CN104447188B - The preparation method of a kind of two (trichloromethyl) benzene and two (chloroformyl) benzene - Google Patents

Abstract

The application relates to a kind of photochemical reaction and prepares two (trichloromethyl) benzene, and it is further reacted to the method for preparing two (chloroformyl) benzene. In reactor, add two (methyl) benzene, under the control illuminance of incident light source and the condition of reaction temperature, pass into chlorine; Gained reactant mixture can obtain high-purity two (trichloromethyl) benzene through simple post processing. Use two (trichloromethyl) of the present invention benzene can obtain easily highly purified two (chloroformyl) benzene---manufacture one of raw material of aramid fiber. The application's advantage is not introduce solvent, radical initiator, sensitising agent grade in an imperial examination three components, only by wavelength and the intensity of stage control reaction condition and light source, just can improve the purity of product.

Description

The preparation method of a kind of two (trichloromethyl) benzene and two (chloroformyl) benzene

Technical field

The application relates to a kind of optical chlorinating reaction method, relates in particular to a kind of by two (methyl) benzeneFirst prepare two (trichloromethyl) benzene with chlorine generation photochemical reaction, and the latter enters one againThe method of step reaction preparation two (chloroformyl) benzene. The application's method by control temperature,Illuminance (also can be described as luminous intensity) and consumption amount of chlorine can significantly improve two (trichloromethyls)The purity of benzene, and further can prepare at lower cost polymer grade two (chloroformyl) benzene.

Background technology

Aramid fiber is the spy that a class has high strength, high-wearing feature, the advantageous property such as high temperature resistantPlant fiber. Due to its good application performance, aramid fiber all has boundless in many industriesApplication prospect. World market is ever-increasing situation to the demand of aramid fiber, the coming years,Aramid fiber market, the whole world will increase at a high speed with annual 20% left and right. But due to technical difficultyGreatly, the reason such as cost of investment height, aramid fiber market is monopolized by minority developed countries such as America and Japan always.The Technora fiber of the Kevlar fiber of du pont company, Japanese Di Ren company is currentThe matured product of position oneself at the forefront on market.

Aramid fiber market is enormously potential at home, and according to statistics, China is directly annual and indirect importingAramid fiber and correlated product are in hundred million yuan. In recent years, the machine such as Donghua University, Shanghai Textile research instituteStructure has successively been carried out the research and development of aramid fiber. But also rare domestic manufacturers and research aircraft at presentStructure can be developed competitive matured product.

Two (trichloromethyl) benzene can react with water, phthalic acid etc. the centre of preparing aramid fiberBody---two (chloroformyl) benzene.

The method of preparation two (trichloromethyl) benzene is with radical initiator and/or light-initiated side chainFree radical chlorination, sometimes also need to add second even the 3rd component to prevent on phenyl ringChlorine substitution reaction, the light source of employing is generally mercury lamp. Because the purity of two (trichloromethyl) benzeneUndesirable, this technology does not but realize industrialization volume production.

Present inventor thinks, in prior art, the method for light chlorination two (methyl) benzene is depositedDefect mainly in the following aspects.

1) optical chlorinating reaction is free chain reaction, because there being side reaction, chlorination site andThe control of depth of chlorination relative difficult. For the photochemical chlorination product of separate complex, DE3146868,JP47-130931 has to carry out a large amount of distillation operations, greatly improved this series productsProduction cost. In order to prevent the substitution reaction of benzene chlorine in ring, US1,345,373 add sulphur andChloroacetic chloride, US1,384,909 add metal carbonate, US1,733,268 interpolation p and s sulphurs,US2,034,962 adds organic base, US2, and 695,873 add acid amides, US2,817,632 HesUS2,844,635 use amine substance, US3, and 363,013 use triphenylphosphine etc. These volumesOuter component certainly will affect purity and the subsequent purification step of two (trichloromethyl) benzene. US4029560Report with US4048033: at 1,3-bis-(methyl) benzene chlorination process with 1,3-bis-(three chloromethanesBase) benzene is solvent, to suppress reaction and the accessory substance that on phenyl ring, chlorine replaces, this needs a large amount of 1,3-Two (trichloromethyl) benzene recycles, thereby the method process complexity, and cost is higher.

In a word, in prior art, in order to realize phenyl ring hydrogen atom not by chloro, pendant methyl hydrogen is formerSon, all by chloro, need to be introduced multiple auxiliary element, these auxiliary element meeting " pollution " targetsProduct two (trichloromethyl) benzene, is unsuitable for the preparation of high purity product.

2) optical chlorinating reaction also needs to add radical initiator to start reaction.

Grinding of the people such as Wang Lumin (Tonghua Teachers College's journal, 2005,26 (4): 46-47)Study carefully and show light chlorination 1, in the reaction of 3-bis-(methyl) benzene, need to add radical initiator to maintainReaction.

CN102211975A discloses three temperature stage neighbours two (methyl) benzene light chlorination preparationThe method of tetrachloro neighbour two (methyl) benzene. In the method, the temperature of light chlorination be divided into 120-125 DEG C,125-130 DEG C, 130-135 DEG C three phases, the amount of chlorine passing in each temperature stage is dividedWei in 1/3,1/2 and 1/6 this reaction of total amount, also not need to add benzoyl peroxide conductLight-sensitive catalyst three phase temperature reactions finish rear tetrachloro neighbour two (methyl) benzene yield and are only65%, pentachloro-neighbour two (methyl) benzene yield is owing to having added photoactivate in 10% this reactionCatalyst, causes gained tetrachloro neighbour two (methyl) even if benzene passes through further purifying, purityAlso 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's discovery, the short-wavelength light of low pressure mercury lamp can bring out other photochemistry pairsReaction, declines product purity; And the long wavelength light of high pressure, medium pressure mercury lamp is not enough to cause chlorineRadical reaction, increases energy consumption. In addition while using mercury lamp as light source, because caloric value is large, need,Be equipped with corresponding cooling device, make structure of reactor complexity.

CN1948245 discloses wave-length coverage 300-600nm, power bracket isThe light emitting diode (LED) of 0.1W～1000W carries out optical chlorinating reaction as light source and produces chlorineBenzyl, reaction temperature maintains 90～150 DEG C. It is to carry that the document is recorded its technical problem that will solveThe light chlorination low for a kind of power consumption, light source caloric value is little, by selecting light emitting diodeCan improve light source utilization rate as light source. Although the document mentioned and can use between two (methyl)Benzene is as raw material, but whole embodiment of the document all do not disclose purity and the product of productRate.

Applicant also finds, prior art is not also ground the illuminance of this reaction light sourceStudy carefully.

In addition, producing aramid fiber needs highly purified two (chloroformyl) benzene as initial formerMaterial, otherwise aramid fiber difficult quality reaches regulation requirement. Two (chloroformyls) of the prior artIn the preparation method of benzene, the most often thionyl chloride method taking phthalic acid as raw material of application(for example, referring to, CN102516060A, CN102344362A). But need in this techniqueWant 99.99% high-purity benzene dioctyl phthalate could obtain satisfied two (chloroformyl) benzene, this makesThis route preparation cost significantly raises, technology difficulty strengthens.

Summary of the invention

In order to overcome above-mentioned shortcoming, inventor has completed the application. The application provides a kind of and producesThe method of high-purity two (trichloromethyl) benzene and polymer grade two (chloroformyl) benzene. The applicationMethod products obtained therefrom is because purity is higher, therefore subsequent purification step is simple, purifying cost is low, thisJust make the application's method become a kind of method capable of being industrialized. In addition, the application is with two (threeChloromethyl) benzene is that raw material reacts with 99.5% phthalic acid, just can prepare high through rectifyingPurity two (chloroformyl) benzene, this highly purified two (chloroformyl) benzene can be for the preparation of virtueSynthetic fibre fiber. The application significantly reduces the cost of preparing two (chloroformyl) benzene.

The application relates to the photochemical method that one is prepared two (trichloromethyl) benzene in one aspect,It is characterized in that two (methyl) benzene and chlorine react preparation two (trichloromethyls) under illumination conditionBenzene, the optical source wavelength of wherein said illumination is that about 350nm-700nm, light wave width are for the most about50nm, wherein at approximately 55 DEG C-85 DEG C of reaction temperatures, the about 20000Lux-of illuminance approximately 55000Under Lux, start to pass into chlorine, experience reaction temperature under described illuminance is no more than approximately 120 DEG CFirst stage of reaction; Then under higher reaction temperature, continue to pass into surplus chlorine untilReaction completes.

Further, can be used for system by the inventive method gained high-purity two (trichloromethyl) benzeneStandby high-purity two (chloroformyl) benzene. High-purity two (chloroformyl) benzene can be used as aramid fiber fibreDimension raw material. The application's method greatly reduces the one-tenth of preparation high-purity two (chloroformyl) benzeneThis.

The application also has an aspect to relate to the method that one is prepared two (chloroformyl) benzene, bagContain following steps: a) prepare two (trichloromethyl) benzene according to any method described in the application;B) reaction of two (trichloromethyl) benzene in a) preparation two (chloroformyl) benzene by step. StepRapid b) in preferably two (trichloromethyl) benzene react with water or phthalic acid, more preferably with benzene twoFormic acid reaction.

The application also has another one aspect to relate to the method that one is prepared two (chloroformyl) benzene,Comprise: be the work that more than 99.2% two (trichloromethyl) benzene and purity are 99.5% by purityThe reaction of industry level phthalic acid.

Brief description of the drawings

Fig. 1 is embodiment 1 product gas chromatogram.

Fig. 2 is embodiment 9 product gas chromatograms.

Fig. 3 is embodiment 12 product gas chromatograms.

Fig. 4 is embodiment 18 product gas chromatograms.

Fig. 5 is comparative example's 1 product gas chromatogram.

Fig. 6 is comparative example's 2 product gas chromatograms.

Fig. 7 is comparative example's 7 product gas chromatograms.

Detailed Description Of The Invention

In prior art in existing smooth xylyl chloride method, in products therefrom except target is producedBeyond thing two (trichloromethyl) benzene, also contain the accessory substance that is much difficult to separate with target product.Be difficult in order to remove these accessory substance separating, need to carry out repeatedly distillation operation. Repeatedly rectifyingOperation makes the light xylyl chloride method of prior art very inadvisable on cost, and this is alsoThe industrial main cause that does not adopt the extensive preparation of the method two (trichloromethyl) benzene.

Inventor finds through research, is difficult to separate in the light xylyl chloride method of prior artAccessory substance in distillation operation, concentrate in light fraction. Through inventor's research, find that these are lightCut accessory substance is mainly the accessory substance that phenyl ring chloro occurs, for example phenyl ring one chloro side chain simultaneouslyThe accessory substance of methyl tetrachloro generation or pentachloro-. The accessory substance of these phenyl ring chloros and two (three chloromethanesBase) benzene boiling point is comparatively approaching, thereby separation process needs the very much higher time rectifying of cost.

And the inventor creatively finds, in photochemical reaction, pass through two (methyl) benzene to existUnder specified temp, illuminance condition, carry out first stage of reaction with the chlorine of controlled quentity controlled variable and react, energyEnough accessory substances that significantly reduces aforementioned phenyl ring chloro, realize high-purity and prepare two (trichloromethyls)Benzene.

Therefore, the application relates in one aspect one and prepares the photochemical of two (trichloromethyl) benzeneMethod, is characterized in that two (methyl) benzene and chlorine react preparation two (three under illumination conditionChloromethyl) benzene, the optical source wavelength of wherein said illumination is that about 350nm-700nm, light wave width areThe most about 50nm, wherein at approximately 55 DEG C-85 DEG C of reaction temperatures, the about 20000Lux-of illuminanceUnder about 55000Lux, start to pass into chlorine, experience reaction temperature under described illuminance is no more thanFirst stage of reaction of approximately 120 DEG C; Then under higher reaction temperature, continue to pass into surplusChlorine is until reacted. Of the method preferred aspect, light source is preferably LEDLamp.

The inventor finds, controls initial reaction temperature and illuminance pair well in first stage of reactionIt is very necessary after reaction, obtaining reaction mixture in high purity (before purifying). Particularly,Carry out the first stage of reaction reaction according to described condition, can significantly reduce aforementioned phenyl ring chloroAccessory substance, and do not need strictly to control the reaction condition in later stage, as long as along with depth of chlorinationImprove and corresponding raising reaction temperature and/or illuminance.

The minimum of first stage of reaction continues degree or the duration can be according to concrete reactionSystem is determined by simple test, to control the content of impurity in final reacting mixtureOr the purity of two (trichloromethyl) benzene. Maximum for first stage of reaction continues degree or holdsThe continuous time has no particular limits. In the incipient stage of chlorination reaction, due to the heat release of reaction,The speed that passes into that need to control chlorine makes reaction temperature be no more than approximately 120 DEG C. But along with chlorinationThe carrying out of reaction and the raising of depth of chlorination, the reaction speed under the condition of first stage of reactionCan be slack-off, so that need to improve temperature and/or illuminance reaches rational or economically feasibleReaction speed. Therefore in the first stage of reaction later stage, need to improve temperature and/or illuminance.

Inventor's discovery, in first stage of reaction, it is total that preferably consumption accounts for the required chlorine of reactionIt is favourable that amount ratio is at least about raise after 1/6 amount of chlorine temperature and illuminance. At thisSome bright preferred aspects, in first stage of reaction, consume amount of chlorine and account for the required chlorine of reactionTotal amount ratio raises warm again after being more than or equal to approximately 1/6,1/5,1/4,1/3,2/5 or 1/2Degree and illuminance. More of the present invention preferred aspect, in first stage of reaction, consume chlorineTolerance account for reaction required chlorine total amount ratio between about 1/6-1/5, between 1/6-1/4,1/6-1/3Between, between 1/6-2/5, between 1/6-1/2, between 1/5-1/4, between 1/5-1/3,1/5-2/5Between, between 1/5-1/2, between 1/4-1/3, between 1/4-2/5, between 1/4-1/2,1/3-2/5Between, temperature and illuminance again raise after between 1/3-1/2 or between 2/5-1/2.

More of the present invention preferred aspect, in first stage of reaction, illuminance also can suitably be adjustedWhole. More of the present invention preferred aspect, the illuminance of first stage of reaction is preferably approximatelyBetween the about 25000Lux of 20000Lux-, between the about 30000Lux of about 20000Lux-, approximatelyBetween the about 35000Lux of 20000Lux-, between the about 40000Lux of about 20000Lux-, approximatelyBetween the about 45000Lux of 20000Lux-, between the about 50000Lux of about 20000Lux-, approximatelyBetween the about 55000Lux of 20000Lux-, between the about 30000Lux of about 25000Lux-, approximatelyBetween the about 35000Lux of 25000Lux-, between the about 40000Lux of about 25000Lux-, approximatelyBetween the about 45000Lux of 25000Lux-, between the about 50000Lux of about 25000Lux-, approximatelyBetween the about 55000Lux of 25000Lux-, between the about 35000Lux of about 30000Lux-, approximatelyBetween the about 40000Lux of 30000Lux-, between the about 45000Lux of about 30000Lux-, approximatelyBetween the about 50000Lux of 30000Lux-, between the about 55000Lux of about 30000Lux-, approximatelyBetween the about 40000Lux of 35000Lux-, between the about 45000Lux of about 35000Lux-, approximatelyBetween the about 50000Lux of 35000Lux-, between the about 55000Lux of about 35000Lux-, approximatelyBetween the about 45000Lux of 40000Lux-, between the about 50000Lux of about 40000Lux-, approximatelyBetween the about 55000Lux of 40000Lux-, between the about 50000Lux of about 45000Lux-, approximatelyBetween the about 55000Lux of 45000Lux-, between the about 55000Lux of about 50000Lux-.

More of the present invention preferred aspect, in first stage of reaction, reaction temperature also can suitably be adjustedWhole. More of the present invention preferred aspect, the reaction temperature of first stage of reaction is preferably approximatelyBetween 55 DEG C-Yue 60 DEG C, between approximately 55 DEG C-Yue 65 DEG C, between approximately 55 DEG C-Yue 70 DEG C, approximatelyBetween 55 DEG C-Yue 75 DEG C, between approximately 55 DEG C-Yue 80 DEG C, between approximately 55 DEG C-Yue 85 DEG C, approximatelyBetween 60 DEG C-Yue 65 DEG C, between approximately 60 DEG C-Yue 70 DEG C, between approximately 60 DEG C-Yue 75 DEG C, approximatelyBetween 60 DEG C-Yue 80 DEG C, between approximately 60 DEG C-Yue 85 DEG C, between approximately 65 DEG C-Yue 70 DEG C, approximatelyBetween 65 DEG C-Yue 75 DEG C, between approximately 65 DEG C-Yue 80 DEG C, between approximately 65 DEG C-Yue 85 DEG C, approximatelyBetween 70 DEG C-Yue 75 DEG C, between approximately 70 DEG C-Yue 70 DEG C, between approximately 70 DEG C-Yue 85 DEG C, approximatelyBetween 75 DEG C-Yue 80 DEG C, between approximately 75 DEG C-Yue 85 DEG C, between approximately 80 DEG C-Yue 85 DEG C. At thisInvention some preferred aspects, the reaction temperature of first stage of reaction preferably approximately 55 DEG C, approximately60 DEG C, approximately 65 DEG C, approximately 70 DEG C, approximately 75 DEG C, approximately 80 DEG C, approximately 85 DEG C.

Preferably, in the application aspect another, it is first anti-that light chlorination two (methyl) benzene reactsShould the process after the stage be in approximately 120 DEG C of initial temperatures, approximately 180 DEG C of final temperatures, incidentIlluminance is initiated with under the condition of about 50000Lux, final about 100000Lux and passes into surplus chlorineGas. Process described in the application after method first stage of reaction can be a single reactionStage, or be divided into several stages of reaction be for example divided into two, three, four, five, six, seven,Eight, the stages of reaction such as nine, ten. After first stage of reaction in process, the temperature in each stageIlluminance optionally also raises when degree rising. Inventor's discovery, after first stage of reactionIn process, reaction condition is more flexible, can have multiple choices. Mistake after first stage of reactionThe main purpose that regulates different temperature and illuminance in journey is to impel to have reacted. Invention human hairExisting, strictly control in the present invention on the basis of first stage reaction, after first stage of reactionIn process, the variation of reaction condition is little for the purity impact of final products.

More preferred, light chlorination two (methyl) benzene reacts the process after first stage of reactionCan also be further divided into second stage of reaction and the 3rd stage of reaction. The second stage of reaction controlReaction temperature is that approximately 160 DEG C of about 120-, incident light illumination are the about 70000Lux of about 50000-, logicalThe amount of chlorine entering is 1/4～2/5 of total amount; The 3rd stage of reaction control temperature be about 160-approximately180 DEG C, incident light illumination are the about 100000Lux of about 70000-, pass into surplus chlorine. ?Two, in three stages, rising temperature and rising illuminance sequencing each other. Inventor's discovery,In this three stages embodiment, two (trichloromethyl) benzene in reactant mixture when reaction finishesPurity can reach more than 95%.

Inventor's discovery, key of the present invention is to control first stage of reaction in the manner describedCarry out; Through the first stage of reaction reaction of given temperature and illuminance condition, subsequently anti-Should as the condition of temperature, illuminance and chlorine feed amount in second, third stage of reaction forThe impact of reaction result concentrates on reaction time aspect. Reaction is subsequently as second, third reactionTemperature and illumination combinations different in stage can obviously extend or shorten the first stage of reaction reactionAfter reaction time but can significantly not change the indexs such as the purity of reaction. For example,, in the first reactionAfter elementary reaction, when second and third phase temperature maintains 120 DEG C-130 DEG C, even illuminanceBring up to 70000Lux, reaction can not be carried out completely; And on the basis of illuminance 70000LuxUpper, while improving temperature to 140 DEG C, reaction can complete in approximately 30 hours; And ought further carryWhen intensification degree to 180 DEG C, the reaction time is corresponding foreshortened to approximately 10 hours from approximately 30 hours.And in the time that second, third stage of reaction is controlled at 160 DEG C of temperature, illuminance existsUnder 30000-40000Lux condition, reaction can not be carried out completely; In 160 DEG C of conditions of holding temperatureUnder, rising illuminance is during to 50000Lux, and reaction is carried out completely through approximately 36 hours ability;When further rising illuminance is to 90000Lux, the time of carrying out of reacting completely is little from approximately 36Time foreshorten to approximately 10 hours.

Described in the application, reaction is in the adjusting of the second and the 3rd temperature in the stage of reaction and illuminanceOrder is special requirement not. For example, both can first regulate temperature, also can first regulating illuminationDegree; Pass into that chlorine can the two carries out with regulating temperature and illuminance simultaneously, also can divide and drive intoOK. Reaction after the application's first stage of reaction can also at the uniform velocity pass into chlorine and rise graduallyIn the situation of high-temperature and illumination, carry out.

" starting to pass into chlorine " described herein refers to reaction system is heated to approximately from normal temperatureBefore 55 DEG C-85 DEG C, control amount of chlorine in reaction system and be no more than 5% of chlorine total amount. PreferablyOriginal state in, reaction system was heated to before approximately 55 DEG C-85 DEG C from normal temperature, control anti-The chlorine absorption amount in system of answering be no more than chlorine total amount 4%, 3%, 2%, 1%, 0.5%,0.1%. In highly preferred original state, reaction system is heated to approximately 55 DEG C-85 DEG C from normal temperatureBefore, in reaction system, substantially do not pass into chlorine, do not contain chlorine yet.

The total amount of chlorine described herein is can be by six whole chlorine of side chain hydrogen atom of two (methyl) benzeneThe amount of chlorine in generation, chlorine total amount is at least the mole of six times of raw material two (methyl) benzene mole numbers.Preferably, in the inventive method chlorine total amount be with respect to six times of two (methyl) benzene mole numbers withOn mole; The excessive quantity of chlorine can be determined routinely. Preferably, anti-for savingObject between seasonable, the amount of chlorine passing into separately in each stage described herein also can be according to reaction prisonSurveying result suitably adjusts.

Inventor finds, uses the light source of narrow wave amplitude to reducing the pair in the reaction of light xylyl chlorideProduct content has additional benefit. In some embodiments, light source used in this application is excellentSelect LED lamp. In the application, using LED light source peak wavelength scope is 350nm～700nmBetween, between preferred 350nm-490nm, or preferred peak wavelength 460nm～490nm; ThisApplication LED light source peak wavelength can be for example 265nm, 280nm, 310nm,360-365nm, 365-370nm, 375-380nm, 385-390nm, 405-410nm etc. ThisThe light wave width of application LED light source can be in 50nm, and preferably 40nm is with interior, preferred 30nmWith interior, preferred 20nm with interior, most preferably in 10nm. In the application, LED light source canBe made up of multiple spot lights, general power can be 15W, 30W, 45W, 60W, 75W, 90WDeng. The application's LED light source preferably 410-470nm LED blue-ray light,The LED yellow fluorescent lamp of 586-596nm, the LED green light lamp of 502-574nm. In some enforcementIn mode, light source used in this application is the LED blue-ray light of 460-490nm more preferably. OneIn a little embodiments, light source light wave amplitude used in this application is the about 30nm of about 10-, more preferably from about15-25nm。

Described in the application, light wave width refers to that light source sends the wave-length coverage of the half-peak eminence of light, and notRefer to the peak wavelength of certain light. For example, light wave width 50nm refers to that light source sends the half-peak of lightThe wave-length coverage of eminence is no more than 50nm. The peak wavelength of the application's LED light source can be 350Variation within the scope of nm～700nm, for any given wavelength, the application's incident light light source allCan realize and control light wave width within 50nm, for example 465nm is peak value wave amplitude 50nm, 360nmFor peak value wave amplitude 50nm or 586nm are peak value wave amplitude 50nm. The application finds, LED lightSource also has advantages of that heating is little, therefore can reduce the cost of production equipment, for example, do not needExtra heat sink, needs corresponding cooling dress when high-pressure sodium lamp light source light chlorination reactionPut (for example, referring to US5514254).

Illuminance described in the application can be measured by this area conventional instrument, for example luxmeterDeng. Wavelength described in the application can be measured by this area conventional instrument, such as monochromator etc.

" approximately " described in the application, refers to that for temperature value changes up and down centered by given figureBe 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, referring to centered by given figure that value changes is up and down no more than 2500Lux and (representsFor 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-bis-(methyl)Benzene. Accordingly, described in the application, two (trichloromethyl) benzene refers to 1,3-bis-(trichloromethyl)Benzene or Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene; Described in the application, phthalic acid refers to 1,3-phthalic acidOr Isosorbide-5-Nitrae-phthalic acid; Described in the application, two (chloroformyl) benzene refers to 1,3-, bis-(chloroformylsBase) benzene or Isosorbide-5-Nitrae-bis-(chloroformyl) benzene.

In the reaction system of the application's method, preferably not containing plus solvent and initator, more preferably removeBeyond two (methyl) benzene and chlorine, do not add other component. In the application, particularly embodimentDescribed product purity is through gas-chromatography (area normalization method) before reactant mixture separating treatmentQuantitative assay. Described in the application, yield refers to that crude product two (trichloromethyl) benzene is converted to sterling two(trichloromethyl) benzene and raw material two (methyl) benzene can obtain in theory by chlorination reactionThe mass ratio of two (trichloromethyl) benzene.

The application's method can different phase by the monitoring of routine sampling and detection method react intoDegree, for example gas-chromatography, thus suitably regulate above-mentioned parameter and save the reaction time. HereinBe not restrictive for the description of three phases-time aspects, the staged reaction time can be according to chlorinationProgress monitoring result and freely adjusting. The chlorine speed that passes into described herein is not limited to specificallyFeed rate. When using slowly, when gradually etc. term is described and passed into chlorine speed, its implication alsoNon-unclear. Can be by those skilled in the art according to reaction monitoring because pass into the speed of chlorineResult is suitably adjusted.

It is very high that the application's method makes product purity. In some embodiments, direct after reactionObtain purity and be approximately 90.0%, approximately 90.5%, approximately 91.0%, approximately 91.5%, approximately 92.0%, approximately92.5%, approximately 93.0%, approximately 93.5%, approximately 94.0%, approximately 94.5%, approximately 95.0%, approximately 95.5%,Approximately 96.0%, approximately 96.5%, approximately 97.0%, approximately 97.5%, approximately 98.0%, approximately 98.5%, approximately99.0%, approximately 99.1%, approximately 99.2%, approximately 99.3%, approximately 99.4%, approximately 99.5%, approximately 99.6%,Approximately 99.7%, approximately 99.8% mixture. In some embodiments, after reaction, directly obtainPurity exceedes approximately 90.0%, approximately 90.5%, approximately 91.0%, approximately 91.5%, approximately 92.0%, approximately92.5%, approximately 93.0%, approximately 93.5%, approximately 94.0%, approximately 94.5%, approximately 95.0%, approximately 95.5%,Approximately 96.0%, approximately 96.5%, approximately 97.0%, approximately 97.5%, approximately 98.0%, approximately 98.5%, approximately99.0%, approximately 99.1%, approximately 99.2%, approximately 99.3%, approximately 99.4%, approximately 99.5%, approximately 99.6%,Approximately 99.7%, approximately 99.8% or approximately 99.9% mixture. In some embodiments, preferredAfter reaction, directly obtain purity and be approximately 95.0%, approximately 95.5%, approximately 96.0%, approximately 96.5%,Approximately 97.0%, approximately 97.5%, approximately 98.0%, approximately 98.5%, approximately 99.0%, approximately 99.1%, approximately99.2%, approximately 99.3%, approximately 99.4%, approximately 99.5%, approximately 99.6%, approximately 99.7%, approximately 99.8%Or approximately 99.9% mixture. In some embodiments, after reaction, obtain purity at about 90.0%-Approximately between 90.5, about 90.0%-approximately between 91.0, about 90.0%-approximately between 91.5, about 90.0%-Approximately between 92.0, about 90.0%-approximately between 92.5, about 90.0%-approximately between 93.0, about 90.0%-Approximately between 93.5, about 90.0%-approximately between 94.0, about 90.0%-approximately between 94.5, about 90.0%-Approximately between 95.0, about 90.0%-approximately between 95.5, about 90.0%-approximately between 96.0, about 90.0%-Approximately between 96.5, about 90.0%-approximately between 97.0, about 90.0%-approximately between 97.5, about 90.0%-Approximately between 98.0, about 90.0%-approximately between 98.5, about 90.0%-approximately between 99.0, about 90.0%-Approximately between 99.1, about 90.0%-approximately between 99.2, about 90.0%-approximately between 99.3, about 90.0%-Approximately between 99.4, about 90.0%-approximately between 99.5, about 90.0%-approximately between 99.6, about 90.0%-Approximately between 99.7, about 90.0%-approximately between 99.8, the approximately mixture between 99.9 of about 90.0%-.

, also can be further purified according to conventional purification process for example rectifying or heavily knot if neededBrilliant. In some embodiments, reactant mixture for example, through simple purifying, a rectifyingAfter, can obtain purity approximately 99.0%, approximately 99.1%, approximately 99.2%, approximately 99.3%, approximately 99.4%,Approximately 99.5%, approximately 99.6%, approximately 99.7%, approximately 99.8%, approximately 99.9%, approximately 99.95%Two (trichloromethyl) benzene. In some embodiments, the simple purifying of reactant mixture process,For example, after a rectifying, can obtain purity exceed approximately 99.0%, approximately 99.1%, approximately 99.2%,Approximately 99.3%, approximately 99.4%, approximately 99.5%, approximately 99.6%, approximately 99.7%, approximately 99.8%, approximately99.9%, approximately 99.95% two (trichloromethyl) benzene.

Little in two (trichloromethyl) benzene reactant mixture directly obtaining according to the method for inventionContain lower boiling impurity, therefore can obtain highly purified by simple distillation or a rectifyingTwo (trichloromethyl) benzaldehyde product. Certainly, through light chlorination two of the present invention (methyl) benzene method instituteObtain product and also can obtain high-purity two (trichloromethyl) benzene by recrystallization purifying.

As mentioned above, the method for the application's light xylyl chloride can obtain high-purity two (trichlorinesMethyl) benzene. Gained high-purity two (trichloromethyl) benzene can be at purifying or not when purifying and benzeneDioctyl phthalate is prepared high-purity two (chloroformyl) benzene with the magnitude of industrialization reaction. Preferably,In the application, use high-purity two (trichloromethyl) benzene after purifying to react with phthalic acid or waterPreparation high-purity two (chloroformyl) benzene. Therefore the application also has an aspect to relate to preparation twoThe method of (chloroformyl) benzene, comprises following steps:

A) prepare two (trichloromethyl) benzene according to any method described in the application, reaction knotAfter bundle, there is or not exist purification step, for example rectifying or recrystallization;

B) reaction of two (trichloromethyl) benzene in a) preparation two (chloroformyl) benzene by step.

Step b) in preferably two (trichloromethyl) benzene react with water or phthalic acid, more preferablyReact with phthalic acid.

Of the application preferred aspect, step b) further comprises following steps:

I) rising temperature melts two (trichloromethyl) benzene completely, then adds water or phthalic acidAnd catalyst, stir;

Ii) heating reaction system maintains to react and carries out, for example, reaction system is warming up to90～125 DEG C, thus product two (chloroformyl) benzene obtained;

Iii) there is or not exist purification step, for example rectifying or recrystallization.

Preferably, preferably there is the step of purifying two (trichloromethyl) benzene in a) in step. StepRapid two (trichloromethyl) benzene in i) and the molar ratio of phthalic acid are that chemical reaction is completeThe variable entirely carrying out, for example preferred 1:1.01～1.03. Step I) in reaction catalyst beLewis acid, such as alchlor, zinc chloride, ferric trichloride etc., preferably ferric trichloride; StepRapid preferably also there is a small amount of phthalic acid while reacting with water in i). Step I) in catalystAddition is preferably 0.2%～0.3% of two (trichloromethyl) benzene quality.

The application two (trichloromethyl) benzene reacts preparation two (chloroformyl) benzene with phthalic acidMethod there is following beneficial effect: technique is simple, with short production cycle, does not add Jie such as solventMatter, environmental pollution is little; In the method due to the purity of raw material two (trichloromethyl) benzeneVery high, therefore another kind of raw material needn't adopt the high-purity benzene that needs use in thionyl chloride techniqueDioctyl phthalate (99.99% or more than, 99.5% purity of non-general industry level), this obviously reducesProduction cost. In addition, product can pass through conventional method purifying, a for example rectifying or heavyCrystallization; Due to the strict reaction condition of controlling in optical chlorinating reaction method, significantly reduce lightCut impurity and the impurity approaching with two (trichloromethyl) benzene boiling point, make to use this two (threeChloromethyl) purity of product two (chloroformyl) benzene that makes of benzene is very high, for example two (chloromethanesAcyl group) purity of benzene to approximately 99.95%, approximately 99.96%, approximately 99.97%, approximately 99.98%,Approximately 99.99%, the purity of gained two (chloroformyl) benzene reaches polymer grade.

Therefore, the application also has another one aspect to relate to one to prepare two (chloroformyl) benzeneMethod, comprise: be more than 99.2% two (trichloromethyl) benzene (for example this Shen by purityPlease prepared two (trichloromethyl) benzene of method) with the purity technical grade benzene diformazan that is 99.5%Acid reaction. The method technique effect is that products therefrom passes through a for example rectifying of simple purification and isCan obtain polymer grade two (chloroformyl) benzene of purity to 99.95%.

Below, the application will describe with detailed description of the invention. These detailed description of the invention allExemplary, instead of restrictive.

Detailed description of the invention

Materials and methods

In following embodiment, the purity of two (trichloromethyl) benzene, two (chloroformyl) benzene is to makeWith gas chromatograph, carry out quantitative assay by area normalization method. Gas chromatograph for determination conditionFor:

The typical retention time of each material of measuring via reference substance is:

1,3-bis-(trichloromethyl) benzene 9.49min;

Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene 9.93min;

1,3-bis-(chloroformyl) benzene 4.58min;

Isosorbide-5-Nitrae-bis-(chloroformyl) benzene 4.35min.

The gas chromatograph using in embodiment is: Agilent 7820AGC. When mensuration, adoptWith hand sampling, those skilled in the art can understand the error that manual operation brings and also can acceptWithin scope.

It in enforcement, is illumination photometer for measuring the instrument of illuminance: the uncommon intelligent number of agate AR823+Word luxmeter.

The wave amplitude of the LED lamp source using in embodiment is 20-50nm.

Embodiment 1

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 212.32 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 460nm, and illuminance is 49000Lux, then passes into chlorine anti-Should, the speed that passes into of controlling chlorine makes system temperature be no more than 120 DEG C, consumes amount of chlorine to be290 grams, 4 hours 35 minutes hours consuming time of first stage of reaction. Adjusting intensity of illumination to 61000Lux, rising system temperature to 145 DEG C, continues to pass into chlorine, consumes 290 grams, chlorine, the3 hours 30 minutes hours consuming time of two stages of reaction. Adjusting intensity of illumination is to 87000Lux again,

System temperature to 180 DEG C is improved on logical chlorine limit, limit, maintains 180 DEG C and continues logical chlorine, consumes chlorineTolerance is 300 grams, the 3rd stage of reaction consuming time 5 hours 55 minutes altogether. Reaction amounts to and consumesAmount of chlorine is 880 grams. From finishing, reaction samples in gained reactant mixture, at gas phase lookOn spectrometer, analyze this sample, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 97.61% (to seeChromatogram 1), product yield 95.45%.

Embodiment 2

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 206.17 grams of benzene, stop heating up after being warming up to 80 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 360nm, and illuminance is 49000Lux, passes 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 280Gram, first stage of reaction consuming time 4 hours 30 minutes. Adjusting intensity of illumination is to 60000Lux,After rising system temperature to 140 DEG C, continue to pass into chlorine, consume 280 grams, chlorine, second is anti-Should consuming time 3 hours 55 minutes stage. Maintain illuminance to 60000Lux, rising system temperatureDegree, after 160 DEG C, passes into 320 grams, chlorine, the 3rd stage of reaction 16 hours 35 consuming time altogetherMinute. Reaction amounts to and consumes amount of chlorine is 880 grams. From reaction finishes, gained reaction mixesIn thing, sample, on gas chromatograph, analyze this sample, wherein 1,3-bis-(trichloromethyl)The purity of benzene is 96.28%, product yield 94.01%.

Embodiment 3

In the 500ml four-hole boiling flask that has thermometric, condensing reflux and solvent recovery unit, add201.50 grams of 1,3-bis-(methyl) benzene, add 100 grams, solvent carbon tetrachloride, are warming up to 60 DEG CAfter stop heating up, open LED light irradiation, incident light central peak wavelength is 465nm, lightIllumination is 43000Lux, passes into chlorine reaction, and the speed that passes into of controlling chlorine makes system temperatureDegree is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, 4 hours consuming time of first stage of reaction30 minutes. Adjusting intensity of illumination is to 66000Lux, after rising system temperature to 145 DEG C, continuesPass into chlorine, consume 270 grams, chlorine, second stage of reaction consuming time 3 hours 30 minutes. AdjustJoint illuminance, to 91000Lux, after rising system temperature to 180 DEG C, passes into 300 grams, chlorine,The 3rd stage of reaction consuming time 4 hours 50 minutes altogether. Reaction amounts to and consumes amount of chlorine is 840 grams.Reclaim 74 grams, solvent carbon tetrachloride. From finishing, reaction samples in gained reactant mixture,On gas chromatograph, analyze this sample, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is95.89％。

Embodiment 4

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 202.12 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 405nm, and illuminance is 31000Lux, passes 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 135Gram, first stage of reaction consuming time 3 hours 20 minutes. Adjusting intensity of illumination is to 58000Lux,After rising system temperature to 160 DEG C, continue to pass into chlorine, consume 405 grams, chlorine, second is anti-Should consuming time 4 hours 30 minutes stage. Adjusting intensity of illumination is to 86000Lux, rising system temperatureDegree, after 170 DEG C, passes into 300 grams, chlorine, and the 3rd stage of reaction is total to consuming time 4 hours 45 pointsClock. Reaction amounts to and consumes amount of chlorine is 840 grams. Gained reactant mixture from reaction finishesThis sample is analyzed in middle sampling on gas chromatograph, and wherein 1,3-bis-(trichloromethyl) benzenePurity be 95.03%.

Embodiment 5

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-dimethyl200.37 grams of benzene, stop after being warming up to 60 DEG C heating up, and open LED light irradiation, in incident lightHeart peak wavelength is 465nm, and illuminance is 49000Lux, passes into chlorine reaction, controls chlorinePass into speed and make system temperature be no more than 120 DEG C, consuming amount of chlorine is 270 grams, reaction time consumption4 hours 30 minutes. The illuminance that raises is subsequently to 70000Lux, and rising temperature of reaction system extremelyAfter 160 DEG C, continue logical chlorine, the amount of chlorine of consumption is 570 grams, reaction time consumption 25 hours 35Point. Reaction amounts to and consumes amount of chlorine is 840 grams. From reaction finishes in gained reactant mixtureThis sample is analyzed in sampling on gas chromatograph, and wherein 1,3-bis-(trichloromethyl) benzene pureDegree is 95.17%.

Embodiment 6

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 202.40 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 586nm, and illuminance is 20000Lux, passes 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 270Gram, first stage of reaction consuming time 4 hours 50 minutes. Adjusting intensity of illumination is to 67000Lux,Pass into chlorine and the system temperature to 135 DEG C of raising after, pass into chlorine a period of time, consume chlorine270 grams; System temperature to 180 DEG C is improved on logical chlorine limit, limit, then adjusting intensity of illumination extremely86000Lux, maintains 180 DEG C and continues logical chlorine, and consuming amount of chlorine is 330 grams, second,Three elementary reactions consuming time 10 hours 35 minutes altogether. Reaction amounts to and consumes amount of chlorine is 870 grams.From reaction finishes, in gained reactant mixture, sample, on gas chromatograph, analyze this sample,Wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 91.32%.

Embodiment 7

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 203.10 grams of benzene, open LED light irradiation, incident light central peak wavelength is 505nm,Illuminance is 43000Lux, since 55 DEG C of intensifications, and progressively passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, first stage of reaction consuming time 4Hours 50 minutes. Adjusting intensity of illumination is to 66000Lux, after rising system temperature to 142 DEG C,Pass into chlorine a period of time, consume 270 grams, chlorine; System temperature is improved extremely in logical chlorine limit, limit180 DEG C, then adjusting intensity of illumination is to 96000Lux, maintains 180 DEG C and continues logical chlorine, consumes chlorineTolerance is 310 grams, consuming time 9 hours 40 minutes altogether second and third stage. Reaction amounts to and consumesAmount of chlorine is 850 grams. From finishing, reaction samples in gained reactant mixture, at gas phase lookOn spectrometer, analyze this sample, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 93.28%.

Embodiment 8

Embodiment 1-7 gained reactant mixture is obtained to 1 of purifying, 3-after a rectifying purifyingTwo (trichloromethyl) benzene. Again use gas chromatographic analysis, 1 of purifying, 3-bis-(trichloromethyl)99.42%, 99.28%, 99.26%, 99.24%, 99.28%, 99.06% benzene purity is respectively:,99.20％。

Embodiment 9

In the 500ml four-hole bottle with thermometric, condensing reflux and agitating device, add purity to be99.42% 1,402.45 grams of 3-bis-(trichloromethyl) benzene, heat up and make 1,3-bis-(trichloromethyl) benzeneFusing, adds purity to be according to 1.01 times of 1,3-bis-(trichloromethyl) benzene mole number completely99.50% 1,216.94 grams of 3-bis-(formyl) benzene, then according to 1,3-bis-(trichloromethyl) benzene weightAmount 0.30% add 1.21 grams of ferric chloride catalysts, maintain 60 after continuing to be warming up to 110 DEG CMinute reaction finish. Products therefrom is carried out to rectifying, obtain 1 of purifying, 3-bis-(chloroformyl)Benzene. Gas chromatographic analysis result shows 1 of purifying, and the purity of 3-bis-(chloroformyl) benzene is99.97% (chromatogram 2).

Embodiment 10

In the 500ml four-hole bottle with thermometric, condensing reflux and agitating device, add purity to be99.20% 1,400.16 grams of 3-bis-(trichloromethyl) benzene, heat up and make 1,3-bis-(trichloromethyl) benzeneFusing, adds purity to be according to 1.03 times of 1,3-bis-(trichloromethyl) benzene mole number completely99.50% 1,219.98 grams of 3-bis-(formyl) benzene, then according to 1,3-bis-(trichloromethyl) benzene weightAmount 0.20% add 0.80 gram of ferric chloride catalyst, maintain 30 after continuing to be warming up to 105 DEG CMinute reaction finish. Products therefrom is carried out to rectifying, obtain 1 of purifying, 3-bis-(chloroformyl)Benzene. Gas chromatographic analysis result shows 1 of purifying, and the purity of 3-bis-(chloroformyl) benzene is99.95％。

Embodiment 11

In the 500ml four-hole bottle with thermometric, condensing reflux and agitating device, add purityBe 99.28% 1,400.12 grams of 3-bis-(trichloromethyl) benzene, heat up and make 1,3-bis-(trichloromethyl)Benzene melts completely, adds purity to be according to 1.02 times of 1,3-bis-(trichloromethyl) benzene mole number99.50% 1,217.82 grams of 3-bis-(formyl) benzene, then according to 1,3-bis-(trichloromethyl) benzene weightAmount 0.25% add 1.00 grams of ferric chloride catalysts, maintain after continuing to be warming up to 100 DEG CReaction in 45 minutes finishes. Products therefrom is carried out to rectifying, obtain 1 of purifying, 3-bis-(chloromethanesAcyl group) benzene. Gas chromatographic analysis result shows 1 of purifying, 3-bis-(chloroformyl) benzenePurity is 99.96%.

Embodiment 12

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add Isosorbide-5-Nitrae-bis-(firstBase) 208.4 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, incidentLight center peak wavelength is 460nm, and illuminance is 49000Lux, starts 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 280Gram, 4 hours consuming time of first stage of reaction. Adjusting intensity of illumination is to 56000Lux, rising systemAfter temperature to 155 DEG C, consume 280 grams, chlorine, 20 points of second stages of reaction consuming time 3 hoursClock. System temperature to 180 DEG C is improved on logical chlorine limit, limit, and adjusting intensity of illumination is to 97000Lux,Maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, and the 3rd stage of reaction is consuming time altogether6 hours 10 minutes. Reaction amounts to and consumes amount of chlorine is 860 grams. Gained from reaction finishesIn reactant mixture, sample, on gas chromatograph, analyze this sample, wherein Isosorbide-5-Nitrae-bis-(threeChloromethyl) purity of benzene is 97.75% (seeing chromatogram 3), product yield 95.20%.

Embodiment 13

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add Isosorbide-5-Nitrae-bis-(firstBase) 200.00 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 465nm, and illuminance is 49000Lux, passes 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 270Gram, 5 hours consuming time of first stage of reaction. Adjusting intensity of illumination is to 66000Lux, rising systemTemperature to 143 DEG C, consumes 270 grams, chlorine, and second stage of reaction is total to consuming time 3 hours 50 pointsClock. System temperature to 180 DEG C is improved on logical chlorine limit, limit, then adjusting intensity of illumination is to 90000Lux,Maintain 180 DEG C and continue logical chlorine, consuming amount of chlorine is 300 grams, and the 3rd stage of reaction consumes altogetherTime 5 hours 25 minutes. Reaction amounts to and consumes amount of chlorine is 840 grams. Institute from reaction finishesObtain in reactant mixture and sample, on gas chromatograph, analyze this sample, wherein Isosorbide-5-Nitrae-bis-(threeChloromethyl) purity of benzene is 97.04%, product yield 94.11%.

Embodiment 14

In the 500ml four-hole boiling flask that has thermometric, condensing reflux and solvent recovery unit, add200.16 grams of Isosorbide-5-Nitrae-bis-(methyl) benzene, add 100 grams, solvent carbon tetrachloride, are warming up to 60 DEG CAfter stop heating up, open LED light irradiation, incident light central peak wavelength is 405nm, lightIllumination is 43000Lux, starts to pass into chlorine reaction, and control chlorine passes into speed and makes systemTemperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, and first stage of reaction is consuming time 4 littleTime 50 minutes. Adjusting intensity of illumination is to 66000Lux, after rising system temperature to 150 DEG C, disappears270 grams, consumption chlorine, second stage of reaction consuming time 3 hours 55 minutes. Adjusting intensity of illumination extremely97000Lux, after rising system temperature to 180 DEG C, passes into 310 grams, chlorine, the 3rd reaction rankSection 5 hours consuming time altogether. Reaction amounts to and consumes amount of chlorine is 850 grams. Reclaim solvent tetrachloro63 grams, carbon. From reaction finishes, in gained reactant mixture, sample, on gas chromatograph, divideAnalyse this sample, wherein the purity of Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene is 96.02%.

Embodiment 15

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add Isosorbide-5-Nitrae-bis-(firstBase) 200.21 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 505nm, and illuminance is 31000Lux, starts to pass into chlorine anti-Should, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, consumes amount of chlorine and is135 grams, first stage of reaction consuming time 3 hours 55 minutes. Adjusting intensity of illumination is to 58000Lux,After rising system temperature to 150 DEG C, consume 405 grams, chlorine, second stage of reaction consuming time 4Hours 55 minutes. Adjusting intensity of illumination is to 86000Lux, after rising system temperature to 170 DEG C,Consume 310 grams, chlorine, the 3rd stage of reaction consuming time 5 hours 20 minutes altogether. Reaction amounts to and disappearsConsumption amount of chlorine is 850 grams. From finishing, reaction samples in gained reactant mixture, in gas phaseOn chromatograph, analyze this sample, wherein the purity of Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene is 95.52%.

Embodiment 16

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add Isosorbide-5-Nitrae-bis-(firstBase) 203.21 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 360nm, and illuminance is 49000Lux, starts to pass into chlorine anti-Should, control chlorine passes into speed and makes system temperature be no more than 120 DEG C, consumes amount of chlorine and is270 grams, reaction time consumption 4 hours 25 minutes; Adjusting intensity of illumination, to 70000Lux, raisesAfter system temperature to 140 DEG C, consume 650 grams, chlorine, reaction 31 hours consuming time altogether. ReactionAmounting to and consuming amount of chlorine is 920 grams. From finishing, reaction samples in gained reactant mixture,On gas chromatograph, analyze this sample, wherein the purity of Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene is96.64％。

Embodiment 17

Embodiment 12-16 gained reactant mixture is obtained to purifying after a rectifying purifyingIsosorbide-5-Nitrae-bis-(trichloromethyl) benzene. Again use gas chromatographic analysis, the Isosorbide-5-Nitrae-bis-(trichlorine of purifyingMethyl) benzene purity is respectively: 99.45%, 99.38%, 99.36%, 99.22%, 99.32%.

Embodiment 18

In the 500ml four-hole bottle with thermometric, condensing reflux and agitating device, add purityBe 400.32 grams of 99.45% Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene, system is heated up and makes Isosorbide-5-Nitrae-bis-(threeChloromethyl) benzene melts completely, adds pure according to 1.01 times of Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene mole numberDegree is 215.79 grams of 99.50% Isosorbide-5-Nitrae-bis-(formyl) benzene, then according to Isosorbide-5-Nitrae-bis-(trichloromethyl)0.25% of benzene weight adds 1.00 grams of ferric chloride catalysts, continue to be warming up to 125 DEG C after dimensionHolding reaction in 60 minutes finishes; Products therefrom is carried out to rectifying, obtain the Isosorbide-5-Nitrae-bis-(chlorine of purifyingFormoxyl) benzene. Isosorbide-5-Nitrae-bis-(chloroformyl) benzene of gas chromatographic analysis result demonstration purifyingPurity is 99.96%. (seeing chromatogram 4)

Embodiment 19

In the 500ml four-hole bottle with thermometric, condensing reflux and agitating device, add purityBe 402.36 grams of 99.22% Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene, system is heated up and makes Isosorbide-5-Nitrae-bis-(threeChloromethyl) benzene melts completely, adds pure according to 1.02 times of Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene mole numberDegree is 219.04 grams of 99.50% Isosorbide-5-Nitrae-bis-(formyl) benzene, then according to Isosorbide-5-Nitrae-bis-(trichloromethyl)0.30% of benzene weight adds 1.21 grams of ferric chloride catalysts, continue to be warming up to 120 DEG C after dimensionHolding reaction in 45 minutes finishes; Products therefrom is carried out to rectifying, obtain the Isosorbide-5-Nitrae-bis-(chlorine of purifyingFormoxyl) benzene. Isosorbide-5-Nitrae-bis-(chloroformyl) benzene of gas chromatographic analysis result demonstration purifyingPurity is 99.95%.

Embodiment 20

In the 500ml four-hole bottle with thermometric, condensing reflux and agitating device, add purityBe 405.12 grams of 99.32% Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene, system is heated up and makes Isosorbide-5-Nitrae-bis-(threeChloromethyl) benzene melts completely, adds pure according to 1.03 times of Isosorbide-5-Nitrae-bis-(trichloromethyl) benzene mole numberDegree is 222.70 grams of 99.50% Isosorbide-5-Nitrae-bis-(formyl) benzene, then according to Isosorbide-5-Nitrae-bis-(trichloromethyl)0.20% of benzene weight adds 0.81 gram of ferric chloride catalyst, continue to be warming up to 115 DEG C after dimensionHolding reaction in 30 minutes finishes; Products therefrom is carried out to rectifying, obtain the Isosorbide-5-Nitrae-bis-(chlorine of purifyingFormoxyl) benzene. Isosorbide-5-Nitrae-bis-(chloroformyl) benzene of gas chromatographic analysis result demonstration purifyingPurity is 99.96%.

Comparative example 1

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 201.00 grams of benzene, open LED light irradiation, incident light central peak wavelength is 465nm,Illuminance is 60000Lux, since 20 DEG C of intensifications, and progressively passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, reacts 20 hours, and consuming amount of chlorine is 1200 grams. From insteadShould finish to sample in rear gained reactant mixture, on gas chromatograph, analyze this sample, chromatogramOn figure, show key reaction product be 4-5 chlorine replacement mixture 1,3-bis-(methyl) benzene chlorineChange product. (seeing chromatogram 5)

Comparative example 2

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 200.30 grams of benzene, open LED light irradiation, incident light central peak wavelength is 460nm,Illuminance is 43000Lux, since 20 DEG C of intensifications, and progressively passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first stage of reaction reaction consumptionTime 5 hours 55 minutes. Adjusting intensity of illumination is to 63000Lux, rising system temperature to 142 DEG CAfter, consume 270 grams, chlorine. System temperature to 180 DEG C is improved on logical chlorine limit, limit, then regulates lightIllumination, to 91000Lux, maintains 180 DEG C and continues logical chlorine, and 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 900Gram. From reaction finishes, in gained reactant mixture, sample, on gas chromatograph, analyze this sampleProduct, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 88.93%. (seeing chromatogram 6)

Comparative example 3

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 201.46 grams of benzene, open LED light irradiation, incident light central peak wavelength is 505nm,Illuminance is 43000Lux, since 30 DEG C of intensifications, and progressively passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, first stage of reaction consuming time 5Hours 40 minutes. Adjusting intensity of illumination is to 61000Lux, after rising system temperature to 145 DEG C,Pass into chlorine a period of time, consume chlorine 270g; System temperature is improved extremely in logical chlorine limit, limit180 DEG C, then adjusting intensity of illumination is to 89000Lux, maintains 180 DEG C and continues logical chlorine, consumes chlorineTolerance is 300 grams, consuming time 11 hours 5 minutes altogether second and third stage. Reaction amounts to and consumesAmount of chlorine is 840 grams. From finishing, reaction samples in gained reactant mixture, in gas-chromatographyOn instrument, analyze this sample, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 89.44%.

Comparative example 4

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 200.90 grams of benzene, open LED light irradiation, incident light central peak wavelength is 465nm,Illuminance is 43000Lux, since 40 DEG C of intensifications, and progressively passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, first stage of reaction consuming time 5Hours 10 minutes. Adjusting intensity of illumination is to 63000Lux, after rising system temperature to 142 DEG C,Pass into chlorine a period of time, consume chlorine 270g. System temperature is improved extremely in logical chlorine limit, limit180 DEG C, then adjusting intensity of illumination is to 93000Lux, maintains 180 DEG C and continues logical chlorine, consumes chlorineTolerance is 320 grams. Second and third elementary reaction 10 hours consuming time altogether. Reaction amounts to and consumes chlorineTolerance is 860 grams. From finishing, reaction samples in gained reactant mixture, at gas chromatographThis sample of upper analysis, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 89.51%.

Comparative example 5

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 199.08 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, incidentLight center peak wavelength is 405nm, and illuminance is 10000Lux, progressively passes into chlorine reaction,Hierarchy of control temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, the first stage of reaction consumptionTime 4 hours 55 minutes. Adjusting intensity of illumination is to 56000Lux, rising system temperature to 133 DEG CAfter, pass into chlorine a period of time, consume chlorine 270g; System temperature is improved extremely in logical chlorine limit, limit180 DEG C, then adjusting intensity of illumination is to 97000Lux, maintains 180 DEG C and continues logical chlorine, consumes chlorineTolerance is 300 grams, consuming time 15 hours 20 minutes altogether second and third stage. Reaction amounts to and consumesAmount of chlorine is 840 grams. From finishing, reaction samples in gained reactant mixture, in gas-chromatographyOn instrument, analyze this sample, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 88.03%.

Comparative example 6

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 200.60 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, incidentLight center peak wavelength is 586nm, and illuminance is 5000Lux, passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, first stage of reaction consuming time 5Hours 5 minutes. Adjusting intensity of illumination is to 6.9Lux, after rising system temperature to 147 DEG C, passes intoChlorine a period of time, consume 270 grams, chlorine; System temperature to 180 DEG C is improved on logical chlorine limit, limit,Adjusting intensity of illumination, to 98000Lux, maintains 180 DEG C and continues logical chlorine again, consumes amount of chlorine and is300 grams, second and third stage is total to consuming time 18 hours 30 points. Reaction amounts to consumption amount of chlorine840 grams. From reaction finishes, in gained reactant mixture, sample, on gas chromatograph, analyzeThis sample, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 78.70%.

Comparative example 7

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 200.05 grams of benzene, stop heating up after being warming up to 60 DEG C, open LED light irradiation, incidentLight center peak wavelength is 465nm, and illuminance is 500Lux, passes into chlorine reaction, controlsSystem temperature is no more than 120 DEG C, and consuming amount of chlorine is 270 grams, first stage of reaction consuming time 5Hours 30 minutes; Adjusting intensity of illumination is to 69000Lux, after rising system temperature to 150 DEG C,Pass into chlorine a period of time, consume 270 grams, chlorine; System temperature is improved extremely in logical chlorine limit, limit180 DEG C, then adjusting intensity of illumination is to 9.8Lux, maintains 180 DEG C and continues logical chlorine, consumes chlorineAmount is 300 grams, consuming time 20 hours 25 minutes altogether second and third stage; Reaction amounts to and consumes chlorineTolerance is 940 grams. From finishing, reaction samples in gained reactant mixture, at gas chromatographThis sample of upper analysis, wherein 1, the purity of 3-bis-(trichloromethyl) benzene is 70.12%. (seeChromatogram 7)

Comparative example 8

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 200.00 grams of benzene, stop heating up after being warming up to 110 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 405nm, and illuminance is 60000Lux, passes into chlorine reaction,Reaction starts acutely to heat up after a period of time, temperature cannot be maintained below 120 DEG C to reactionThe very fast carbonization blackening of liquid, reacts unsuccessfully.

Comparative example 9

In the 500ml four-hole boiling flask that has thermometric and condensation reflux unit, add 1,3-, bis-(firstBase) 202.10 grams of benzene, stop heating up after being warming up to 120 DEG C, open LED light irradiation, enterPenetrating light center peak wavelength is 360nm, and illuminance is 43000Lux, passes into chlorine reaction,Reaction starts acutely to heat up after a period of time, temperature cannot be maintained below 120 DEG C to reactionThe very fast carbonization blackening of liquid, reacts unsuccessfully.

Claims (25)

1. a photochemical method of preparing two (trichloromethyl) benzene, is characterized in that two (firstBase) benzene and chlorine reacts preparation two (trichloromethyl) benzene, wherein said light under illumination conditionAccording to optical source wavelength be that 350nm-700nm, light wave width are maximum 50nm, wherein in reaction temperatureSpend under 55 DEG C-85 DEG C, illuminance 20000Lux-55000Lux and start to pass into chlorine, experience existsUnder described illuminance, reaction temperature is no more than first stage of reaction of 120 DEG C; Then higherUnder reaction temperature, continue to pass into surplus chlorine until reacted.

2. the method for claim 1, is characterized in that described first stage of reaction disappearsAt least 1/6 of the required chlorine total amount of consumption reaction.

3. the method for claim 1, is characterized in that described first stage of reaction disappearsThe 1/6-1/2 of the required chlorine total amount of consumption reaction.

4. method as claimed in claim 3, is characterized in that described first stage of reaction disappearsThe 1/4-1/3 of the required chlorine total amount of consumption reaction.

5. the method as described in claim 1-4 any one, is characterized in that described illuminanceFor 25000Lux-50000Lux.

6. method as claimed in claim 5, is characterized in that described illuminance is30000Lux-50000Lux。

7. method as claimed in claim 6, is characterized in that described illuminance is35000Lux-45000Lux。

8. the method as described in claim 1-4 any one, is characterized in that the first reaction rankAfter section, reaction is no more than 180 DEG C, illuminance in reaction temperature and is no more than 100000LuxUnder condition, pass into surplus chlorine.

9. method as claimed in claim 8, is characterized in that after first stage of reactionReaction is divided into second stage of reaction and the 3rd stage of reaction, wherein the second stage of reaction reaction temperatureBe no more than 160 DEG C, illuminance and be no more than 70000Lux; The 3rd stage of reaction reaction temperature is not superCross 180 DEG C, illuminance and be no more than 100000Lux.

10. method as claimed in claim 9, is characterized in that the second stage of reaction reaction temperatureDegree is not less than 120 DEG C, illuminance and is not less than 50000Lux.

11. methods as claimed in claim 9, is characterized in that the 3rd stage of reaction reaction temperatureDegree is not less than 160 DEG C, illuminance and is not less than 70000Lux.

12. methods as described in claim 9-11 any one, is characterized in that described secondThe chlorine consumption of the stage of reaction is the 1/4-2/5 of the required chlorine total amount of reaction.

13. methods as claimed in claim 12, is characterized in that each institute in three stagesThe amount of chlorine consuming is 1/3 of the required chlorine total amount of reaction.

14. methods as described in any one in claim 1-4, is characterized in that described light sourceFor LED lamp.

15. methods as claimed in claim 14, is characterized in that described LED lamp is wavelengthThe LED blue-ray light of 460nm-490nm.

16. methods as claimed in claim 14, is characterized in that the light wave width of described light sourceFor 10-30nm.

17. methods as claimed in claim 16, is characterized in that the light wave width of described light sourceFor 15-25nm.

18. as described in any one in claim 1-4 method, it is characterized in that the anti-of the methodAnswer in system not containing plus solvent and initator.

19. as described in any one in claim 1-4 method, it is characterized in that further comprisingThe purification step of rectifying or recrystallization after chlorination reaction finishes.

Prepare the method for two (chloroformyl) benzene, comprise following steps for 20. 1 kinds:

A) prepare two (trichloromethyl) benzene according to method described in any one in claim 1-19;

B) by a) middle two (trichloromethyl) benzene reaction preparation, two (chloroformyls) that obtain of stepBenzene.

21. methods as claimed in claim 20, is characterized in that two (trichlorines during step b)Methyl) benzene react with water or phthalic acid preparation two (chloroformyl) benzene.

22. methods as described in claim 20 or 21, is characterized in that step b) enters oneStep comprises following steps:

I) rising temperature melts two (trichloromethyl) benzene completely, then add water or phthalic acid,Catalyst, stirs;

Ii) heating reaction system maintains to react and carries out, thereby obtains product two (chloroformyl)Benzene; And

Iii) optional purification step.

23. methods as claimed in claim 22, is characterized in that: step I) in catalyst beLewis acid; Step I) in react with water in time reaction and contain a small amount of phthalic acid.

24. methods as claimed in claim 23, is characterized in that: step I) in catalyst beAlchlor, zinc chloride or ferric trichloride.

Prepare the method for two (chloroformyl) benzene for 25. 1 kinds, it comprises:

Preparing purity according to method described in claim 1-19 any one is more than 99.2% two(trichloromethyl) benzene, the technical grade that is 99.5% by described two (trichloromethyl) benzene and purityPhthalic acid reaction.