Method for removing metal ions in polybenzene ring hydroxyfluorene compound

Abstract

The invention provides a method for efficiently removing metal ions in a polybenzene ring hydroxyfluorene compound, which efficiently removes transition / non-transition metal ions through two-time purification by using multistage cationic resin and chelate resin, and promotes desorption of metal ions in a product by adopting a mode of two-time water-phase solid separation at the same time. Under the combined action of the two modes, the content of metal ions in the sample can be reduced to be less than 1ppb, and the requirements of electronic-grade high-purity chemicals are met.

Description

TECHNICAL FIELD

[0001] The application discloses a method for efficiently removing metal ions in a multi-benzene ring hydroxyl fluorene compound and belongs to the field of chemical synthesis. BACKGROUND

[0002] Fluorene phenol derivatives are popular in the field of fine chemical industry and photoelectric material, and synthesis of various derivatives thereof has been reported in many documents, and the derivatives exhibit excellent photochemical properties. Existing patents mainly authorize protection of synthesis and application of the compounds, and few patents study purity of metal impurities. Patent CN116332730A discloses a method for purifying the compounds by using resin and recrystallization, and the total content of metal can be reduced to less than 9.4 ppb. The patent method has obvious effect on removal of Na, K and Ca non-transition metal ions, but the amount of the absorbed transition metal is far less than that of the non-transition metal, and the method cannot be used to efficiently remove all metal ions. In addition, multi-benzene ring hydroxyl and carboxyl derivatives with active hydrogen have coordination chelation capacity with Ca, Fe and other metals, and usually cause the metal content of the derivatives to be abnormally high. Therefore, the metal ion content of industrial-grade fluorene phenol is unstable, and the metal ion content of Na, K, Fe and Cu is usually higher than 1 ppm. The purification effect of a single resin is not ideal, and there is no method for removing transition metal ions. SUMMARY

[0003] The application is used to solve the problem of purification of all metal ions in fluorene phenol derivatives, and a new method for efficiently removing all metal ions is provided for hydroxyl organic compounds containing transition and non-transition metal ions.

[0004] The multi-benzene ring hydroxyl compound includes one or more of 2,7-dihydroxy-9,9-dimethylfluorene, 2-hydroxy-9,9-dimethylfluorene, 4-hydroxy-9,9-dimethylfluorene, 2-hydroxy-9,9-diphenylfluorene, bisphenol fluorene, 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol, 9,9-di(3,5-dimethyl-4-hydroxyphenyl)fluorene and 9,9-bis(6-hydroxy-2-naphthol)fluorene, and the structural formulae are respectively as follows: .

[0005] The multi-benzene ring hydroxyl compound has certain similarity in structure, and therefore can be used as a removal process of the same type.

[0006] The content of each metal ion in the multi-benzene ring hydroxyl fluorene compound is greater than 50 ppb, and the total content of the metal ions is greater than 1 ppm. The metal ions include at least one of Na, Mg, Al, K, Ca, Mn, Fe, Ni, and Cu.

[0007] A method for efficiently removing transition metal ions from a polycyclic hydroxyl fluorene compound, the purification step comprising: (1) dissolving the polycyclic hydroxyl compound in a polar organic solvent.

[0008] (2) purifying the polycyclic hydroxyl compound organic solution using ion exchange resin, the ion exchange resin including strong acid cation resin and chelating resin.

[0009] (3) crystallization: adding twice the volume of ultrapure water to the solution to precipitate the product solid.

[0010] (4) filtration and drying: filtering the precipitated solid and drying the water under vacuum at 30-40°C.

[0011] The method for efficiently removing transition metal ions from a polycyclic hydroxyl fluorene compound can be single purification or double purification, the difference being that the product obtained by single purification is dissolved again and purified a second time using a different resin to become double purification.

[0012] The method for efficiently removing transition metal ions from a polycyclic hydroxyl fluorene compound, the organic solvent for dissolving the polycyclic hydroxyl fluorene compound including N,N-dimethylformamide, methanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, 1,4-dioxane, and acetone.

[0013] The resin purification includes at least two stages of purification resin composed of strong acid cation resin and chelating resin.

[0014] In a preferred embodiment, the resin purification is two-stage purification resin composed of strong acid cation resin and chelating resin. That is, the resin purification is column purification using a resin column filled with strong acid cation resin, followed by column purification using a resin column filled with chelating resin; the column purification order can be adjusted arbitrarily.

[0015] In a preferred embodiment, the resin purification is three-stage purification resin composed of strong acid cation resin, chelating resin, and strong acid cation resin. That is, the resin purification is column purification using a resin column filled with strong acid cation resin, followed by column purification using a resin column filled with chelating resin, and finally column purification using a resin column filled with strong acid cation resin; the column purification order can be adjusted arbitrarily.

[0016] In the preferred embodiment, the resin purification is a three-stage purification resin composed of strong acid cation resin + chelating resin + mixed resin of strong acid cation resin and chelating resin. That is, after column purification using a resin column filled with strong acid cation resin, column purification is performed using a resin column filled with chelating resin, and finally column purification is performed using a resin column filled with mixed resin of strong acid cation resin and chelating resin; the order of column purification can be adjusted arbitrarily.

[0017] In the preferred embodiment, after each column purification, the purified resin is dissolved again with the selected product, and the second purification process is performed to become the next purification.

[0018] The cation exchange resin involved in the method for efficient removal of transition metal ions in the multi-benzene ring hydroxyl fluorene compound includes one or more of D113, ZGER8415, Lewatit UP 1213MD, Amberlite IRC83H, Amberlite HPR650H, and SQ-608EC.

[0019] The chelating resin involved in the method for efficient removal of transition metal ions in the multi-benzene ring hydroxyl fluorene compound includes one or more of Monojet LSC 6100, D870B, D405, D850, Monojet LSC 500, and D401.

[0020] The purification method is divided into first-stage purification, second-stage purification, and third-stage purification, in which strong acid cation exchange resin and chelating resin are respectively filled into a chromatographic column, and the multi-benzene ring hydroxyl fluorene compound organic solution is passed through the chromatographic column to achieve the purification process.

[0021] The cation resin mentioned in the method for efficient removal of transition metal ions in the multi-benzene ring hydroxyl fluorene compound can efficiently remove non-transition metal ions such as Na, Mg, Al, K, and Ca, and the chelating resin has obvious removal effect on transition metal ions such as Cr, Mn, Fe, Ni, Cu, and Zn.

[0022] The crystallization process mentioned in the method for efficient removal of transition metal ions in the multi-benzene ring hydroxyl fluorene compound involves adding poor solvent ultrapure water to the organic solution, which can easily extract the organic solvent in the solution, causing the product solid to be precipitated in large quantities in the solution system, and the ultrapure water will further dissolve the metal ions during the precipitation process.

[0023] In the resin purification method mentioned in the method for efficient removal of transition metal ions in the multi-benzene ring hydroxyl fluorene compound, the solution mass concentration is 5-10%, the column flow rate is 3-9 Bv / h, the resin filling height-diameter ratio is 5-9:1, and the column temperature is room temperature.

[0024] The content of each metal ion in the polycyclic hydroxyl fluorene compound is reduced to below 10 ppb, preferably below 5 ppb, and further preferably below 1 ppb; the total content of metal ions is reduced to below 30 ppb, preferably below 20 ppb, further preferably below 10 ppb, and further preferably below 5 ppb; the metal ions include at least one of Na, Mg, Al, K, Ca, Mn, Fe, Ni, and Cu.

[0025] The present application has the following advantages: 1. The hydroxyl benzene ring organic compound has stronger coordination with metal ions, and the present application provides a method for efficiently removing transition / non-transition metal ions, which has a general effect on the purification of such organic compounds.

[0026] 2. The multi-stage resin purification form has higher flexibility, and can be adjusted according to the content level of metal ions in the product, and is adjusted as a customized purification process by changing the height-diameter ratio and the number of stages, which is simple in principle and easy to operate. DETAILED DESCRIPTION

[0027] The present application will be further described below in conjunction with examples, but the scope of the present application claimed is not limited to the scope expressed by the examples.

[0028] Example 1: 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol was dissolved in electronic grade N,N-dimethylformamide (total metal less than 0.1 ppb) to prepare a 10% mass fraction test solution, and the metal ions in the solution were tested by ICP-MS, and the tested metals included Na, Mg, Al, K, Ca, Mn, Fe, Ni, Cu, and Zn. The test results were converted into solid metal ion content as follows: Table 1 Metal test results of 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol

[0029] The content of Na, Al, Ca, and Fe metal ions in the unpurified sample was higher than 1.0 ppm, the content of Mg, K, and Cu ions was between 0.5-1.0 ppm, and the content of Mn, Ni, and Zn ions was lower than 0.5 ppm. The metal content of the sample was at a relatively high level, and the purification difficulty was relatively large.

[0030] Example 2-10: 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol is dissolved in an organic solvent acetone to prepare a 10%wt mother liquor, and after purification by 6 strong acid cation resins and 5 chelating resins, the metal ion content is tested, the 6 strong acid resins include: D113, ZGER8415, Lewatit UP 1213MD, Amberlite IRC83H, Amberlite HPR650H, SQ-608EC, and the 5 chelating resins include: Monojet LSC 6100, D870B, D405, D850, Monojet LSC 500, D401, and the specific purification steps are as follows: (1) Resin pretreatment: select a quartz chromatography column with a diameter of 3 cm and a height of 35 cm, fill all the resins according to a height-diameter ratio of 5:1, and call it a resin tower, wherein D401 is a Na-type chelating resin, first replace the Na ion with 5% dilute sulfuric acid, then flush the remaining resin tower with ultrapure water until the conductivity of the effluent no longer changes, and then replace the ultrapure water with 3Bv of acetone, which completes the pretreatment; (2) Resin purification: at 25°C, the 10%wt mother liquor is passed through the column at a flow rate of 3Bv / h, the first 2Bv of the purified solution is discarded, and the subsequent 3-6Bv of the purified solution is collected, and the resin purification is completed; (3) Solid separation and post-treatment: pour the purified solution into 2 times the volume of ultrapure water to separate the product solid, mechanically stir for 30 min, then use a fluorotetra funnel to filter, collect the filter cake solid, and dry in a 40°C oven for 10h, to obtain the purified white product solid.

[0031] (4) Test the metal ion content: the dried product is sent for ICP-MS testing according to the method of Example 1, and the metal ion content is calculated.

[0032] Table 2 Metal ion content after purification by different 12 resins and sample comparison

[0033] The test results show that cation resins generally have better removal effect on non-transition metal ions than on transition metal ions, among which Amberlite IRC83H, Amberlite HPR650H, and SQ-608EC have a removal rate of about 80% or more for most non-transition metal ions, but have a relatively low removal rate for transition metals, especially Fe and Cu, and the purification effect is particularly poor; in addition, chelating resin Monojet LSC 6100 is opposite to cation resin, and has a removal rate of more than 80% for Fe and Cu ions, but a removal rate of 30-60% for non-transition metal ions.

[0034] Table 3 Removal rate of metal ions by three cation resins and one chelating resin

[0035] Examples 14-16: The 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol was dissolved in an organic solvent, acetone, to prepare a 10%wt mother liquor. The cation resin used in Examples 5-7 and the chelating resin used in Example 8 were connected in series to form a two-stage resin column, and purification tests were performed again. The specific purification steps were as follows: (1) Resin pretreatment: a quartz chromatography column with a diameter of 3 cm and a height of 35 cm was selected, and all resins were filled according to a height-diameter ratio of 5:1. One cation resin and one chelating resin were connected in series, and there were three connection modes: 1) Amberlite IRC83H as the first-stage resin column and Monojet LSC 6100 as the second-stage resin column; 2) Amberlite HPR650H as the first-stage resin column and Monojet LSC 6100 as the second-stage resin column; 3) SQ-608EC as the first-stage resin column and Monojet LSC 6100 as the second-stage resin column; Each set of two-stage resin columns was washed with ultrapure water until the conductivity of the effluent no longer changed, and then 3Bv of acetone was used to replace the ultrapure water and complete the pretreatment; (2) Resin purification: at 25°C, the 10%wt mother liquor was passed through the column at a flow rate of 3Bv / h. The first 2Bv of the purified solution was discarded, and the subsequent 3-6Bv of the purified solution was collected to complete the resin purification; (3) Solid separation and post-treatment: the purified solution was poured into 2 times the volume of ultrapure water to precipitate the product solid. After mechanical stirring for 30 min, the product solid was collected by suction filtration using a fluoroteflon funnel, and was dried in a 40°C oven for 10 h to obtain the purified white product solid.

[0036] (4) Test the metal ion content: the dried product was sent for ICP-MS testing according to the method of Example 1, and the metal ion content was calculated.

[0037] Table 4 Test results of metal ions in Examples 14-16 and sample comparison

[0038] Example 14, 16 are very good, all have reached the standard of electronic grade products, in which the metal ion level of example 16 is the lowest, reduced to below 20 ppb, then the resin Amberlite IRC83H and SQ-608EC are better used with chelating resin Monojet LSC 6100.

[0039] Examples 17-19: 9, 9-bis (4-hydroxyphenyl) -9H-fluorene-2, 7-diol is dissolved in organic solvent acetone to prepare a 10% wt mother liquor, and the resins Amberlite IRC83H, Amberlite HPR650H and Monojet LSC 6100 are combined as a three-stage resin tower for further purification test, and the specific purification steps are as follows: (1) Resin pretreatment: select a quartz chromatography column with a diameter of 3 cm and a height of 35 cm, fill all resins according to the height-diameter ratio of 5:1, and connect the three resins in series, with three ways: 1) SQ-608EC is the first-stage resin tower, Monojet LSC 6100 is the second-stage resin tower, and Amberlite IRC83H is the third-stage resin tower; 2) SQ-608EC is the first-stage resin tower, Amberlite IRC83H is the second-stage resin tower, and Monojet LSC 6100 is the third-stage resin tower; 3) Monojet LSC 6100 is the first-stage resin tower, SQ-608EC is the second-stage resin tower, and Amberlite IRC83H is the third-stage resin tower; Each set of two-stage resin tower is washed with ultrapure water until the conductivity of the outlet water no longer changes, and then replaced with 3Bv of acetone to complete the pretreatment; (2) Resin purification: under the condition of 25℃, the 10% wt mother liquor is passed through the column at a flow rate of 3Bv / h, the first 2Bv volume of purified solution is discarded, and the subsequent 3-6Bv purified solution is collected to complete the resin purification; (3) Solid separation and post-treatment: pour the purified solution into 2 times the volume of ultrapure water to separate the product solid, mechanically stir for 30 min, then use a fluorotetra funnel to filter, collect the filter cake solid, and dry in a 40℃ oven for 10h, to obtain the purified white product solid.

[0040] (4) Test the metal ion content: the dried product is sent for ICP-MS test according to the method of example 1, and the metal ion content is calculated.

[0041] Table 5 Metal ion test results of examples 17-19 and sample comparison

[0042] The product metal ion content can be reduced to below 10 ppb by the three-stage resin purification of Examples 17 and 18, especially the Fe and Cu contents are reduced to 3 ppb and 1 ppb respectively in Example 18.

[0043] Examples 20-21: The flow rate through the column was changed to 6 Bv / h in Example 20 and 9 Bv / h in Example 21, while the other conditions were the same as in Example 18.

[0044] Table 6 Effect of flow rate through the column on the metal content of the sample

[0045] The metal content in Example 20 was reduced more obviously than in Example 18, so the flow rate of 6 Bv / h through the column is a better condition.

[0046] Examples 22-23: The height-diameter ratio of the three-stage chromatography column was changed to 7:1 in Example 22 and 9:1 in Example 23, while the other conditions were the same as in Example 20.

[0047] Table 7 Effect of height-diameter ratio on the metal content of the sample

[0048] The metal content in Example 22 was the lowest, and the height-diameter ratio of 7:1 was the best condition.

[0049] Examples 24-26 Examples 17-23 used the three-stage resin purification method, which is a one-time purification plus one-time solid precipitation operation. Examples 24-26 divided the three-stage purification into one-stage purification and two-stage purification, which involved two times of solid precipitation. The specific resin classification method was as follows: (1) Example 24: first purified by one-stage resin plus one-time solid precipitation operation and suction filtration and drying operation, then prepared into a 10% wt solution, purified by two-stage resin, precipitated the solid again, suction filtered and dried to obtain the final product, and the metal ion content of the product was tested. The one-stage resin was SQ-608EC, and the two-stage resin was Amberlite IRC83H+Monojet LSC 6100.

[0050] (2) Example 25: first purified by two-stage resin plus one-time solid precipitation, then prepared into a 10% wt solution after suction filtration and drying, then purified by one-stage resin and one-time solid precipitation, and the final product was obtained after suction filtration and drying, and the metal ion content of the product was tested. The one-stage resin was Monojet LSC 6100, and the two-stage resin was SQ-608EC+Amberlite IRC83H.

[0051] (3) Example 26: First purification by primary resin, then solid precipitation and filtration drying, second purification by secondary resin, again solid precipitation and filtration drying to get final product, test the metal ion content of the product. Primary resin: Monojet LSC 6100, secondary resin: SQ-608EC + Amberlite IRC83H.

[0052] Resin pretreatment, purification, and test process are the same as Example 23.

[0053]

[0054] Examples 24-26 all use two resin adsorption and two water phase solid precipitation purification methods, only Example 24 has the lowest residual metal ions, and it is special that the Fe and Cu ion residues in Example 25 are abnormally high, indicating that the use of cation resin and chelating resin in series has better purification effect.

[0055] In summary, after reducing a large number of non-transition metal ions by cation resin, the use of cation resin and chelating resin in series can reduce the metal ion content of the sample to the lowest value, and the two water phase solid precipitation plays a role in promoting metal adsorption, removing most of the metal ions in hydroxyphenolic compounds.

[0056] It should be noted that the embodiments of the present application have better implementation, and do not limit the present application in any form, and any skilled person in the art can change or modify the above disclosed technical content to equivalent effective embodiments, as long as it does not deviate from the content of the technical solution of the present application, and any modification or equivalent change and modification of the above embodiments according to the technical essence of the present application, still belongs to the scope of the technical solution of the present application.

Claims

1. A method for removing metal ions from a polycyclic hydroxyfluorene compound, characterized by, The steps are as follows: The polycyclic hydroxyl fluorene compound is dissolved in an organic solvent, and then purified by a resin, and the purified solution is added to ultrapure water to precipitate a solid, which is extracted and dried to obtain a polycyclic hydroxyl fluorene compound with metal ions removed.

2. The method of removing metal ions from a polycyclic hydroxyfluorene compound according to claim 1, wherein The content of each metal ion in the polycyclic hydroxyl fluorene compound is greater than 50 ppb, and the total content of metal ions is greater than 1 ppm. The metal ions include at least one of Na, Mg, Al, K, Ca, Mn, Fe, Ni, and Cu.

3. The method of claim 1, wherein the metal ion is removed from the polycyclic hydroxyfluorene compound by adding a metal ion removing agent to the polycyclic hydroxyfluorene compound. The organic solvent can include any one of N,N-dimethylformamide, methanol, tetrahydrofuran, dimethyl sulfoxide, acetonitrile, 1,4-dioxane, and acetone.

4. The method of removing metal ions from a multi-benzorikylhydroxyfluorene compound according to claim 1, wherein The resin purification includes at least two-stage purification resin composed of strong acid cation resin and chelating resin.

5. The method of removing metal ions from a polycyclic hydroxyfluorene compound according to claim 4, wherein The resin purification is two-stage purification resin composed of strong acid cation resin and chelating resin.

6. The method of removing metal ions from a multi-benzoriketolylfluorene compound according to claim 4, wherein The resin purification is three-stage purification resin composed of strong acid cation resin, chelating resin, and strong acid cation resin.

7. The method of removing metal ions from a multi-benzoriketolyl compound according to claim 4, wherein The resin purification is three-stage purification resin composed of strong acid cation resin, chelating resin, and a mixture of strong acid cation resin and chelating resin.

8. The method for removing metal ions from a polyphenylhydroxyfluorene compound according to any one of claims 4 to 7, characterized by, The strong acid cation resin includes any one of D113, ZGER8415, Lewatit UP 1213MD, Amberlite IRC83H, Amberlite HPR650H, and SQ-608EC; and the chelating resin includes any one of Monojet LSC6100, D870B, D405, D850, Monojet LSC 500, and D401.

9. The method of removing metal ions from a multi-benzoriketol compound according to claim 1, wherein The polycyclic hydroxyl fluorene compound includes one or more of 2,7-dihydroxy-9,9-dimethylfluorene, 2-hydroxy-9,9-dimethylfluorene, 4-hydroxy-9,9-dimethylfluorene, 2-hydroxy-9,9-diphenylfluorene, bisphenol fluorene, 9,9-bis(4-hydroxyphenyl)-9H-fluorene-2,7-diol, 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)fluorene, and 9,9-bis(6-hydroxy-2-naphthol)fluorene.

10. The method of removing metal ions from a multi-benzoriketol compound according to claim 1, wherein The content of each metal ion in the polycyclic hydroxyl fluorene compound is reduced to 10 ppb or less, and the total content of metal ions is reduced to 30 ppb or less; and the metal ions include at least one of Na, Mg, Al, K, Ca, Mn, Fe, Ni, and Cu.

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