CN100335451C - Method for preparing tetrachloro ortho xylene - Google Patents
Method for preparing tetrachloro ortho xylene Download PDFInfo
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- CN100335451C CN100335451C CNB2006100182490A CN200610018249A CN100335451C CN 100335451 C CN100335451 C CN 100335451C CN B2006100182490 A CNB2006100182490 A CN B2006100182490A CN 200610018249 A CN200610018249 A CN 200610018249A CN 100335451 C CN100335451 C CN 100335451C
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Abstract
The present invention provides a method for preparing tetrachloro ortho benzylidene. Ortho-xylene is dissolved in an inert solvent medium such as chlorobenzene or dichlorobenzene, chlorine gas is supplied under the functions of catalysts to realize the reaction, a proper conversion rate, a proper speed rate, a proper temperature, etc. are controlled, and crude products are obtained by distilling recovered solvent and low-boiling point materials; finished products are obtained by recrystallization of the crude products by solvent. When the present invention is used, in the presence of ensuring the quality of the products, the yield of the products is enhanced as much as possible. The present invention has the advantages of simple technological operation processes and little three waste pollution, and is suitable for industrial production.
Description
Technical field
The present invention relates to the manufacture method of the manufacture method of Chemicals, particularly a kind of tetrachloro ortho xylene.
Background technology
O-Xylol polychloride such as tetrachloro ortho xylene (claiming α again, α, α `, α `-tetrachloro o-Xylol), it is a kind of important organic chemical industry's intermediate, is mainly used in to make o-phthalaldehyde(OPA), agricultural chemicals and medicine etc.
Mostly aromatic hydrocarbon side alkyl chloride preparation is to be obtained by corresponding aroma alkyl hydrocarbon and chlorine reaction.This well-known process is described in Tang banking up chief editor " Minute Organic Synthesis chemistry and technology " (in January, 2002 first version, the 85th～85 page) to some extent.
In above-mentioned technological process, be raw material with aromatic alkyl hydrocarbon and chlorine, in glass reactor or glass lined reaction vessel, be installed with ultraviolet lighting device and stirring, under the catalysis of light and chemical catalyst such as Diisopropyl azodicarboxylate, react in 80～150 ℃.Stopped reaction (most typical example such as toluene system Benzyl Chloride) when to be reacted to certain phase be the chlorination transformation efficiency 30～70 of raw material aromatic alkyl hydrocarbon carries out rectification under vacuum with reaction product and can get product.Unreacted raw material and middle runnings recycling.The HCl gas that reaction produces absorbs the attached product technical hydrochloric acid in back by the absorption tower.
The polychloride principle of o-Xylol is the same, and its side chain chlorination is a multistep consecutive reaction process, and mechanism also is free radical lock reaction, and its reaction formula is as follows:
Main reaction:
Side reaction:
But when above-mentioned technology is used to make things such as many chlorine of o-Xylol thing such as adjacent benzyl dichloride, adjacent trichlorine benzal and adjacent tetrachloro benzal, there is following difficult point on its Technology:
1, its transformation efficiency of many chlorinations of o-Xylol is more much higher than single chlorating, and its adjacent dimethylated transformation efficiency almost reaches 100% as will obtain the o-Xylol tetrachloride time.
2, many chlorine of o-Xylol thing one dichloride, trichloride, particularly tetrachloride are solid mostly, when chlorination reaction proceeds to the middle and later periods, its reaction mass system very thickness that becomes already, even semicure, make chlorination reaction wayward, also can't carry out smoothly.
3, because of reaction mass system thickness or semicure, its reaction system material mass transfer and heat transfer are all not good, go on as chlorination reaction again, and the side reaction odds can rise significantly, thereby sharply strengthens consumption of raw materials.
4, refining can not the employing as single muriate sample of many chlorine of o-Xylol thing undertaken by rectification method, and many chlorine thing because of influenced by pyritous polycondensation takes place very easily when rectifying.
Summary of the invention
The object of the present invention is to provide a kind of easy and simple to handle, efficient is high, production cost is low, be easy to preparation technology's method of the tetrachloro ortho xylene of suitability for industrialized production.
Technical scheme of the present invention is: o-Xylol is dissolved in the inert solvent medium, feeds chlorine and make it reaction under the catalysis of Diisopropyl azodicarboxylate and UV-light; Selected weight of material is than being o-Xylol: inert solvent=1: 2～0.5, speed of reaction are 6～12%/h, and temperature of reaction is 80～150 ℃, and control product production rate is 20～50%; Obtain crude product through distillating recovering solvent and low-boiling-point substance, again crude product can be obtained finished product with solvent recrystallization.
Above-mentioned inert solvent is selected chlorobenzene C for use
6H
5-Cl or dichlorobenzene Cl-C
6H
4-Cl.
In above-mentioned reaction mass system, add inert solvent medium such as chlorobenzene or dichlorobenzene, reaction mass transfer and heat transfer problem of non-uniform in its solution system well.Under the dilution of inert solvent, reduced the contact probability of chlorine and many chlorine product, reduced the generation of side reaction, make its chlorination reaction will become more steady, operate also more easy to control.After reaction finishes, the material crystallisation by cooling to specified temperature, is separated obtaining crude product, its content is 85～90% (GC), mother liquor can be handled to reclaim and reuse.The product crude product with same inert solvent recrystallization once can obtain finished product, and its content is more than 99% (GC), and mother liquor can not treated recovery be re-used in chlorination, so can reduce production costs.
In the production process of the present invention,,, only retain a small amount of organic detritus, can send to burning disposal by distilling recyclable 95% solvent in the final stage of mother liquor recycling.So this technological process three-waste pollution seldom.
We can find from following table, when the content of o-Xylol tetrachloro thing in the reaction system reaches 20%, the height appearance of boiling are just arranged; When the content of o-Xylol tetrachloro thing reached 40%, height boiled and increases significantly.For the selectivity that guarantees to react, we select to control the one way recovery rate of o-Xylol tetrachloro; The content that suitably reduces product o-Xylol tetrachloro thing in reaction can significantly reduce the generation that height boils, and per pass conversion is controlled at 30～37% for best, and its total recovery rate can reach 70～85%.Utilize the logical chlorine of mother liquor to logical chlorine and not obviously influence of component thereof,, help reducing consumption of raw materials so in chlorination reaction, reduce the height generation of boiling as best one can.
O-Xylol chlorination change of component data statistic
| Time h | Component content (%) | |||||||
| O-Xylol | Adjacent first benzyl chloride | Adjacent methylbenzyl fork | Adjacent benzyl dichloride | Adjacent chloromethane benzal two tritiums | The tetrachloro o-Xylol | Ring chlorine thing | The pentachloro-o-Xylol | |
| 0 | 100.00 | / | / | / | / | / | / | / |
| 3 | 72.09 | 19.27 | 0.41 | 6.69 | / | / | / | / |
| 5 | 55.20 | 30.28 | 1.09 | 13.35 | 0.08 | / | / | / |
| 7 | 11.65 | 56.87 | 4.49 | 23.53 | 2.00 | / | / | / |
| 9 | / | 12.14 | 6.75 | 56.96 | 21.01 | 1.69 | 0.37 | / |
| 11 | / | / | / | 22.62 | 55.22 | 18.43 | 0.72 | 0.92 |
| 13 | / | / | / | 7.23 | 46.49 | 39.33 | 1.02 | 3.62 |
| 15 | / | / | / | 3.04 | 37.53 | 50.15 | 1.49 | 6.20 |
| 18 | / | / | / | / | 3.34 | 65.22 | 1.98 | 27.84 |
In the technology of the present invention, when containing water in material or the reaction system, same byproduct of reaction, particularly encircling the chlorine thing also can obviously increase.
In sum, technology of the present invention is easy, and is easy to operate, the production efficiency height, and cost is low, is suitable for suitability for industrialized production.
Embodiment
Example 1.
In the four-hole boiling flask of 1000ml, successively drop into o-Xylol and the 300g chlorobenzene of 300g, be warmed up to 70 ℃, add catalyzer Diisopropyl azodicarboxylate (1%wt o-Xylol), under the condition of illumination, import chlorine; Being warmed up to 110 ℃-140 ℃ again reacts.Timing sampling analysis in the process of logical chlorine, introduce chlorine gas to make reaction to predetermined transformation efficiency stops.The importing nitrogen replacement goes out sour gas and the chlorine in the reaction solution.Restir cools to 3～-3 ℃.Suction filtration obtains crude product filter cake 386g.Fresh chlorobenzene with 300g carries out recrystallization with filter cake again, and suction filtration obtains filter cake, and drying obtains finished product 214g, and content analysis (GC) is 99.56%; Once through yield: 35%.Filtrate can add the logical chlorine of fresh o-Xylol circulation.
Mother liquor proximate analysis data statistic (1050g)
| Chlorobenzene | Adjacent benzyl dichloride | Adjacent chloromethyl benzal two tritiums | The tetrachloro o-Xylol | Ring chlorine thing | The pentachloro-o-Xylol | |
| Content % | 61.46 | / | 18.11 | 15.38 | 1.15 | 2.00 |
Example 2.
In the four-hole boiling flask of 1000ml, drop into 300g o-Xylol and 200g chlorobenzene, operation is the same fully, obtains finished product 130.5g, and content analysis (GC) is 99.45%; Once through yield: 18.5%.
Example 3.
In the four-hole boiling flask of 1000ml, drop into the 300g o-Xylol, the mother liquor of 300g chlorobenzene use-case 1 substitutes, and operation is the same fully, obtains finished product 186.0g, and content analysis (GC) is 99.05%; Once through yield: 28.5%.
O-Xylol chlorination change of component data statistic
| Lot number | Component content % | |||||||
| O-Xylol | Adjacent first benzyl chloride | Adjacent methylbenzyl fork | Adjacent benzyl dichloride | Adjacent chloromethane benzal two tritiums | The tetrachloro o-Xylol | Ring chlorine thing | The pentachloro-o-Xylol | |
| Raw material | 82.80 | / | / | 0.84 | 9.45 | 6.55 | 0.06 | 0.30 |
| Terminal point | / | / | / | 6.19 | 45.32 | 43.38 | 1.08 | 4.03 |
Claims (2)
1, a kind of manufacture method of tetrachloro ortho xylene is characterized in that: o-Xylol is dissolved in the inert solvent medium, feeds chlorine and make it reaction under the catalysis of Diisopropyl azodicarboxylate and UV-light; Selected weight of material is than being o-Xylol: inert solvent=1: 2～0.5, speed of reaction are 6～12%/h, and temperature of reaction is 80～150 ℃, and control product production rate is 20～50%; Obtain crude product through distillating recovering solvent and low-boiling-point substance, again crude product can be obtained finished product with solvent recrystallization.
2, by the manufacture method of the described tetrachloro ortho xylene of claim 1, it is characterized in that: above-mentioned inert solvent is selected chlorobenzene C for use
6H
5-Cl or dichlorobenzene Cl-C
6H
4-Cl.
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| CNB2006100182490A CN100335451C (en) | 2006-01-19 | 2006-01-19 | Method for preparing tetrachloro ortho xylene |
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| CNB2006100182490A CN100335451C (en) | 2006-01-19 | 2006-01-19 | Method for preparing tetrachloro ortho xylene |
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| CN100335451C true CN100335451C (en) | 2007-09-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211975B (en) * | 2011-04-27 | 2013-07-17 | 湖北祥云(集团)化工股份有限公司 | Preparation process of a,a,a',a'-tetrachloroortho-xylene |
| CN104230653A (en) * | 2014-09-22 | 2014-12-24 | 潜江新亿宏有机化工有限公司 | Manufacturing technology of p-xylylene dichloride |
| CN104860792B (en) * | 2015-05-04 | 2017-01-25 | 山东汉兴医药科技有限公司 | Production method of 4, 4'-bis (ehloromethyl) biphenyl |
| CN111825520A (en) * | 2020-07-27 | 2020-10-27 | 西安思科赛实业有限公司 | Preparation process of alpha, alpha' -tetrachloro-o-xylene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU537063A1 (en) * | 1975-06-05 | 1976-11-30 | Киевский Технологический Институт Пищевой Промышленности | The method of obtaining -tetrachloro-oxylol |
| US5107032A (en) * | 1990-11-20 | 1992-04-21 | Noramco, Inc. | Process for the preparation of o-phthalaldehydes |
-
2006
- 2006-01-19 CN CNB2006100182490A patent/CN100335451C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU537063A1 (en) * | 1975-06-05 | 1976-11-30 | Киевский Технологический Институт Пищевой Промышленности | The method of obtaining -tetrachloro-oxylol |
| US5107032A (en) * | 1990-11-20 | 1992-04-21 | Noramco, Inc. | Process for the preparation of o-phthalaldehydes |
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