CN103508870A - UV-531 clean synthetic method - Google Patents
UV-531 clean synthetic method Download PDFInfo
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- CN103508870A CN103508870A CN201310437849.0A CN201310437849A CN103508870A CN 103508870 A CN103508870 A CN 103508870A CN 201310437849 A CN201310437849 A CN 201310437849A CN 103508870 A CN103508870 A CN 103508870A
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention discloses a UV-531 clean synthetic method. The method comprises the following steps: using n-octyl alcohol, sulfuric acid and sodium chloride to prepare an intermediate 1-n-octyl chloride in the presence of a catalyst, performing base catalysis and condensation with 2,4- dihydroxy benzophenone (UV-O) in the presence of a phase transfer catalyst to prepare UV-531; using ethyl alcohol to recrystallize and refine the crude product; recycling salt in the wastewater generated in the process of water washing for chlorination, wherein the byproducts are sodium sulfate and hydrochloric acid. In the method, the sulfuric acid with high boiling point is utilized to replace volatile hydrochloric acid in the traditional technology to perform chlorination, so as to obtain 1-n-octyl chloride to condense. The cost is low, and the yield is high. The phase transfer catalyst is utilized to avoid usage of an organic solvent, so that the technology is clean, the raw material utilization rate is high, and the pollution to the environment is effectively controlled.
Description
Technical field
The present invention relates to ultraviolet radiation absorption agent producing process field.Be specifically related to the clean synthesis method of a kind of uv-absorbing agent UV-531.
Background technology
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 to react and make product with Manufactured UV-0 and halo octane or the ester with octane base; Single stage method is in a reactor, to carry out two step chemical reactions, and in process, UV-0 does not separate.One-step technology is simple, but productive rate is low, and raw material availability is not high, and poor product quality is large to environmental influence; The product yield that two-step approach makes is high, good product quality.Due to raw material UV-0 and haloalkane or to have the ester of octane base all water insoluble, in early stage research, be to react in organic solvent.Wang Jing, Deng Zhongming (Wang Jing, the bright .UV-531 synthesising process research of Deng Zhong, Hubei chemical industry, 2003 (3): 25-26) different organic solvents is studied the impact of UV-531 yield, determined that the pimelinketone of higher is as solvent, yield is 92%.Solvent method aftertreatment is complicated, consumes energy high, and environment and technologist are caused to certain injury.Along with the further investigation of phase-transfer catalyst, water-insoluble reactant under existing, consisting of phase-transferring agent is reacted be smoothly industrial widely used new technology in recent years.Adopt the technique of consisting of phase-transferring agent to adopt n-octane bromide to react, raw materials cost is high, is not suitable for suitability for industrialized production more.Meng Bo, (the Meng Bo such as Liu Yuying, Liu Yuying, Zhou Li etc. ultraviolet absorbent UV-531 new synthetic process, Shandong chemical industry, 2004 (1): 7-8) adopting 1-chlorine octane and UV-0 is raw material, tetramethyl ammonium chloride, salt of wormwood and a small amount of sodium bisulfite are catalyzer, preparation UV-531, yield 92 ~ 95%.This technological reaction time is short, and yield is high, but technique is more complicated, needs to need uninterruptedly to steam in fed batch and process water, crude product need to distill energy consumption large.
Summary of the invention
The object of the present invention is to provide a kind of low cost, high yield, be conducive to the clean synthesis method of large-scale industrial production UV-531.
The technical solution that realizes the object of the invention is:
A clean synthesis method of UV-531, comprises the following steps:
Step 1, in reactor, add n-Octanol, sulfuric acid, sodium-chlor and catalyzer zinc chloride, stir and heat, carry out chlorination; Reaction finishes after washing separatory and obtains 1-chlorine octane;
Step 2,1-chlorine octane is mixed with 2,4 dihydroxyl benzophenone, add alkaline catalysts, phase-transfer catalyst, stir and heat, carry out condensation reaction; After reaction finishes, add washing and remove sodium-chlor and water-soluble by product, and reclaim sodium-chlor for step 1, separatory obtains thick product;
Step 3, the thick product of step 2 gained is dissolved in ethanol, stirring heating, adds activated carbon decolorizing, and recrystallization obtains light yellow crystal 2-hydroxyl-4-n-octyloxy-benzophenone.
Wherein, in step 1, Heating temperature is 110 ~ 160 ℃, and sulfuric acid concentration is 98%.
N in step 1 (n-Octanol): n (sodium-chlor): n (sulfuric acid): n (zinc chloride)=1:(2 ~ 3): (1 ~ 1.5): (0.05 ~ 0.1).
N in step 2 (2,4 dihydroxyl benzophenone): n (1-chlorine octane)=1:(1.05 ~ 1.3).
In step 2, alkaline catalysts is K
2cO
3, Na
2cO
3, a kind of in NaOH, KOH.
N in step 2 (2,4 dihydroxyl benzophenone): n (K
2cO
3or Na
2cO
3)=1:(0.5 ~ 0.6), n (2,4 dihydroxyl benzophenone): n (NaOH or KOH)=1:(1 ~ 1.2).
In step 2, phase-transfer catalyst is a kind of in cetyl trimethylammonium bromide, Tetrabutyl amonium bromide, polyethylene glycol type sulfonate ion liquid, polyethylene glycol type quaternary ammonium salt ionic liquid, catalyst levels is 1% ~ 20% of 2,4 dihydroxyl benzophenone quality.
In step 2, Heating temperature is 160 ~ 180 ℃.
The present invention compared with prior art, its remarkable advantage: (1) reaction add consisting of phase-transferring agent, avoided the use of organic solvent, environmental friendliness; (2) in chlorination, with sulfuric acid and sodium-chlor, replace the hydrochloric acid in traditional technology, while having avoided technologist to feed intake, contact the possibility of volatility acid mist, reduced the danger of technique; In technique, realize recovery and the circulation of salt, greatly improved raw material availability; (3) adopt 1-chlorine octane and UV-0 as raw material, cost is low, and yield is high, is beneficial to suitability for industrialized production.
Accompanying drawing explanation
The schema of the clean synthesis method of a kind of UV-531 of Fig. 1 the present invention.
Embodiment
Synthetic route is as follows:
Below in conjunction with embodiment, the present invention will be further described in detail:
Embodiment 1
In four-hole boiling flask, add 20g sulfuric acid (98% H
2sO
4), 23.4g sodium-chlor, 1.36g zinc chloride, 26g n-Octanol, stirs and is heated to 110 ℃ of reactions, after GC detection n-Octanol reacts completely, reaction system is cooled to 80 ℃, adds moisture liquid, separates 1-chlorine octane and carries out the next step, yield 77%.
In four-hole boiling flask, add 21.4g 2,4 dihydroxyl benzophenone, 15.5g 1-chlorine octane, 5.3g sodium carbonate, 0.21g cetyl trimethylammonium bromide, is heated with stirring to 160 ℃ of reactions, and GC detects 2, after 4-dihydroxy benaophenonel reacts completely, reaction system is cooled to 80 ℃, washing separatory, separating organic phase is UV-531 crude product, water carries out the recovery of salt and for the first step reaction, waste water removes treatment process.UV-531 crude product obtains light yellow crystal through activated carbon decolorizing, ethyl alcohol recrystallization, yield 90%.
Embodiment 2
In four-hole boiling flask, add 25g sulfuric acid (98% H
2sO
4), 29.4g sodium-chlor, 2.2g zinc chloride, 26g n-Octanol, stirs and is heated to 130 ℃ of reactions, after GC detection n-Octanol reacts completely, reaction system is cooled to 80 ℃, adds moisture liquid, separates 1-chlorine octane and carries out the next step, yield 83%.
In four-hole boiling flask, add 21.4g 2,4 dihydroxyl benzophenone, 17.7g 1-chlorine octane, 7.6g salt of wormwood, 1.07g Tetrabutyl amonium bromide, is heated with stirring to 170 ℃ of reactions, and GC detects 2, after 4-dihydroxy benaophenonel reacts completely, reaction system is cooled to 80 ℃, washing separatory, separating organic phase is UV-531 crude product, water carries out the recovery of salt and for the first step reaction, waste water removes treatment process.UV-531 crude product obtains light yellow crystal through activated carbon decolorizing, ethyl alcohol recrystallization, yield 93%.
Embodiment 3
In four-hole boiling flask, add 25g sulfuric acid (98% H
2sO
4), 29.4g sodium-chlor, 2.7g zinc chloride, 26g n-Octanol, stirs and is heated to 150 ℃ of reactions, after GC detection n-Octanol reacts completely, reaction system is cooled to 80 ℃, adds moisture liquid, separates 1-chlorine octane and carries out the next step, yield 89%.
In four-hole boiling flask, add 21.4g 2,4 dihydroxyl benzophenone, 17.7g 1-chlorine octane, 4g sodium hydroxide, 2.1g polyethylene glycol type sulfonate ion liquid PEG[SO
2]-IL, is heated with stirring to 170 ℃ of reactions, and GC detects 2, after 4-dihydroxy benaophenonel reacts completely, reaction system is cooled to 80 ℃, washing separatory, separating organic phase is UV-531 crude product, and water carries out the recovery of salt and for the first step reaction, waste water removes treatment process.UV-531 crude product obtains light yellow crystal through activated carbon decolorizing, ethyl alcohol recrystallization, yield 93%.
Embodiment 4
In four-hole boiling flask, add 30g sulfuric acid (98% H
2sO
4), 35.1g sodium-chlor, 2.7g zinc chloride, 26g n-Octanol, stirs and is heated to 160 ℃ of reactions, after GC detection n-Octanol reacts completely, reaction system is cooled to 80 ℃, adds moisture liquid, separates 1-chlorine octane and carries out the next step, yield 93%.
In four-hole boiling flask, add 21.4g 2,4 dihydroxyl benzophenone, 17.7g 1-chlorine octane, 5.6g potassium hydroxide, 2.1g polyethylene glycol type quaternary ammonium salt ionic liquid PEG[bmim]-IL, be heated with stirring to 170 ℃ of reactions, GC detects 2, after 4-dihydroxy benaophenonel reacts completely, reaction system is cooled to 80 ℃, washing separatory, separating organic phase is UV-531 crude product, water carries out the recovery of salt and for the first step reaction, waste water removes treatment process.UV-531 crude product obtains light yellow crystal through activated carbon decolorizing, ethyl alcohol recrystallization, yield 95%.
Embodiment 5
In four-hole boiling flask, add 30g sulfuric acid (98% H
2sO
4), 35.1g sodium-chlor, 2.7g zinc chloride, 26g n-Octanol, stirs and is heated to 160 ℃ of reactions, after GC detection n-Octanol reacts completely, reaction system is cooled to 80 ℃, adds moisture liquid, separates 1-chlorine octane and carries out the next step, yield 93%.
In four-hole boiling flask, add 21.4g 2,4 dihydroxyl benzophenone, 17.7g 1-chlorine octane, 4g potassium hydroxide, 4.3g polyethylene glycol type sulfonate ion liquid PEG[SO
2]-IL, is heated with stirring to 180 ℃ of reactions, and GC detects 2, after 4-dihydroxy benaophenonel reacts completely, reaction system is cooled to 80 ℃, washing separatory, separating organic phase is UV-531 crude product, and water carries out the recovery of salt and for the first step reaction, waste water removes treatment process.UV-531 crude product obtains light yellow crystal through activated carbon decolorizing, ethyl alcohol recrystallization, yield 97%.
Embodiment 6
In four-hole boiling flask, add 30g sulfuric acid (98% H
2sO
4), 35.1g sodium-chlor, 2.7g zinc chloride, 26g n-Octanol, stirs and is heated to 160 ℃ of reactions, after GC detection n-Octanol reacts completely, reaction system is cooled to 80 ℃, adds moisture liquid, separates 1-chlorine octane and carries out the next step, yield 93%.
In four-hole boiling flask, add 21.4g 2,4 dihydroxyl benzophenone, 17.7g 1-chlorine octane, 4g potassium hydroxide, 4.3g polyethylene glycol type quaternary ammonium salt ionic liquid PEG[bmim]-IL, be heated with stirring to 180 ℃ of reactions, GC detects 2, after 4-dihydroxy benaophenonel reacts completely, reaction system is cooled to 80 ℃, washing separatory, separating organic phase is UV-531 crude product, water carries out the recovery of salt and for the first step reaction, waste water removes treatment process.UV-531 crude product obtains light yellow crystal through activated carbon decolorizing, ethyl alcohol recrystallization, yield 96%.
Claims (7)
1. a clean synthesis method of UV-531, is characterized in that, comprises the following steps:
Step 1, in reactor, add n-Octanol, sulfuric acid, sodium-chlor and catalyzer zinc chloride, stir and heat, carry out chlorination; Reaction finishes after washing separatory and obtains 1-chlorine octane;
Step 2,1-chlorine octane is mixed with 2,4 dihydroxyl benzophenone, add alkaline catalysts, phase-transfer catalyst, stir and heat, carry out condensation reaction; After reaction finishes, add washing and remove sodium-chlor and water-soluble by product, and reclaim sodium-chlor for step 1, separatory obtains thick product;
Step 3, the thick product of step 2 gained is dissolved in ethanol, stirring heating, adds activated carbon decolorizing, and recrystallization obtains light yellow crystal 2-hydroxyl-4-n-octyloxy-benzophenone.
2. the clean synthesis method of UV-531 according to claim 1, is characterized in that: in step 1, Heating temperature is 110 ~ 160 ℃, and sulfuric acid concentration is 98%.
3. the clean synthesis method of UV-531 according to claim 1, is characterized in that: n in step 1 (n-Octanol): n (sodium-chlor): n (sulfuric acid): n (zinc chloride)=1:(2 ~ 3): (1 ~ 1.5): (0.05 ~ 0.1).
4. the clean synthesis method of UV-531 according to claim 1, is characterized in that: n in step 2 (2,4 dihydroxyl benzophenone): n (1-chlorine octane)=1:(1.05 ~ 1.3).
5. the clean synthesis method of UV-531 according to claim 1, is characterized in that: in step 2, alkaline catalysts is K
2cO
3, Na
2cO
3, a kind of in NaOH and KOH; N (2,4 dihydroxyl benzophenone): n (K
2cO
3or Na
2cO
3)=1:(0.5 ~ 0.6), n (2,4 dihydroxyl benzophenone): n (NaOH or KOH)=1:(1 ~ 1.2).
6. the clean synthesis method of UV-531 according to claim 1, it is characterized in that: in step 2, phase-transfer catalyst is a kind of in cetyl trimethylammonium bromide, Tetrabutyl amonium bromide, polyethylene glycol type sulfonate ion liquid, polyethylene glycol type quaternary ammonium salt ionic liquid, catalyst levels is 1% ~ 20% of 2,4 dihydroxyl benzophenone quality.
7. the clean synthesis method of UV-531 according to claim 1, is characterized in that: in step 2, Heating temperature is 160 ~ 180 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588611A (en) * | 2016-11-17 | 2017-04-26 | 江苏富比亚化学品有限公司 | Process for producing benzophenone ultraviolet ray absorbent |
| CN107652172A (en) * | 2017-09-15 | 2018-02-02 | 襄阳金达成精细化工有限公司 | A kind of ultra-violet absorber UV 531 synthetic method |
| CN110613630A (en) * | 2019-09-30 | 2019-12-27 | 汕头大学 | Sunscreen cream containing benzophenone derivative nanocrystals and preparation method thereof |
| CN112125793A (en) * | 2020-09-16 | 2020-12-25 | 宜都市华阳化工有限责任公司 | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
| CN112142581A (en) * | 2019-06-27 | 2020-12-29 | 江苏紫奇化工科技有限公司 | Process for synthesizing UV-531 from chloro-n-octane |
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| CN1510022A (en) * | 2002-12-24 | 2004-07-07 | 上海高维化学有限公司 | Ultraviolet absorbent UV-1200 synthesis |
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2013
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| CN1510022A (en) * | 2002-12-24 | 2004-07-07 | 上海高维化学有限公司 | Ultraviolet absorbent UV-1200 synthesis |
Non-Patent Citations (2)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588611A (en) * | 2016-11-17 | 2017-04-26 | 江苏富比亚化学品有限公司 | Process for producing benzophenone ultraviolet ray absorbent |
| CN106588611B (en) * | 2016-11-17 | 2018-02-13 | 江苏富比亚化学品有限公司 | A kind of production technology of benzophenone ultraviolet absorbent |
| CN107652172A (en) * | 2017-09-15 | 2018-02-02 | 襄阳金达成精细化工有限公司 | A kind of ultra-violet absorber UV 531 synthetic method |
| CN112142581A (en) * | 2019-06-27 | 2020-12-29 | 江苏紫奇化工科技有限公司 | Process for synthesizing UV-531 from chloro-n-octane |
| CN110613630A (en) * | 2019-09-30 | 2019-12-27 | 汕头大学 | Sunscreen cream containing benzophenone derivative nanocrystals and preparation method thereof |
| CN110613630B (en) * | 2019-09-30 | 2022-08-30 | 汕头大学 | Sunscreen cream containing benzophenone derivative nanocrystals and preparation method thereof |
| CN112125793A (en) * | 2020-09-16 | 2020-12-25 | 宜都市华阳化工有限责任公司 | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
| CN112125793B (en) * | 2020-09-16 | 2024-05-10 | 宜都市华阳化工有限责任公司 | 2, 4-Di-n-octoxybenzophenone and synthetic method and application thereof |
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Application publication date: 20140115 |