether seed crystal, growing the crystal for 0.5h, then performing temperature control cooling, performing temperature control adjustment once every 15min, wherein the nth cooling rate is 2n ℃/15min, n is the temperature control adjustment times, performing temperature adjustment 8 times, cooling for 108min to 10 ℃, stopping cooling, growing the crystal for 1h, filtering, washing and drying to obtain 63.5g of 4,4' -diaminodiphenyl ether product, wherein the 10-50 mesh accounts for 38.56%, the 50-100 mesh accounts for 52.8%, and the HPLC content is 99.45%.
The optical microscope photograph of the 4,4 '-diaminodiphenyl ether crystal prepared in the comparative example is shown in fig. 2, and it can be seen from the figure that the particle size distribution of the 4,4' -diaminodiphenyl ether product prepared by the method is uneven, coalesced and the product is yellow.
Comparative example 2
This comparative example provides a crystallization process of 4,4' -diaminodiphenyl ether, which is identical to example 1, except that propylene glycol dimethyl ether in example 1 is replaced with an equivalent amount of butyl vinyl ether, and the remaining conditions are identical to example 1.
The comparative example produced 87.3g of 4,4' -diaminodiphenyl ether crystalline product with a 10-50 mesh content of 42% and an HPLC content of 99.75%.
Comparative example 3
The comparative example provides a crystallization process of 4,4' -diaminodiphenyl ether, which is identical to that of example 1, except that the gradient temperature-controlled cooling in step two of example 1 is replaced by constant temperature cooling at a rate of 10 ℃/15min, and the temperature is lowered to 10 ℃ at a rate of 10 ℃/15min, and the other conditions are identical to those of example 1.
89.8g of 4,4' -diaminodiphenyl ether crystal product with the 10-50 mesh ratio of 34 percent and the HPLC content of 99.84 percent 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 the medium crystal tween 60 in example 1 is replaced with sodium citrate, and the remaining conditions are identical to example 1.
The comparative example produced 90.1g of 4,4' -diaminodiphenyl ether crystalline product with a 10-50 mesh ratio of 55.3% and an HPLC content of 99.86%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A process for crystallizing 4,4' -diaminodiphenyl ether, comprising the steps of:
step one, adding a crude 4,4 '-diaminodiphenyl ether product into a crystallization solvent, uniformly mixing, adding a crystallization agent and a protective agent, heating to 80-90 ℃ for dissolution, and obtaining a crude 4,4' -diaminodiphenyl ether solution;
the crystallization solvent is a mixed solvent of dicyclohexylamine, propylene glycol dimethyl ether and water; the medium crystal agent is Tween 60; the protective agent is hydrazine hydrate;
step two, under the stirring condition, cooling the crude 4,4' -diaminodiphenyl ether solution to 1-3 ℃ above the crystallization point temperature, adding 4,4' -diaminodiphenyl ether seed crystals, growing crystals for 30-40 min, cooling in a gradient way, 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: every 15min of temperature control and adjustment, the degree of temperature reduction at the nth time is (2 n-0.5) to (2n+0.5) DEG C, and n is a natural number greater than 1.
2. The crystallization process of 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 to 20:100:1 to 10.
3. The crystallization process of 4,4 '-diaminodiphenyl ether according to 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 crystallization process of 4,4' -diaminodiphenyl ether according to claim 1, wherein the addition amount of the crystallization agent is 0.1 to 0.5 per mill of the mass of the crystallization solvent.
5. The crystallization process of 4,4' -diaminodiphenyl ether according to claim 1, wherein the protective agent is hydrazine hydrate with a mass concentration of 75-85%.
6. The crystallization process of 4,4' -diaminodiphenyl ether according to claim 1 or 5, wherein the amount of the protective agent added is 0.1 to 0.5% by mass of the crystallization solvent.
7. The process for crystallizing 4,4 '-diaminodiphenyl ether as claimed in claim 1, wherein the particle size of the 4,4' -diaminodiphenyl ether seed crystal is 80 to 200 mesh.
8. The process for crystallizing 4,4 '-diaminodiphenyl ether as claimed in claim 1 or 7, wherein the addition amount of the seed crystal of 4,4' -diaminodiphenyl ether is 0.2 to 0.7%o by mass of the crystallization solvent.
9. The crystallization process of 4,4' -diaminodiphenyl ether according to claim 1, wherein in the second step, the temperature is controlled once every 15min, the cooling rate of the nth time is (2 n-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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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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