CN103467266A - Method for recycling UV-531 crystallization mother liquor - Google Patents
Method for recycling UV-531 crystallization mother liquor Download PDFInfo
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- CN103467266A CN103467266A CN2013104314959A CN201310431495A CN103467266A CN 103467266 A CN103467266 A CN 103467266A CN 2013104314959 A CN2013104314959 A CN 2013104314959A CN 201310431495 A CN201310431495 A CN 201310431495A CN 103467266 A CN103467266 A CN 103467266A
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Abstract
The invention discloses a method for recycling UV-531 crystallization mother liquor. According to the method, the side product of 2,4-di-n-octyloxybenzophenone in the UV-531 crystallization mother liquor is converted to the target product UV-531 in the Lewis acid catalytic condition. The reaction is high in conversion ratio, and the purity of the prepared product is higher than 99%. By adopting the method for recycling the UV-531 crystallization mother liquor, the utilization ratio of the raw materials and the yield of the product are improved, the cost is saved, the generation of solid waste in a traditional process is reduced, and thus the method is an economical and green technical process.
Description
Technical field
The present invention relates to ultraviolet radiation absorption agent producing process field.Be specifically related to a kind of method of recycling of uv-absorbing agent UV-531 crystalline mother solution.
Background technology
The UV light absorber Octabenzone, commodity are called UV-531, be most important kind in O-hydroxyl-diphenyl ketone class uv-absorbing agent, account for 80% of such product consumption amount, be widely used in polyethylene, polypropylene, polystyrene, ABS resin, polyester, polymeric amide etc.
The synthetic method of this product is divided into two classes substantially, i.e. single stage method and two-step approach, and two-step approach is reacted and is made product with Manufactured UV-0 and halo octane or ester with octane base; Single stage method is to carry out two step chemical reactions in a reactor, and in process, UV-0 does not separate.Industrial production UV-531 adopts the technique that 1-chlorine octane or 1-bromine octane react with UV-0 at present, can produce 2 in the time of preparation UV-531,4-bis-oxy-octyl benzophenone by products, be present in the middle of crystalline mother solution, to this, mostly chemical industry producer processes in the mode of solid waste, has caused the waste of raw material and to the pressure of environment.Yet 2,4-, bis-oxy-octyl benzophenones can make target product by the selectivity dealkylation, this recycling that is by product provides may.Report about the de-alkyl of Lewis acid catalysis is more, (the Su Daishi such as Su Daishi, et al.Biaryl Ethers as Novel Non-nucleoside Reverse Transcriptase Inhibitors with Improved Potency against Key Mutant Viruses.Journal of Medicinal Chemistry, 2009,52 (22), 7163-7169) use BBr in methylene dichloride
3catalysis 1-is fluoro-3, the fluoro-5-methoxyphenol of 5-dimethoxy benzene hydrolysis preparation 3-, yield 67%.For making boron salt catalyst stable existence, need to react at a lower temperature, energy consumption is larger, and yield is not high.Dong Yan (synthesizing of Dong Yan .2-hydroxyl-4-methoxy benzophenone. chemical reagent, 1997,19 (6), 376 ~ 377) with AlCl
3after catalysis Friedel-Crafts reaction preparation 2,4-dimethoxy-benzophenone, the hydrolysis demethylation has prepared UV-9, yield 84.6%.This synthetic route severe reaction conditions, complex process, be not suitable for suitability for industrialized production, but this synthetic route has proved in recovery UV-531 crystalline mother solution 2, the feasibility of 4-bis-oxy-octyl benzophenone by products.
Summary of the invention
The object of the present invention is to provide a kind of recycling method that is applicable to the simple UV-531 crystalline mother solution of low cost, technique in industrial production.
The technical solution that realizes the object of the invention is: a kind of UV-531 crystalline mother solution recovery and treatment method, it is characterized in that, and comprise the following steps:
Step 1, reclaim solvent by the mother liquor evaporate to dryness after the UV-531 recrystallization, and obtaining solid matter is the mixture of 2,4-, bis-oxy-octyl benzophenones and UV-531, and wherein 2,4-bis-oxy-octyl benzophenone massfractions account for 30% ~ 40%; Above-mentioned solid mixes with anhydrous Lewis acid catalyst, adds solvent, stirring and dissolving, and reacting by heating, reaction is cooled to room temperature after finishing;
Step 2 adds appropriate water in step 1 gained system, under room temperature, continues stirring reaction, and standing separatory after reaction finishes, obtain UV-531 after organic phase washing, recrystallization, drying; Water is the concentration and recovery catalyzer in hydrogenchloride atmosphere.
Wherein, the acid catalyst of Lewis described in step 1 is AlCl
3, ZnCl
2, FeCl
3, preferred AlCl
3.
In step 1, in solid 2, the mol ratio of 4-bis-oxy-octyl benzophenones and Lewis acid catalyst is 1:1.2 ~ 2.
In step 1, solvent is a kind of of toluene, chlorobenzene, acetone, methylene dichloride, preferably chlorobenzene.
In step 1, Heating temperature is 40 ~ 120 ℃.
Compared with prior art, its remarkable advantage: (1) there are no the relevant report of recycling about the UV-531 crystalline mother solution, has abandoned the treatment process of solid waste in the traditional technology at present, has controlled the pollution to environment in the present invention; (2) by product in mother liquor is converted into to target product, improves raw material availability, reduced cost, improve product yield; (3) selected the catalyzer of anhydrous Lewis acid as de-alkyl, technique is simple, and mild condition is applicable to industrial production.
Embodiment
Below in conjunction with embodiment, the present invention will be further described in detail:
The method of UV-531 crystalline mother solution recycling comprises the following steps:
Step 1, reclaim solvent by the mother liquor evaporate to dryness after the UV-531 recrystallization, and obtaining solid matter is the mixture of 2,4-, bis-oxy-octyl benzophenones and UV-531, and wherein 2,4-bis-oxy-octyl benzophenone massfractions account for 30% ~ 40%; Above-mentioned solid mixes with anhydrous Lewis acid catalyst, adds solvent, stirring and dissolving, and reacting by heating, reaction is cooled to room temperature after finishing;
Step 2 adds appropriate water in step 1 gained system, under room temperature, continues stirring reaction, and standing separatory after reaction finishes, obtain UV-531 after organic phase washing, recrystallization, drying; Water is the concentration and recovery catalyzer in hydrogenchloride atmosphere.
Wherein, the acid catalyst of Lewis described in step 1 is AlCl
3, ZnCl
2, FeCl
3, preferred AlCl
3.
In step 1, in solid 2, the mol ratio of 4-bis-oxy-octyl benzophenones and Lewis acid catalyst is 1:1.2 ~ 2.
In step 1, solvent is a kind of of toluene, chlorobenzene, acetone, methylene dichloride, preferably chlorobenzene.
In step 1, Heating temperature is 40 ~ 120 ℃.
Embodiment 1
Get the UV-531 crystalline mother solution of certain volume, obtain solid matter after evaporate to dryness and (measure its composition, containing 2,4-bis-oxy-octyl benzophenones 36%), take 24.5g(containing 2,4-bis-oxy-octyl benzophenone 0.02mol) drop in four-hole boiling flask, add 3.2g(0.024mol) Powdered anhydrous AlCl
3, add chlorobenzene 20mL, be heated with stirring to 120 ℃ of reaction 4h, be cooled to room temperature.Add 30mL water in reaction system, continue stirring reaction, vapor detection 2, after 4-bis-oxy-octyl benzophenones have reacted, standing separatory, organic phase is washed twice rear evaporate to dryness and is obtained the UV-531 crude product, and after recrystallization, purity is more than 99%, yield 89%, water is concentration and recovery catalyst A lCl in hydrogenchloride atmosphere
3.
Embodiment 2
Get the UV-531 crystalline mother solution of certain volume, obtain solid matter after evaporate to dryness and (measure its composition, containing 2,4-bis-oxy-octyl benzophenones 30%), take 29.2g(containing 2,4-, bis-oxy-octyl benzophenone 0.02mol) drop in four-hole boiling flask, add 4g(0.03mol) Powdered anhydrous ZnCl
2, add toluene 20mL, be heated with stirring to 110 ℃ of reaction 4h, be cooled to room temperature.Add 30mL water in reaction system, continue stirring reaction, vapor detection 2, after 4-bis-oxy-octyl benzophenones have reacted, standing separatory, organic phase is washed twice rear evaporate to dryness and is obtained the UV-531 crude product, and after recrystallization, purity is more than 99%, yield 85%, water is concentration and recovery catalyst Z nCl in hydrogenchloride atmosphere
2.
Embodiment 3
Get the UV-531 crystalline mother solution of certain volume, obtain solid matter after evaporate to dryness and (measure its composition, containing 2,4-bis-oxy-octyl benzophenones 33%), take 26.5g(containing 2,4-bis-oxy-octyl benzophenone 0.02mol) drop in four-hole boiling flask, add 6.5g(0.04mol) Powdered anhydrous FeCl
3, add methylene dichloride 20mL, be heated with stirring to 50 ℃ of reaction 4h, be cooled to room temperature.Add 30mL water in reaction system, continue stirring reaction, vapor detection 2, after 4-bis-oxy-octyl benzophenones have reacted, standing separatory, organic phase is washed twice rear evaporate to dryness and is obtained the UV-531 crude product, and after recrystallization, purity is more than 99%, yield 69%, water is concentration and recovery catalyst Fe Cl in hydrogenchloride atmosphere
3.
Embodiment 4
Get the UV-531 crystalline mother solution of certain volume, obtain solid matter after evaporate to dryness and (measure its composition, containing 2,4-bis-oxy-octyl benzophenones 40%), take 21.9g(containing 2,4-bis-oxy-octyl benzophenone 0.02mol) drop in four-hole boiling flask, add 3.2g(0.04mol) Powdered anhydrous AlCl
3, add acetone 20mL, stir low-grade fever to 40 ℃ reaction 4h, be cooled to room temperature.Add 30mL water in reaction system, continue stirring reaction, vapor detection 2, after 4-bis-oxy-octyl benzophenones have reacted, standing separatory, organic phase is washed twice rear evaporate to dryness and is obtained the UV-531 crude product, and after recrystallization, purity is more than 99%, yield 72%, water is concentration and recovery catalyst A lCl in hydrogenchloride atmosphere
3.
Claims (7)
1. the recovery method of a UV-531 crystalline mother solution, is characterized in that, comprises the following steps:
Step 1, reclaim solvent by the mother liquor evaporate to dryness after the UV-531 recrystallization, the mixture that the solid matter obtained is 2,4-, bis-oxy-octyl benzophenones and UV-531, and wherein 2,4-bis-oxy-octyl benzophenone massfractions account for 30% ~ 40%; Above-mentioned solid mixes with anhydrous Lewis acid catalyst, adds solvent, stirring and dissolving, and reacting by heating, reaction is cooled to room temperature after finishing;
Step 2 adds appropriate water in step 1 gained system, under room temperature, continues stirring reaction, and standing separatory after reaction finishes, obtain UV-531 after organic phase washing, recrystallization, drying; Water is the concentration and recovery catalyzer in hydrogenchloride atmosphere.
2. the method for UV-531 crystalline mother solution according to claim 1 recycling, it is characterized in that: the acid catalyst of Lewis described in step 1 is AlCl
3, ZnCl
2, FeCl
3.
3. the method for UV-531 crystalline mother solution according to claim 2 recycling, it is characterized in that: the acid catalyst of Lewis described in step 1 is AlCl
3.
4. the method for UV-531 crystalline mother solution according to claim 1 recycling is characterized in that: in step 12, the mol ratio of 4-bis-oxy-octyl benzophenones and Lewis acid catalyst is 1:1.2 ~ 2.
5. the method for UV-531 crystalline mother solution according to claim 1 recycling is characterized in that: in step 1, solvent is a kind of of toluene, chlorobenzene, acetone, methylene dichloride.
6. the method for UV-531 crystalline mother solution according to claim 5 recycling, it is characterized in that: in step 1, solvent is chlorobenzene.
7. the method for UV-531 crystalline mother solution according to claim 1 recycling, it is characterized in that: in step 1, Heating temperature is 40 ~ 120 ℃.
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|---|---|---|---|---|
| CN112142580A (en) * | 2019-06-27 | 2020-12-29 | 江苏紫奇化工科技有限公司 | Clean production method of UV-9 crystallization mother liquor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584773A (en) * | 2011-01-11 | 2012-07-18 | 昆明制药集团股份有限公司 | Method for preparing mangiferin aglycone |
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| CN102584773A (en) * | 2011-01-11 | 2012-07-18 | 昆明制药集团股份有限公司 | Method for preparing mangiferin aglycone |
Non-Patent Citations (3)
| Title |
|---|
| HASHEM SHARGHI AND FATEMEH TAMADDON: "《BeCI2 as a New Highly Selective Reagent for Dealkylation of Aryl-Methyl Ethers》", 《TETRAHEDRON》, vol. 52, no. 43, 31 December 1996 (1996-12-31), pages 13623 - 13640 * |
| M.J. AURELL，ET AL.: "《The synthesis of 1,8-dihydroxy-2,3,4,6-tetramethoxyxanthone and 1,6-dihydroxy-3,5,7,8-tetramethoxyxanthone，a confirmation of structure》", 《JOURNAL OF NATURAL PRODUCTS》, vol. 52, no. 4, 31 December 1989 (1989-12-31), pages 852 - 857 * |
| 赵德明等: "《2-羟基-4-甲氧基-5-磺酸基二苯甲酮的合成》", 《化工进展》, vol. 30, no. 4, 31 December 2011 (2011-12-31), pages 857 - 861 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142580A (en) * | 2019-06-27 | 2020-12-29 | 江苏紫奇化工科技有限公司 | Clean production method of UV-9 crystallization mother liquor |
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