CN104447188A - Preparation method for bis(trichloromethyl)benzene and bis(chloroformyl)benzene - Google Patents
Preparation method for bis(trichloromethyl)benzene and bis(chloroformyl)benzene Download PDFInfo
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Abstract
The present invention relates to a method for preparing bis(trichloromethyl)benzene through a photochemical reaction and preparing bis(chloroformyl)benzene through the further reaction of the bis(trichloromethyl)benzene. According to the present invention, di(methyl)benzene is added to a reactor, chlorine gas is introduced under the control of the illuminance of an incident light source and the reaction temperature, the obtained reaction mixture is subjected to a simple treatment so as to obtain the high purity bis(trichloromethyl)benzene; with the bis(trichloromethyl)benzene of the present invention, the high purity bis(chloroformyl)benzene, one of the aramid fiber production raw materials, can be conveniently obtained; and the preparation method of the present invention has the following advantages that the solvent, the free radical initiator, the photosensitizer and other third components can not be inproduced, and only the stage-control of the reaction condition and the wavelength and the intensity of the light source are required so as to improve the product purity.
Description
Technical field
The application relates to a kind of optical chlorinating reaction method; particularly relate to one and first prepare two (trichloromethyl) benzene with chlorine generation photochemical reaction by two (methyl) benzene, and the latter reacts the method for preparation two (chloroformyl) benzene more further.The method of the application is by control temperature, illuminance (also can be described as light intensity) and consume the purity that amount of chlorine significantly can improve two (trichloromethyl) benzene, and can prepare polymerization-grade two (chloroformyl) benzene at lower cost further.
Background technology
Aramid fiber is the special fibre that a class has high strength, high-wearing feature, the advantageous property such as high temperature resistant.Due to the application performance that it is good, aramid fiber all has boundless application prospect in many industries.The demand of world market to aramid fiber is ever-increasing situation, the coming years, and global aramid fiber market will increase with annual about 20% high speed.But due to reasons such as technical difficulty are large, cost of investment is high, aramid fiber market is monopolized by minority developed countries such as America and Japan always.The Kevlar fiber of du pont company, the Technora fiber of Japanese Di Ren company are the matured products of position oneself at the forefront in the market.
Aramid fiber market is enormously potential at home, according to statistics, China annual directly and the aramid fiber of indirect importing and correlated product in hundred million yuan.In recent years, the mechanism such as Donghua University, Shanghai Textile institute has successively carried out the research and development of aramid fiber.But at present, also rare domestic manufacturers and research institution can develop competitive matured product.
Two (trichloromethyl) benzene can react with water, phthalic acid etc. the intermediate preparing aramid fiber---two (chloroformyl) benzene.
The method of preparation two (trichloromethyl) benzene is with radical initiator and/or light-initiated side chain free radical chlorination, and even three components is to prevent the chlorine substitution reaction on phenyl ring sometimes also to need to add second, and the light source of employing is generally mercury lamp.Because the purity of two (trichloromethyl) benzene is undesirable, this technology does not but realize industrial volume production.
Present inventor thinks, the defect that in prior art, the method for Light chlorimation two (methyl) benzene exists is mainly in the following aspects.
1) optical chlorinating reaction is free chain reaction, and because there is side reaction, chlorination site and depth of chlorination relative difficult control.In order to the photochemical chlorination product of separate complex, DE3146868, JP47-130931 have to carry out a large amount of distillation operations, drastically increase the production cost of this series products.In order to prevent the substitution reaction of benzene chlorine in ring, US1,345,373 add sulphur and Acetyl Chloride 98Min., US1, and 384,909 add metal carbonate, US1,733,268 add p and s sulphur, US2,034,962 add organic bases, US2, and 695,873 add acid amides, US2,817,632 and US2,844,635 use amine substance, US3, and 363,013 uses triphenylphosphine etc.These extra components certainly will affect purity and the following purification steps of two (trichloromethyl) benzene.US4029560 and US4048033 reports: 1,3-bis-(methyl) benzene chlorination process is with 1,3-bis-(trichloromethyl) benzene is solvent, to suppress reaction and the by product of chlorine replacement on phenyl ring, this needs a large amount of 1,3-bis-(trichloromethyl) benzene recycles, and thus the method process is complicated, and cost is higher.
In a word, in prior art in order to realize phenyl ring hydrogen atom not by chloro pendant methyl hydrogen atom all by chloro, need to introduce multiple ancillary component, these ancillary component meeting " pollution " target product two (trichloromethyl) benzene, are unsuitable for the preparation of high purity product.
2) optical chlorinating reaction also needs to add radical initiator to start reaction.
The research of the people such as Wang Lumin (Tonghua Teachers College's journal, 2005,26 (4): 46-47) shows to need to add radical initiator to maintain reaction in the reaction of Light chlorimation 1,3-bis-(methyl) benzene.
CN102211975A discloses the method that three temperature stage neighbours two (methyl) benzene Light chlorimation prepares tetrachloro neighbour two (methyl) benzene.In the method, the temperature of Light chlorimation is divided into 120-125 DEG C, 125-130 DEG C, 130-135 DEG C of three phases, the amount of chlorine passed in each temperature stage is respectively 1/3 of total amount, also need to add benzoyl peroxide in 1/2 and 1/6 this reaction to terminate rear tetrachloro neighbour two (methyl) benzene yield as the reaction of light-sensitive catalyst three phase temperature and be only 65%, pentachloro-neighbour two (methyl) benzene yield is owing to adding photosensitization catalyzer in 10% this reaction, cause gained tetrachloro neighbour two (methyl) even if benzene is through further purifying, purity also only can reach 90%
3) optical chlorinating reaction Ordinary Light Sources Have is mercury lamp, and this light source exists many weak points
Present inventor finds, the short-wavelength light of low pressure mercury lamp can bring out other photochemistry side reactions, and product purity is declined; And the long wavelength light of high pressure, medium pressure mercury lamp is not enough to cause chlorine radical reaction, increase energy consumption.In addition, use mercury lamp as during light source because thermal value is large, need to be equipped with corresponding refrigerating unit, make structure of reactor complicated.
The photodiode (LED) that CN1948245 discloses wavelength region 300-600nm, power range is 0.1W ~ 1000W carries out optical chlorinating reaction as light source and produces benzyl chloride, and temperature of reaction maintains 90 ~ 150 DEG C.The document is recorded its technical problem that will solve and is to provide a kind of Light chlorimation method that current consumption is low, light source thermal value is little, can improve light source utilization rate by selecting photodiode as light source.Although two (methyl) benzene is as raw material between the document is referred to and can uses, whole embodiments of the document all do not disclose purity and the productive rate of product.
Applicant also finds, prior art is not also studied the illuminance of this reaction light source.
In addition, producing aramid fiber needs highly purified two (chloroformyl) benzene as starting raw material, otherwise aramid fiber difficult quality reaches specified requirement.In the preparation method of two (chloroformyl) of the prior art benzene, application is most often the sulfur oxychloride method (such as, see, CN102516060A, CN102344362A) of raw material with phthalic acid.But need 99.99% high-purity benzene dioctyl phthalate could obtain satisfied two (chloroformyl) benzene in this technique, this makes, and this route preparation cost significantly raises, technology difficulty strengthens.
In prior art in existing Light chlorimation xylene process, in products therefrom except target product two (trichloromethyl) benzene, also containing the by product being much difficult to target product be separated.In order to remove the by product that these are difficult to be separated, need to carry out repeatedly distillation operation.Repeatedly distillation operation makes the Light chlorimation xylene process of prior art very inadvisable on cost, and this is also the industrial major cause not adopting the method to prepare two (trichloromethyl) benzene on a large scale.
Contriver finds through research, and the by product being difficult in the Light chlorimation xylene process of prior art be separated concentrates in lighting end in distillation operation.Through contriver's research, find that the by product of phenyl ring chloro mainly occurs these lighting end by products, such as, the while of the phenyl ring one chloro by product of pendant methyl four chloro or pentachloro-.The by product of these phenyl ring chloros and two (trichloromethyl) benzene boiling point is comparatively close, and thus sepn process needs the very much higher time rectifying of cost.
And the present inventor creatively finds, by two (methyl) benzene is carried out the first step of reaction reaction with the chlorine of manipulated variable under specified temp, level conditions in photochmeical reaction, significantly can reduce the by product of aforementioned phenyl ring chloro, realize high purity and prepare two (trichloromethyl) benzene.
Therefore, the application relates to the photochemical method that one prepares two (trichloromethyl) benzene in one aspect, it is characterized in that two (methyl) benzene and chlorine react preparation two (trichloromethyl) benzene under illumination condition, the optical source wavelength of wherein said illumination is about 350nm-700nm, light wave width is the most about 50nm, wherein be about under 20000Lux-is about 55000Lux start to pass into chlorine in temperature of reaction about 55 DEG C-85 DEG C, illuminance, experience the first step of reaction that temperature of reaction under described illuminance is no more than about 120 DEG C; Then continue to pass into residual content chlorine until reacted under higher temperature of reaction.In of the method is preferred, light source is preferably LED.
The present inventor finds, the first step of reaction control well initial reaction temperature and illuminance for reaction after to obtain reaction mixture in high purity (before purifying) be very necessary.Specifically, the first step of reaction reaction is carried out according to described condition, significantly can reduce the by product of aforementioned phenyl ring chloro, and not need the reaction conditions strictly controlling the later stage, if along with the raising of depth of chlorination corresponding raising temperature of reaction and/or illuminance.
The minimum lasting degree of the first step of reaction or time length can be determined by simply testing according to concrete reaction system, to control the content of impurity in final reacting mixture or the purity of two (trichloromethyl) benzene.The maximum lasting degree of the first step of reaction or time length are had no particular limits.In the initial stage of chlorination reaction, due to the heat release of reaction, the speed that passes into controlling chlorine is needed to make temperature of reaction be no more than about 120 DEG C.But along with the carrying out of chlorination reaction and the raising of depth of chlorination, the speed of response under the condition of the first step of reaction can be slack-off, so that need raising temperature and/or illuminance to reach rational or economically feasible speed of response.Therefore the first step of reaction later stage, need to improve temperature and/or illuminance.
The present inventor finds, in the first step of reaction, preferably consume account for the required chlorine sum-rate of reaction be at least about the amount of chlorine of 1/6 after raised temperature and illuminance be favourable.More of the present invention preferred in, in the first step of reaction, consume amount of chlorine and to account for after the required chlorine sum-rate of reaction is more than or equal to about 1/6,1/5,1/4,1/3,2/5 or 1/2 raised temperature and illuminance again.More of the present invention preferred in, in the first step of reaction, consume amount of chlorine account for the required chlorine sum-rate of reaction about between 1/6-1/5, between 1/6-1/4, between 1/6-1/3, between 1/6-2/5, between 1/6-1/2, between 1/5-1/4, between 1/5-1/3, between 1/5-2/5, between 1/5-1/2, between 1/4-1/3, between 1/4-2/5, between 1/4-1/2, between 1/3-2/5, between 1/3-1/2 or between 2/5-1/2 after raised temperature and illuminance again.
More of the present invention preferred in, in the first step of reaction, illuminance also can suitably adjust.More of the present invention preferred in, the illuminance of the first step of reaction is preferably about between 25000Lux at about 20000Lux-, about 20000Lux-is about between 30000Lux, about 20000Lux-is about between 35000Lux, about 20000Lux-is about between 40000Lux, about 20000Lux-is about between 45000Lux, about 20000Lux-is about between 50000Lux, about 20000Lux-is about between 55000Lux, about 25000Lux-is about between 30000Lux, about 25000Lux-is about between 35000Lux, about 25000Lux-is about between 40000Lux, about 25000Lux-is about between 45000Lux, about 25000Lux-is about between 50000Lux, about 25000Lux-is about between 55000Lux, about 30000Lux-is about between 35000Lux, about 30000Lux-is about between 40000Lux, about 30000Lux-is about between 45000Lux, about 30000Lux-is about between 50000Lux, about 30000Lux-is about between 55000Lux, about 35000Lux-is about between 40000Lux, about 35000Lux-is about between 45000Lux, about 35000Lux-is about between 50000Lux, about 35000Lux-is about between 55000Lux, about 40000Lux-is about between 45000Lux, about 40000Lux-is about between 50000Lux, about 40000Lux-is about between 55000Lux, about 45000Lux-is about between 50000Lux, about 45000Lux-is about between 55000Lux, about 50000Lux-is about between 55000Lux.
More of the present invention preferred in, in the first step of reaction, temperature of reaction also can suitably adjust.More of the present invention preferred in, the temperature of reaction of the first step of reaction is preferably between about 55 DEG C of-Yue 60 DEG C, between about 55 DEG C of-Yue 65 DEG C, between about 55 DEG C of-Yue 70 DEG C, between about 55 DEG C of-Yue 75 DEG C, between about 55 DEG C of-Yue 80 DEG C, between about 55 DEG C of-Yue 85 DEG C, between about 60 DEG C of-Yue 65 DEG C, between about 60 DEG C of-Yue 70 DEG C, between about 60 DEG C of-Yue 75 DEG C, between about 60 DEG C of-Yue 80 DEG C, between about 60 DEG C of-Yue 85 DEG C, between about 65 DEG C of-Yue 70 DEG C, between about 65 DEG C of-Yue 75 DEG C, between about 65 DEG C of-Yue 80 DEG C, between about 65 DEG C of-Yue 85 DEG C, between about 70 DEG C of-Yue 75 DEG C, between about 70 DEG C of-Yue 70 DEG C, between about 70 DEG C of-Yue 85 DEG C, between about 75 DEG C of-Yue 80 DEG C, between about 75 DEG C of-Yue 85 DEG C, between about 80 DEG C of-Yue 85 DEG C.More of the present invention preferred in, the temperature of reaction of the first step of reaction is preferably at about 55 DEG C, about 60 DEG C, about 65 DEG C, about 70 DEG C, about 75 DEG C, about 80 DEG C, about 85 DEG C.
Preferably, in the application in another, Light chlorimation two (methyl) the benzene process of reacting after the first step of reaction passes into surplus chlorine in starting temperature about 120 DEG C, outlet temperature about 180 DEG C, incident light illumination under being initiated with the condition of about 50000Lux, final about 100000Lux.Process after method first step of reaction described in the application can be a single step of reaction, or is divided into several step of reaction to be such as divided into the step of reaction such as two, three, four, five, six, seven, eight, nine, ten.After first step of reaction in process, when the temperature in each stage raises, optionally also raise illuminance.The present inventor finds, in the process after the first step of reaction, reaction conditions is relatively more flexible, can have multiple choices.The main purpose of different temperature and light illumination is regulated to be impel reaction to complete in process after first step of reaction.Contriver finds, strictly control in the present invention on the basis of first stage reaction, in the process after the first step of reaction, the change of reaction conditions is little for the impurities affect of the finished product.
More preferred, Light chlorimation two (methyl) the benzene process of reacting after the first step of reaction can also be further divided into the second step of reaction and the 3rd step of reaction.Second step of reaction controls that temperature of reaction is about 120-about 160 DEG C, incident light illumination is that about 50000-is about 70000Lux, the amount of chlorine that passes into is 1/4 ~ 2/5 of total amount; 3rd step of reaction control temperature is about 160-about 180 DEG C, incident light illumination is about 100000Lux for about 70000-, passes into surplus chlorine.In second and third stage, raised temperature and raise illuminance can sequencing each other.Contriver finds, in this three phase implementation, at the end of reaction, in reaction mixture, the purity of two (trichloromethyl) benzene can reach more than 95%.
Contriver finds, key of the present invention is that control first step of reaction is carried out in the manner described; Through the first step of reaction reaction of given temperature and light illumination conditions, such as the condition of temperature, illuminance and chlorine feed amount in second, third step of reaction of reaction subsequently concentrates on reaction times aspect for the impact of reaction result.Such as the temperature and light different in second, third step of reaction of reaction subsequently can obviously extend or shorten the first step of reaction reacted reaction times according to combination but can not significantly change the indexs such as the purity of reaction.Such as, after the first step of reaction reaction, when second and third phase temperature maintains 120 DEG C-130 DEG C, even if illuminance brings up to 70000Lux, reaction can not be carried out completely; And on the basis of illuminance 70000Lux, when improving temperature to 140 DEG C, reaction can complete in about 30 hours; And when promoting further temperature to 180 DEG C, the reaction times is then corresponding foreshortened to about 10 hours from about 30 hours.And when second, third step of reaction controls temperature 160 DEG C, illuminance is under 30000-40000Lux condition, reaction can not be carried out completely; Under holding temperature 160 DEG C of conditions, when raising illuminance to 50000Lux, react and carry out completely through about 36 hours ability; When further rising illuminance is to 90000Lux, the time of carrying out that reacts completely then foreshortened to about 10 hours from about 36 hours.
The adjustment order not special requirement in the second and the 3rd temperature and light illumination in step of reaction are reacted described in the application.Such as, both first temperature can be regulated, also can first adjusting intensity of illumination; Pass into chlorine to carry out with both adjustment temperature and light illumination simultaneously, also can separately carry out.Reaction after the application first step of reaction can also when at the uniform velocity pass into chlorine and gradually raised temperature and illumination carry out.
" starting to pass into chlorine " described herein refers to and is heated to before about 55 DEG C-85 DEG C by reaction system from normal temperature, controls amount of chlorine in reaction system and is no more than 5% of chlorine total amount.In preferred original state, be heated to before about 55 DEG C-85 DEG C by reaction system from normal temperature, the chlorine absorption amount in reaction system that controls is no more than 4%, 3%, 2%, 1%, 0.5%, 0.1% of chlorine total amount.In highly preferred original state, reaction system is heated to before about 55 DEG C-85 DEG C from normal temperature, does not substantially pass into chlorine in reaction system, also not containing chlorine.
The total amount of chlorine described herein is can by the amount of chlorine of two (methyl) benzene, six whole chloros of side chain hydrogen atom, and chlorine total amount is at least the molar weight of raw material two (methyl) benzene mole number six times.Preferably, in the inventive method, chlorine total amount is the molar weight of (methyl) benzene mole number more than six times relative to two; The excessive quantity of chlorine can be determined routinely.Preferably, for the object of saving the reaction times, the amount of chlorine passed into separately in each stage described herein also suitably can adjust according to reaction monitoring result.
Contriver finds, uses the light source of narrow wave amplitude to have additional benefit to the by-products content reduced in the reaction of Light chlorimation dimethylbenzene.In some embodiments, the preferred LED of light source used in this application.In the application use LED light source peak wavelength scope between 350nm ~ 700nm, between preferred 350nm-490nm, or preferred peak wavelength 460nm ~ 490nm; The application's LED light source peak wavelength can be such as 265nm, 280nm, 310nm, 360-365nm, 365-370nm, 375-380nm, 385-390nm, 405-410nm etc.The light wave width of the application's LED light source can be within 50nm, within preferred 40nm, preferably within 30nm, preferably within 20nm, most preferably within 10nm.In the application, LED light source can be made up of multiple pointolite, and total power can be 15W, 30W, 45W, 60W, 75W, 90W etc.LED blue-ray light, the LED yellow fluorescent lamp of 586-596nm, the LED green light lamp of 502-574nm of all right preferably 410-470nm of the application's LED light source.In some embodiments, the LED blue-ray light of light source used in this application more preferably 460-490nm.In some embodiments, light source light wave amplitude used in this application is about 30nm for about 10-, more preferably from about 15-25nm.
Light wave width described in the application refers to that light source sends the wavelength region of the half height of light, instead of refers to the peak wavelength of certain light.Such as, light wave width 50nm refers to that the wavelength region that light source sends the half height of light is no more than 50nm.The peak wavelength of the application's LED light source can change within the scope of 350nm ~ 700nm, for any given wavelength, the application's incident light light source can realize controlling light wave width within 50nm, and such as 465nm is peak amplitude 50nm, 360nm be peak amplitude 50nm or 586nm is peak amplitude 50nm.The application finds, LED light source also has the little advantage of heating, therefore can reduce the cost of production unit, such as, not need extra heat sink, during high voltage mercury lamp light source light chlorination reaction, then need corresponding heat sink (for example, see US5514254).
Illuminance described in the application measures by this area conventional instrument, such as luxmeter etc.Wavelength described in the application measures by this area conventional instrument, such as monochromator etc.
" about " described in the application, refers to that for temperature centered by this number, to be worth variation is up and down no more than 2.5 DEG C (being expressed as this numerical value ± 2.5 DEG C), preferably this numerical value ± 2.5 DEG C, ± 2 DEG C or ± 1 DEG C; For illuminance, refer to that centered by this number, be worth variation is up and down no more than 2500Lux (being expressed as this numerical value ± 2500Lux), preferably this numerical value ± 2500Lux, ± 2000Lux, ± 1500Lux, ± 1000Lux, ± 500Lux, ± 200Lux, ± 100Lux.
Described in the application, two (methyl) benzene refers to 1,3-bis-(methyl) benzene or Isosorbide-5-Nitrae-two (methyl) benzene.Accordingly, described in the application, two (trichloromethyl) benzene refers to 1,3-bis-(trichloromethyl) benzene or Isosorbide-5-Nitrae-two (trichloromethyl) benzene; Phthalic acid described in the application refers to 1,3-phthalic acid or Isosorbide-5-Nitrae-phthalic acid; Described in the application, two (chloroformyl) benzene refers to 1,3-bis-(chloroformyl) benzene or Isosorbide-5-Nitrae-two (chloroformyl) benzene.
Preferably not containing plus solvent and initiator in the reaction system of the application's method, more preferably except two (methyl) benzene and chlorine, do not add other component.The application, particularly product purity described in embodiment are through gas-chromatography (area normalization method) quantitative assay before reaction mixture separating treatment.Yield described in the application refers to that crude product two (trichloromethyl) benzene is converted to sterling two (trichloromethyl) benzene and raw material two (methyl) the benzene mass ratio by chlorination reaction available in theory two (trichloromethyl) benzene.
The application's method in different steps such as, by routine sampling and detection method monitoring extent of reaction, gas-chromatography, thus suitably can regulate above-mentioned parameter and saves the reaction times.Description herein for three phases-time aspects is not restrictive, and the staged reaction time freely can adjust according to chlorination progress monitoring result.The chlorine speed that passes into described herein is not limited to specific feeding rate.When using slowly, when gradually etc. term describes and passes into chlorine speed, its implication is not unclear.Because the speed passing into chlorine suitably can be adjusted according to reaction monitoring result by those skilled in the art.
It is very high that the application's method obtains product purity.In some embodiments, directly obtain after reaction that purity is about 90.0%, the mixture of about 90.5%, about 91.0%, about 91.5%, about 92.0%, about 92.5%, about 93.0%, about 93.5%, about 94.0%, about 94.5%, about 95.0%, about 95.5%, about 96.0%, about 96.5%, about 97.0%, about 97.5%, about 98.0%, about 98.5%, about 99.0%, about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.6%, about 99.7%, about 99.8%.In some embodiments, directly obtain after reaction that purity exceedes about 90.0%, about 90.5%, about 91.0%, about 91.5%, about 92.0%, about 92.5%, about 93.0%, about 93.5%, about 94.0%, about 94.5%, about 95.0%, about 95.5%, about 96.0%, about 96.5%, about 97.0%, about 97.5%, about 98.0%, about 98.5%, about 99.0%, about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.6%, about 99.7%, about 99.8% or about 99.9% mixture.In some embodiments, directly obtain after preferred reaction that purity is about 95.0%, about 95.5%, about 96.0%, about 96.5%, about 97.0%, about 97.5%, about 98.0%, about 98.5%, about 99.0%, about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.6%, about 99.7%, about 99.8% or about 99.9% mixture.In some embodiments, purity is obtained after reaction at about 90.0%-about between 90.5, about 90.0%-is about between 91.0, about 90.0%-is about between 91.5, about 90.0%-is about between 92.0, about 90.0%-is about between 92.5, about 90.0%-is about between 93.0, about 90.0%-is about between 93.5, about 90.0%-is about between 94.0, about 90.0%-is about between 94.5, about 90.0%-is about between 95.0, about 90.0%-is about between 95.5, about 90.0%-is about between 96.0, about 90.0%-is about between 96.5, about 90.0%-is about between 97.0, about 90.0%-is about between 97.5, about 90.0%-is about between 98.0, about 90.0%-is about between 98.5, about 90.0%-is about between 99.0, about 90.0%-is about between 99.1, about 90.0%-is about between 99.2, about 90.0%-is about between 99.3, about 90.0%-is about between 99.4, about 90.0%-is about between 99.5, about 90.0%-is about between 99.6, about 90.0%-is about between 99.7, about 90.0%-is about between 99.8, the mixture of about 90.0%-about between 99.9.
, also can be further purified according to conventional purification method, such as rectifying or recrystallization if needed.In some embodiments, reaction mixture is through simple purifying, such as, after a rectifying, two (trichloromethyl) benzene of purity about 99.0%, about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.6%, about 99.7%, about 99.8%, about 99.9%, about 99.95% can be obtained.In some embodiments, reaction mixture is through simple purifying, such as, after a rectifying, can obtain that purity exceedes about 99.0%, two (trichloromethyl) benzene of about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.6%, about 99.7%, about 99.8%, about 99.9%, about 99.95%.
Seldom contain lower boiling impurity according in two (trichloromethyl) benzene reaction mixture that the method for invention directly obtains, therefore can obtain highly purified two (trichloromethyl) benzaldehyde product by simple distillation or a rectifying.Certainly, also high purity two (trichloromethyl) benzene can be obtained by recrystallization purifying through Light chlorimation two (methyl) benzene method products therefrom of the present invention.
As mentioned above, the method for the application's Light chlorimation dimethylbenzene can obtain high purity two (trichloromethyl) benzene.Gained high purity two (trichloromethyl) benzene can purifying or not purifying time and phthalic acid prepare high purity two (chloroformyl) benzene with the magnitude that industrialization is reacted.Preferably, use high purity two (trichloromethyl) benzene after purifying and phthalic acid or water to react in the application and prepare high purity two (chloroformyl) benzene.Therefore the application also has an aspect to relate to the method for preparation two (chloroformyl) benzene, comprises following steps:
A) according to the application, any one method prepares two (trichloromethyl) benzene, and reaction terminates rear presence or absence purification step, such as rectifying or recrystallization;
B) by step a) in two (trichloromethyl) benzene reaction preparation two (chloroformyl) benzene.
Step b) in preferably two (trichloromethyl) benzene and water or phthalic acid react, more preferably react with phthalic acid.
In of the application is preferred, step b) comprise following steps further:
I) raised temperature makes two (trichloromethyl) benzene melt completely, then adds water or phthalic acid and catalyzer, stirs;
Ii) reacting by heating system maintenance reaction is carried out, such as, reaction system is warming up to 90 ~ 125 DEG C, thus obtains product two (chloroformyl) benzene;
Iii) presence or absence purification step, such as rectifying or recrystallization.
Preferably, step a) in preferably there is the step of purifying two (trichloromethyl) benzene.Step I) in two (trichloromethyl) benzene and the molar ratio of phthalic acid be the variable that chemical reaction carries out completely, such as preferred 1:1.01 ~ 1.03.Step I) in reaction catalyzer be Lewis acid, such as aluminum chloride, zinc chloride, iron trichloride etc., preferred iron trichloride; Step I) in preferably also there is a small amount of phthalic acid when reacting with water.Step I) in catalyst charge be preferably 0.2% ~ 0.3% of two (trichloromethyl) benzene quality.
The method that the application two (trichloromethyl) benzene and phthalic acid react preparation two (chloroformyl) benzene has following beneficial effect: technique is simple, and with short production cycle, do not add the media such as solvent, environmental pollution is little; Because the purity of raw material two (trichloromethyl) benzene is very high in the method, therefore another kind of raw material need not adopt in sulfur oxychloride technique the high-purity benzene dioctyl phthalate (99.99% or more needing to use, 99.5% purity of non-generic technical grade), this significantly reduces production cost.In addition, product can pass through ordinary method purifying, such as a rectifying or recrystallization; Owing to strictly controlling reaction conditions in optical chlorinating reaction method; drastically reduce the area lighting end impurity and the impurity close with two (trichloromethyl) benzene boiling point; make the purity of product two (chloroformyl) benzene using this two (trichloromethyl) benzene obtained very high; the purity of such as two (chloroformyl) benzene can reach about 99.95%, about 99.96%, about 99.97%, about 99.98%, about 99.99%, and namely the purity of gained two (chloroformyl) benzene reaches polymerization-grade.
Therefore; the method that the application also has another one aspect to relate to one to prepare two (chloroformyl) benzene, comprises: two (trichloromethyl) benzene being more than 99.2% by purity (two such as prepared by the application's method (trichloromethyl) benzene) and purity be 99.5% technical grade phthalic acid react.The method technique effect is that products therefrom can obtain by a simple purification such as rectifying polymerization-grade two (chloroformyl) benzene that purity can reach 99.95%.
Below, the application will be described with embodiment.These embodiments are all exemplary, instead of restrictive.
summary of the invention
In order to overcome above-mentioned shortcoming, contriver completes the application.The application provides a kind of method of production high purity two (trichloromethyl) benzene and polymerization-grade two (chloroformyl) benzene.The application's method products obtained therefrom due to purity higher, therefore following purification steps is simple, purifying cost is low, and this just makes the application's method become a kind of method capable of being industrialized.In addition; the application with two (trichloromethyl) benzene be raw material and 99.5% phthalic acid react; just can prepare high purity two (chloroformyl) benzene through rectifying, this highly purified two (chloroformyl) benzene can for the preparation of aramid fiber.The application makes the cost of preparation two (chloroformyl) benzene significantly reduce.
The application relates to the photochemical method that one prepares two (trichloromethyl) benzene in one aspect, it is characterized in that two (methyl) benzene and chlorine react preparation two (trichloromethyl) benzene under illumination condition, the optical source wavelength of wherein said illumination is about 350nm-700nm, light wave width is the most about 50nm, wherein be about under 20000Lux-is about 55000Lux start to pass into chlorine in temperature of reaction about 55 DEG C-85 DEG C, illuminance, experience the first step of reaction that temperature of reaction under described illuminance is no more than about 120 DEG C; Then continue to pass into residual content chlorine until reacted under higher temperature of reaction.
Further, can for the preparation of high purity two (chloroformyl) benzene by the inventive method gained high purity two (trichloromethyl) benzene.High purity two (chloroformyl) benzene can be used as aramid fiber raw material.The method of the application greatly reduces the cost of preparation high purity two (chloroformyl) benzene.
The method that the application also has an aspect to relate to one to prepare two (chloroformyl) benzene, comprises following steps: a) any one method prepares two (trichloromethyl) benzene according to the application; B) by step a) in two (trichloromethyl) benzene reaction preparation two (chloroformyl) benzene.Step b) in preferably two (trichloromethyl) benzene and water or phthalic acid react, more preferably react with phthalic acid.
The method that the application also has another one aspect to relate to one to prepare two (chloroformyl) benzene, comprises: by purity be more than 99.2% two (trichloromethyl) benzene and purity be 99.5% technical grade phthalic acid react.
Accompanying drawing explanation
Fig. 1 is embodiment 1 reaction product gas chromatogram.
Fig. 2 is embodiment 9 reaction product gas chromatogram.
Fig. 3 is embodiment 12 reaction product gas chromatogram.
Fig. 4 is embodiment 18 reaction product gas chromatogram.
Fig. 5 is comparative example 1 reaction product gas chromatogram.
Fig. 6 is comparative example 2 reaction product gas chromatogram.
Fig. 7 is comparative example 7 reaction product gas chromatogram.
detailed Description Of The Invention
Embodiment
materials and methods
In following embodiment, the purity of two (trichloromethyl) benzene, two (chloroformyl) benzene uses gas chromatograph, carries out quantitative assay by area normalization method.Gas chromatograph for determination condition is:
The typical retention time of each material measured via reference substance is:
1,3-bis-(trichloromethyl) benzene 9.49min;
Isosorbide-5-Nitrae-two (trichloromethyl) benzene 9.93min;
1,3-bis-(chloroformyl) benzene 4.58min;
Isosorbide-5-Nitrae-two (chloroformyl) benzene 4.35min.
The gas chromatograph used in embodiment is: Agilent 7820A GC.Adopt hand sampling during mensuration, those skilled in the art can understand error that manual operation brings also within tolerance interval.
It is luxmeter for measuring the instrument of illuminance in enforcement: uncommon agate AR823+ Intelligent Digital luxmeter.
The wave amplitude of the LED light source used in embodiment is 20-50nm.
Embodiment 1
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 212.32 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 460nm, and illuminance is 49000Lux, then chlorine reaction is passed into, the speed that passes into controlling chlorine makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 290 grams, 4 hours 35 minutes hours consuming time of the first step of reaction.Adjusting intensity of illumination, to 61000Lux, raises system temperature to 145 DEG C, continues to pass into chlorine, consumes 290 grams, chlorine, 3 hours 30 minutes hours consuming time of the second step of reaction.Adjusting intensity of illumination is to 87000Lux again,
While lead to chlorine limit to improve system temperature to 180 DEG C, maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, the 3rd step of reaction consuming time 5 hours 55 minutes altogether.Reaction amounts to and consumes amount of chlorine is 880 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 97.61% (see color atlas 1), product yield 95.45%.
Embodiment 2
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 206.17 grams, stop after being warming up to 80 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 360nm, and illuminance is 49000Lux, pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 280 grams, the first step of reaction consuming time 4 hours 30 minutes.Adjusting intensity of illumination, to 60000Lux, after raising system temperature to 140 DEG C, continues to pass into chlorine, consumes 280 grams, chlorine, the second step of reaction consuming time 3 hours 55 minutes.Maintain illuminance to 60000Lux, after raising system temperature to 160 DEG C, pass into 320 grams, chlorine, the 3rd step of reaction consuming time 16 hours 35 minutes altogether.Reaction amounts to and consumes amount of chlorine is 880 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 96.28%, product yield 94.01%.
Embodiment 3
1 is added in the 500ml four-hole boiling flask having thermometric, condensing reflux and solvent recovery unit, 3-bis-(methyl) benzene 201.50 grams, add 100 grams, solvent tetracol phenixin, stop after being warming up to 60 DEG C heating up, open LED and irradiate, incident light central peak wavelength is 465nm, illuminance is 43000Lux, passes into chlorine reaction, and the speed that passes into controlling chlorine makes system temperature be no more than 120 DEG C, consuming amount of chlorine is 270 grams, the first step of reaction consuming time 4 hours 30 minutes.Adjusting intensity of illumination, to 66000Lux, after raising system temperature to 145 DEG C, continues to pass into chlorine, consumes 270 grams, chlorine, the second step of reaction consuming time 3 hours 30 minutes.Adjusting intensity of illumination, to 91000Lux, after raising system temperature to 180 DEG C, passes into 300 grams, chlorine, the 3rd step of reaction consuming time 4 hours 50 minutes altogether.Reaction amounts to and consumes amount of chlorine is 840 grams.74 grams, recycling design tetracol phenixin.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 95.89%.
Embodiment 4
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 202.12 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 405nm, and illuminance is 31000Lux, pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 135 grams, the first step of reaction consuming time 3 hours 20 minutes.Adjusting intensity of illumination, to 58000Lux, after raising system temperature to 160 DEG C, continues to pass into chlorine, consumes 405 grams, chlorine, the second step of reaction consuming time 4 hours 30 minutes.Adjusting intensity of illumination, to 86000Lux, after raising system temperature to 170 DEG C, passes into 300 grams, chlorine, the 3rd step of reaction consuming time 4 hours 45 minutes altogether.Reaction amounts to and consumes amount of chlorine is 840 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 95.03%.
Embodiment 5
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-dimethyl benzene 200.37 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 465nm, and illuminance is 49000Lux, pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 270 grams, reaction time consumption 4 hours 30 minutes.Raise illuminance subsequently to 70000Lux, after raising temperature of reaction system to 160 DEG C, continue logical chlorine, the amount of chlorine of consumption is 570 grams, reaction time consumption 25 hours 35 points.Reaction amounts to and consumes amount of chlorine is 840 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 95.17%.
Embodiment 6
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 202.40 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 586nm, and illuminance is 20000Lux, pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 4 hours 50 minutes.Adjusting intensity of illumination, to 67000Lux, passes into chlorine and after raising system temperature to 135 DEG C, passes into chlorine for some time, consume 270 grams, chlorine; While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 86000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 330 grams, second and third elementary reaction consuming time 10 hours 35 minutes altogether.Reaction amounts to and consumes amount of chlorine is 870 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 91.32%.
Embodiment 7
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 203.10 grams, unlatching LED is irradiated, incident light central peak wavelength is 505nm, and illuminance is 43000Lux, heats up from 55 DEG C, and progressively pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 4 hours 50 minutes.Adjusting intensity of illumination, to 66000Lux, after raising system temperature to 142 DEG C, passes into chlorine for some time, consumes 270 grams, chlorine; While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 96000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 310 grams, consuming time 9 hours 40 minutes altogether second and third stage.Reaction amounts to and consumes amount of chlorine is 850 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 93.28%.
Embodiment 8
Embodiment 1-7 gained reaction mixture is obtained after a rectifying purifying 1,3-bis-(trichloromethyl) benzene of purifying.Again use gas chromatographic analysis, 1,3-bis-(trichloromethyl) benzene purity of purifying is respectively: 99.42%, 99.28%, 99.26%, 99.24%, 99.28%, 99.06%, 99.20%.
Embodiment 9
In the 500ml four-hole bottle of band thermometric, condensing reflux and whipping appts, add that purity is 99.42% 1,3-bis-(trichloromethyl) benzene 402.45 grams, intensification makes 1,3-bis-(trichloromethyl) benzene melts completely, according to 1,1.01 times of 3-bis-(trichloromethyl) benzene mole number add purity is 99.50% 1,3-bis-(formyloxy) benzene 216.94 grams, again according to 1,0.30% of 3-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 1.21 grams, maintains reaction in 60 minutes and terminate after continuing to be warming up to 110 DEG C.Products therefrom is carried out rectifying, obtains 1,3-bis-(chloroformyl) benzene of purifying.The purity of 1,3-bis-(chloroformyl) benzene of gas chromatographic analysis result display purifying is 99.97% (color atlas 2).
Embodiment 10
In the 500ml four-hole bottle of band thermometric, condensing reflux and whipping appts, add that purity is 99.20% 1,3-bis-(trichloromethyl) benzene 400.16 grams, intensification makes 1,3-bis-(trichloromethyl) benzene melts completely, according to 1,1.03 times of 3-bis-(trichloromethyl) benzene mole number add purity is 99.50% 1,3-bis-(formyloxy) benzene 219.98 grams, again according to 1,0.20% of 3-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 0.80 gram, maintains reaction in 30 minutes and terminate after continuing to be warming up to 105 DEG C.Products therefrom is carried out rectifying, obtains 1,3-bis-(chloroformyl) benzene of purifying.The purity of 1,3-bis-(chloroformyl) benzene of gas chromatographic analysis result display purifying is 99.95%.
Embodiment 11
In the 500ml four-hole bottle of band thermometric, condensing reflux and whipping appts, add that purity is 99.28% 1,3-bis-(trichloromethyl) benzene 400.12 grams, intensification makes 1,3-bis-(trichloromethyl) benzene melts completely, according to 1,1.02 times of 3-bis-(trichloromethyl) benzene mole number add purity is 99.50% 1,3-bis-(formyloxy) benzene 217.82 grams, again according to 1,0.25% of 3-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 1.00 grams, maintains reaction in 45 minutes and terminate after continuing to be warming up to 100 DEG C.Products therefrom is carried out rectifying, obtains 1,3-bis-(chloroformyl) benzene of purifying.The purity of 1,3-bis-(chloroformyl) benzene of gas chromatographic analysis result display purifying is 99.96%.
Embodiment 12
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 4-bis-(methyl) benzene 208.4 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 460nm, and illuminance is 49000Lux, start to pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 280 grams, 4 hours consuming time of the first step of reaction.Adjusting intensity of illumination, to 56000Lux, after raising system temperature to 155 DEG C, consumes 280 grams, chlorine, the second step of reaction consuming time 3 hours 20 minutes.While lead to chlorine limit to improve system temperature to 180 DEG C, adjusting intensity of illumination is to 97000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, the 3rd step of reaction consuming time 6 hours 10 minutes altogether.Reaction amounts to and consumes amount of chlorine is 860 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of Isosorbide-5-Nitrae-two (trichloromethyl) benzene is 97.75% (see color atlas 3), product yield 95.20%.
Embodiment 13
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 4-bis-(methyl) benzene 200.00 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 465nm, and illuminance is 49000Lux, pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 270 grams, 5 hours consuming time of the first step of reaction.Adjusting intensity of illumination, to 66000Lux, raises system temperature to 143 DEG C, consumes 270 grams, chlorine, the second step of reaction consuming time 3 hours 50 minutes altogether.While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 90000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, the 3rd step of reaction consuming time 5 hours 25 minutes altogether.Reaction amounts to and consumes amount of chlorine is 840 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, and wherein the purity of Isosorbide-5-Nitrae-two (trichloromethyl) benzene is 97.04%, product yield 94.11%.
Embodiment 14
1 is added in the 500ml four-hole boiling flask having thermometric, condensing reflux and solvent recovery unit, 4-bis-(methyl) benzene 200.16 grams, add 100 grams, solvent tetracol phenixin, stop after being warming up to 60 DEG C heating up, open LED and irradiate, incident light central peak wavelength is 405nm, illuminance is 43000Lux, starts to pass into chlorine reaction, and control chlorine passes into speed and makes system temperature be no more than 120 DEG C, consuming amount of chlorine is 270 grams, the first step of reaction consuming time 4 hours 50 minutes.Adjusting intensity of illumination, to 66000Lux, after raising system temperature to 150 DEG C, consumes 270 grams, chlorine, the second step of reaction consuming time 3 hours 55 minutes.Adjusting intensity of illumination, to 97000Lux, after raising system temperature to 180 DEG C, passes into 310 grams, chlorine, the 3rd step of reaction 5 hours consuming time altogether.Reaction amounts to and consumes amount of chlorine is 850 grams.63 grams, recycling design tetracol phenixin.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, and wherein the purity of Isosorbide-5-Nitrae-two (trichloromethyl) benzene is 96.02%.
Embodiment 15
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 4-bis-(methyl) benzene 200.21 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 505nm, and illuminance is 31000Lux, start to pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 135 grams, the first step of reaction consuming time 3 hours 55 minutes.Adjusting intensity of illumination, to 58000Lux, after raising system temperature to 150 DEG C, consumes 405 grams, chlorine, the second step of reaction consuming time 4 hours 55 minutes.Adjusting intensity of illumination, to 86000Lux, after raising system temperature to 170 DEG C, consumes 310 grams, chlorine, the 3rd step of reaction consuming time 5 hours 20 minutes altogether.Reaction amounts to and consumes amount of chlorine is 850 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, and wherein the purity of Isosorbide-5-Nitrae-two (trichloromethyl) benzene is 95.52%.
Embodiment 16
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 4-bis-(methyl) benzene 203.21 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 360nm, and illuminance is 49000Lux, start to pass into chlorine reaction, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, and consuming amount of chlorine is 270 grams, reaction time consumption 4 hours 25 minutes; Adjusting intensity of illumination, to 70000Lux, after raising system temperature to 140 DEG C, consumes 650 grams, chlorine, reaction 31 hours consuming time altogether.Reaction amounts to and consumes amount of chlorine is 920 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, and wherein the purity of Isosorbide-5-Nitrae-two (trichloromethyl) benzene is 96.64%.
Embodiment 17
Embodiment 12-16 gained reaction mixture is obtained after a rectifying purifying Isosorbide-5-Nitrae-two (trichloromethyl) benzene of purifying.Again use gas chromatographic analysis, Isosorbide-5-Nitrae-two (trichloromethyl) the benzene purity of purifying is respectively: 99.45%, 99.38%, 99.36%, 99.22%, 99.32%.
Embodiment 18
In the 500ml four-hole bottle of band thermometric, condensing reflux and whipping appts, add that purity is 99.45% 1,4-bis-(trichloromethyl) benzene 400.32 grams, system is heated up and makes 1,4-bis-(trichloromethyl) benzene melts completely, according to 1,1.01 times of 4-bis-(trichloromethyl) benzene mole number add purity is 99.50% 1,4-bis-(formyloxy) benzene 215.79 grams, again according to 1,0.25% of 4-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 1.00 grams, maintains reaction in 60 minutes and terminate after continuing to be warming up to 125 DEG C; Products therefrom is carried out rectifying, obtains Isosorbide-5-Nitrae-two (chloroformyl) benzene of purifying.The purity of Isosorbide-5-Nitrae-two (chloroformyl) benzene of gas chromatographic analysis result display purifying is 99.96%.(see color atlas 4)
Embodiment 19
In the 500ml four-hole bottle of band thermometric, condensing reflux and whipping appts, add that purity is 99.22% 1,4-bis-(trichloromethyl) benzene 402.36 grams, system is heated up and makes 1,4-bis-(trichloromethyl) benzene melts completely, according to 1,1.02 times of 4-bis-(trichloromethyl) benzene mole number add purity is 99.50% 1,4-bis-(formyloxy) benzene 219.04 grams, again according to 1,0.30% of 4-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 1.21 grams, maintains reaction in 45 minutes and terminate after continuing to be warming up to 120 DEG C; Products therefrom is carried out rectifying, obtains Isosorbide-5-Nitrae-two (chloroformyl) benzene of purifying.The purity of Isosorbide-5-Nitrae-two (chloroformyl) benzene of gas chromatographic analysis result display purifying is 99.95%.
Embodiment 20
In the 500ml four-hole bottle of band thermometric, condensing reflux and whipping appts, add that purity is 99.32% 1,4-bis-(trichloromethyl) benzene 405.12 grams, system is heated up and makes 1,4-bis-(trichloromethyl) benzene melts completely, according to 1,1.03 times of 4-bis-(trichloromethyl) benzene mole number add purity is 99.50% 1,4-bis-(formyloxy) benzene 222.70 grams, again according to 1,0.20% of 4-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 0.81 gram, maintains reaction in 30 minutes and terminate after continuing to be warming up to 115 DEG C; Products therefrom is carried out rectifying, obtains Isosorbide-5-Nitrae-two (chloroformyl) benzene of purifying.The purity of Isosorbide-5-Nitrae-two (chloroformyl) benzene of gas chromatographic analysis result display purifying is 99.96%.
Comparative example 1
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 201.00 grams, unlatching LED is irradiated, incident light central peak wavelength is 465nm, and illuminance is 60000Lux, heats up from 20 DEG C, and progressively pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, reacts 20 hours, and consuming amount of chlorine is 1200 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, color atlas shows 1,3-bis-(methyl) benzene chlorizate that principal reaction product is the mixture that 4-5 chlorine replaces.(see color atlas 5)
Comparative example 2
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 200.30 grams, unlatching LED is irradiated, incident light central peak wavelength is 460nm, and illuminance is 43000Lux, heats up from 20 DEG C, and progressively pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction reaction time consumption 5 hours 55 minutes.Adjusting intensity of illumination, to 63000Lux, after raising system temperature to 142 DEG C, consumes 270 grams, chlorine.While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 91000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 360 grams.Second and third elementary reaction consuming time 12 hours 15 minutes altogether.Reaction amounts to and consumes amount of chlorine is 900 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 88.93%.(see color atlas 6)
Comparative example 3
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 201.46 grams, unlatching LED is irradiated, incident light central peak wavelength is 505nm, and illuminance is 43000Lux, heats up from 30 DEG C, and progressively pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 5 hours 40 minutes.Adjusting intensity of illumination, to 61000Lux, after raising system temperature to 145 DEG C, passes into chlorine for some time, consumes chlorine 270g; While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 89000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, consuming time 11 hours 5 minutes altogether second and third stage.Reaction amounts to and consumes amount of chlorine is 840 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 89.44%.
Comparative example 4
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 200.90 grams, unlatching LED is irradiated, incident light central peak wavelength is 465nm, and illuminance is 43000Lux, heats up from 40 DEG C, and progressively pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 5 hours 10 minutes.Adjusting intensity of illumination, to 63000Lux, after raising system temperature to 142 DEG C, passes into chlorine for some time, consumes chlorine 270g.While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 93000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 320 grams.Second and third elementary reaction 10 hours consuming time altogether.Reaction amounts to and consumes amount of chlorine is 860 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 89.51%.
Comparative example 5
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 199.08 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 405nm, and illuminance is 10000Lux, progressively pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 4 hours 55 minutes.Adjusting intensity of illumination, to 56000Lux, after raising system temperature to 133 DEG C, passes into chlorine for some time, consumes chlorine 270g; While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 97000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, consuming time 15 hours 20 minutes altogether second and third stage.Reaction amounts to and consumes amount of chlorine is 840 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 88.03%.
Comparative example 6
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 200.60 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 586nm, and illuminance is 5000Lux, pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 5 hours 5 minutes.Adjusting intensity of illumination, to 6.9Lux, after raising system temperature to 147 DEG C, passes into chlorine for some time, consumes 270 grams, chlorine; While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 98000Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, and second and third stage is total to consuming time 18 hours 30 points.Reaction amounts to and consumes amount of chlorine is 840 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 78.70%.
Comparative example 7
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 200.05 grams, stop after being warming up to 60 DEG C heating up, unlatching LED is irradiated, and incident light central peak wavelength is 465nm, and illuminance is 500Lux, pass into chlorine reaction, hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first step of reaction consuming time 5 hours 30 minutes; Adjusting intensity of illumination, to 69000Lux, after raising system temperature to 150 DEG C, passes into chlorine for some time, consumes 270 grams, chlorine; While lead to chlorine limit to improve system temperature to 180 DEG C, then adjusting intensity of illumination is to 9.8Lux, and maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, consuming time 20 hours 25 minutes altogether second and third stage; Reaction amounts to and consumes amount of chlorine is 940 grams.Terminate to sample rear gained reaction mixture from reaction, gas chromatograph is analyzed this sample, wherein the purity of 1,3-bis-(trichloromethyl) benzene is 70.12%.(see color atlas 7)
Comparative example 8
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 200.00 grams, stop after being warming up to 110 DEG C heating up, open LED and irradiate, incident light central peak wavelength is 405nm, illuminance is 60000Lux, pass into chlorine reaction, reaction acutely heats up after starting for some time, temperature cannot be maintained less than 120 DEG C, the very fast carbonization blackening of reaction solution, reacts unsuccessfully.
Comparative example 9
1 is added in the 500ml four-hole boiling flask having thermometric and condensation reflux unit, 3-bis-(methyl) benzene 202.10 grams, stop after being warming up to 120 DEG C heating up, open LED and irradiate, incident light central peak wavelength is 360nm, illuminance is 43000Lux, pass into chlorine reaction, reaction acutely heats up after starting for some time, temperature cannot be maintained less than 120 DEG C, the very fast carbonization blackening of reaction solution, reacts unsuccessfully.
Claims (23)
1. prepare the photochemical method of two (trichloromethyl) benzene for one kind, it is characterized in that two (methyl) benzene and chlorine react preparation two (trichloromethyl) benzene under illumination condition, the optical source wavelength of wherein said illumination is about 350nm-700nm, light wave width is the most about 50nm, wherein be about under 20000Lux-is about 55000Lux start to pass into chlorine in temperature of reaction about 55 DEG C-85 DEG C, illuminance, experience the first step of reaction that temperature of reaction under described illuminance is no more than about 120 DEG C; Then continue to pass into residual content chlorine until reacted under higher temperature of reaction.
2. the method for claim 1, it is characterized in that chlorine total amount needed for described first step of reaction consumption reaction at least about 1/6.
3. the method for claim 1, is characterized in that the about 1/6-about 1/2 of chlorine total amount needed for described first step of reaction consumption reaction; Preferably, the about 1/4-about 1/3 of chlorine total amount needed for described first step of reaction consumption reaction.
4. the method as described in any one of claim 1-3, is characterized in that described illuminance is about 50000Lux for about 25000Lux-.
5. method as claimed in claim 4, is characterized in that described illuminance is about 50000Lux for about 30000Lux-.
6. method as claimed in claim 5, is characterized in that described illuminance is about 45000Lux for about 35000Lux-.
7. the method as described in any one of claim 1-6, after it is characterized in that the first step of reaction reaction be no more than about 180 DEG C in temperature of reaction, illuminance passes into surplus chlorine under being no more than the condition of about 100000Lux.
8. method as claimed in claim 7, is characterized in that the reaction after the first step of reaction is divided into the second step of reaction and the 3rd step of reaction, and wherein the second step of reaction temperature of reaction is no more than about 160 DEG C, illuminance is no more than about 70000Lux; 3rd step of reaction temperature of reaction is no more than about 180 DEG C, illuminance is no more than about 100000Lux.
9. method as claimed in claim 8, is characterized in that the second step of reaction temperature of reaction is not less than about 120 DEG C, illuminance is not less than about 50000Lux.
10. method as claimed in claim 8, is characterized in that the 3rd step of reaction temperature of reaction is not less than about 160 DEG C, illuminance is not less than about 70000Lux.
11. methods as described in any one of claim 8-10, is characterized in that the chlorine consumption of described second step of reaction is the about 1/4-about 2/5 of the required chlorine total amount of reaction.
12. methods as claimed in claim 11, is characterized in that each in three stages amount of chlorine of consuming is about 1/3 of the required chlorine total amount of reaction.
13. methods according to any one of claim 1-12, is characterized in that described light source is LED.
14. methods as claimed in claim 13, is characterized in that described LED is the LED blue-ray light of wavelength 460nm-490nm.
15. methods as described in claim 13 or 14, is characterized in that the light wave width of described light source is about 10-30nm.
16. methods as claimed in claim 15, is characterized in that the light wave width of described light source is 15-25nm.
17. according to any one of claim 1-16 method, to it is characterized in that in the reaction system of the method not containing plus solvent and initiator.
18. according to any one of claim 1-17 method, it is characterized in that being included in the purification step that chlorination reaction terminates rear rectifying or recrystallization further.
19. 1 kinds of methods preparing two (chloroformyl) benzene, comprise following steps:
A) according to any one of claim 1-18, method prepares two (trichloromethyl) benzene;
B) by step a) middle two (trichloromethyl) benzene reaction preparation two (chloroformyl) benzene obtained.
20. methods as claimed in claim 19, is characterized in that step b) in two (trichloromethyl) benzene and water or phthalic acid react preparation two (chloroformyl) benzene.
21. methods as described in claim 19 or 20, is characterized in that step b) comprise following steps further:
I) raised temperature makes two (trichloromethyl) benzene melt completely, then adds water or phthalic acid, catalyzer, stirs;
Ii) reacting by heating system maintenance reaction is carried out, thus obtains product two (chloroformyl) benzene; And
Iii) optional purification step.
22. methods as claimed in claim 21, is characterized in that: step I) in catalyzer be Lewis acid, such as aluminum chloride, zinc chloride, iron trichloride etc., preferred iron trichloride; Step I) in react when reacting with water in containing a small amount of phthalic acid.
23. 1 kinds of methods preparing two (chloroformyl) benzene, it comprises:
By purity be more than 99.2% two (trichloromethyl) benzene and purity be 99.5% technical grade phthalic acid react.
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| CN201310422286.8A CN104447188B (en) | 2013-09-13 | 2013-09-13 | The preparation method of a kind of two (trichloromethyl) benzene and two (chloroformyl) benzene |
| PCT/CN2014/086372 WO2015035937A1 (en) | 2013-09-13 | 2014-09-12 | Method for the preparation of trichloromethyl-group-substituted benzene |
| US14/905,775 US9556090B2 (en) | 2013-09-13 | 2014-09-12 | Method for the preparation of trichloromethyl-group-substituted benzene |
| KR1020167009711A KR102353684B1 (en) | 2013-09-13 | 2014-09-12 | Method for the preparation of trichloromethyl substituted benzene |
| EP14843701.5A EP3045440B1 (en) | 2013-09-13 | 2014-09-12 | Method for the preparation of trichloromethyl-group-substituted benzene |
| JP2016541795A JP6311946B2 (en) | 2013-09-13 | 2014-09-12 | Method for preparing trichloromethyl substituted benzene |
| RU2016113954A RU2670436C2 (en) | 2013-09-13 | 2014-09-12 | Method for obtaining trichloromethyl-substituted benzene |
| ES14843701T ES2744453T3 (en) | 2013-09-13 | 2014-09-12 | Method for the preparation of benzene substituted with a trichloromethyl group |
| IL244493A IL244493B (en) | 2013-09-13 | 2016-03-08 | Method for the preparation of trichloromethyl substituted benzene |
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| CN109364847A (en) * | 2018-11-28 | 2019-02-22 | 内蒙古三爱富万豪氟化工有限公司 | Optical chlorinating reaction device and the method for preparing difluoromono-chloroethane |
| CN114516780A (en) * | 2021-12-21 | 2022-05-20 | 宿迁市科莱博生物化学有限公司 | Preparation method of 3,4, 5-trifluorobromobenzene |
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| CN1948245A (en) * | 2006-04-14 | 2007-04-18 | 浙江巍华化工有限公司 | Method of producing chlorobenzyl by photochlorination |
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| CN1948245A (en) * | 2006-04-14 | 2007-04-18 | 浙江巍华化工有限公司 | Method of producing chlorobenzyl by photochlorination |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364847A (en) * | 2018-11-28 | 2019-02-22 | 内蒙古三爱富万豪氟化工有限公司 | Optical chlorinating reaction device and the method for preparing difluoromono-chloroethane |
| CN114516780A (en) * | 2021-12-21 | 2022-05-20 | 宿迁市科莱博生物化学有限公司 | Preparation method of 3,4, 5-trifluorobromobenzene |
| CN114516780B (en) * | 2021-12-21 | 2024-03-29 | 科莱博(江苏)科技股份有限公司 | Preparation method of 3,4, 5-trifluoro-bromobenzene |
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