CN106588735A - Bis(t-butylperoxyisopropyl)benzene production method - Google Patents
Bis(t-butylperoxyisopropyl)benzene production method Download PDFInfo
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Abstract
The present invention provides a bis(t-butylperoxyisopropyl)benzene (abbreviated as BIPB) production method, wherein a condensation dehydration reaction is performed under a negative pressure condition by adopting di-(2-hydroxyisopropyl)benzene and a t-butyl hydrogen peroxide aqueous solution as raw materials, adopting a perchloric acid aqueous solution as a catalyst, and by adopting toluene as a solvent, such that the loss of t-butyl hydrogen peroxide is reduced, the side effect is less, the conversion rate of the raw materials is improved, the BIPB product having high yield and high purity is obtained, and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of production method of organic peroxide, and in particular to a kind of production method of double (t-butylperoxyisopropyl) benzene.
Background technology
1,3 (1,4)-bis- (tert-butylperoxyiso-propyl) benzene (abbreviation BIPB) are the upgrading products of cumyl peroxide (DCP), it is commonly called as " tasteless DCP ", it is dialkyl group organic peroxide cross-linking agent that consumption is only second to DCP, is to realize industrialized production abroad at the beginning of the sixties in last centuryIt is newPeroxide product.Contain two peroxide bridges in BIPB molecules, belong to double per-compound, molecular formula C20H34O4, molecular weight 338, its theoretical active oxygen content are 9.45%.Pure m-BIPB be white crystal, 50～52 DEG C of fusing point；Pure p-BIPB be white crystal, 77～79 DEG C of fusing point；The fusing point of m-BIPB and p-BIPB mixing is 45～55 DEG C.In decades, the BIPB products supplied on market have two kinds always：M-BIPB and p-BIPB mixing；Another kind of is pure m-BIPB, and the purposes and use condition of both products is identical.The free radical for producing is thermally decomposed by BIPB there is higher stability, BIPB can be used as the rubber such as polyethylene, ethylene propylene diene rubber, ethylene-vinyl acetate copolymer, silicone rubber, nitrile rubber and the cross-linking agent of plastics.In the case of equal cross-linking effect, addition is only the 2/3 of DCP.BIPB does not have the stink that DCP is crosslinked in cross-linking process or manufactured goods.BIPB cross-linking efficiencies are high, and the thermostability of product, cryogenic subduing flexibility and pressure morphotropism are all preferable.With the enhancing and the raising of quality of life of people's environmental consciousness, user can be more and more to the demand of BIPB.
1st, BIPB synthetic methods brief introduction
According to patent and document report, common BIPB synthetic methods have four kinds：One is in the presence of acidic, with two-(2- hydroxyisopropyls) benzene and the condensation dehydration of tert-butyl hydroperoxide, to obtain BIPB.Two is in the presence of acidic, to obtain BIPB by double bond additive reaction with two-(isopropenyl) benzene with tert-butyl hydroperoxide.Three is, in the presence of the acid acceptor such as the tertiary alcohol or alkene, to prepare BIPB by the de-hydrogen halide of tert-butyl hydroperoxide and α, α '-dihalo diisopropylbenzene (DIPB).Four is, in the presence of metal ion catalyst, directly to react to synthesize BIPB with tert-butyl hydroperoxide by diisopropylbenzene (DIPB).
Due to other several BIPB synthetic methods industrialized production relatively difficult to achieve, we select condensation reaction synthetic method as the production method of BIPB.The method is, with diisopropylbenzene (DIPB) as base stock, to obtain two-(2- hydroxyisopropyls) benzene (DC) by oxygen or air automatic oxidation reaction and reduction reaction.Then in the presence of acidic, allow DC that condensation reaction occurs with tert-butyl hydroperoxide (TBHP) and generate BIPB.Different according to used catalyst, condensation reaction synthetic method can be divided into perchloric acid catalysis method, hydrochloric acid (nitric acid) catalysis method, sulfuric acid catalysis method and anhydrous oxalic acid catalysis method again.
Organic peroxide is very unstable to temperature, acid, alkali, heavy metal ion etc., and due to the special nature of peroxide, the reaction for synthesizing peroxide is all more complicated.In the presence of acidic, it is by the condensation dehydration of DC and TBHP synthesizing BIPB, in addition to the primary response of list peroxide intermediate MP and final product BIPB is generated, also inevitable while there are other side reactions, its reaction mechanism is shown inFollowing formula instituteShow：
The condensation reaction of BIPB and main side reaction：
- 3 (4)-(2- hydroxyisopropyls) benzene abbreviation MP of wherein 1- (tert-butylperoxyiso-propyl)；- 3 (4)-isopropenylbenzene abbreviation OP of 1- (tert-butylperoxyiso-propyl).
ByAbove formula instituteShow as can be seen that the main side reaction of BIPB condensation reactions has：Single peroxide intermediate MP intramolecular dehydrations generate OP, DC acid-catalyzed dehydrations generate isopropenyl dimethy benzyl alcohol and di isopropenylbenzene, isopropenyl dimethy benzyl alcohol generates OP with TBHP reaction dehydrations, and the bond fission of BIPB, MP and OP acid catalysiss peroxide generates phenol derivativess and acetone.
2nd, prior art and shortcoming
In United States Patent (USP) US3787504 (1974), between disclosing, the sulfuric acid catalysis synthetic method of para-position-BIPB, stirring start with inert carbon dioxide atmosphere, using di-tert-butyl peroxide as solvent, 1 mole of DC is with 1.7 to 4 moles of di-tert-butyl peroxides, catalyst is made with a large amount of excessive 60%～65% sulphuric acid, sulphuric acid is 5～7 to 1 with the mol ratio of DC, with 2 mole of 75% tert-butyl hydroperoxide, about 1 hour is reacted in the case where 0～10 DEG C of ﹣, it is then quickly added into 800 grams of 85 DEG C～90 DEG C hot water, upper organic phase with 4% sodium hydroxide solution and after, wash again.The BIPB contents for obtaining are 35% di-tert-butyl peroxide solution, are removed using the method for anti-phase steam distillation, obtain the BIPB products that water content is 4.25% after being layered eliminating water at 55 DEG C, and the yield for being converted to anhydrous BIPB is 86.6%.Describe in patent Example, the concentration of sulphuric acid is less than 60% or all has considerable influence higher than 65% to the yield of reaction, and the consumption of sulphuric acid is reduced and increased and will affect synthetic reaction yield.In addition, mention in patent making solvent with benzene and normal hexane, the yield for synthesizing BIPB will be reduced to 70%～75%.
This synthetic method has the disadvantage that：
(1) sulphuric acid is significantly excessive, often synthesizes one ton of BIPB product, will produce 3 to 4 tons of pitch black red 50%～60% Waste Sulfuric Acids of concentration; wherein contain tert-butyl hydroperoxide, BIPB and various sour decomposition by-products; can neither recycle, be difficult again to process discharge, it is very unfavorable to environmental conservation；
(2) due to having used a large amount of acid catalysts, response speed too fast (about 1 hour), as tert-butyl hydroperoxide, DC and BIPB and reaction intermediate list peroxide are all to sour very unstable, the speed of side reaction can also be accelerated, can control in laboratory, in the industrial production, once there are the failures such as power failure or refrigeration system, agitator, it is likely that as the vigorous reaction of temperature control or oil-water interfaces occurs security incident；
(3) a large amount of heavy corrosions of the sulphuric acid to production equipment.During reaction end, rapidly join 85 DEG C to 90 DEG C of hot water, as a large amount of sulphuric acid present in reaction system are mixed with hot water, it is likely occurred exothermic reaction, the temperature of the di-tert-butyl peroxide solution of BIPB is caused to raise, so as to cause the acid catalyzed decomposition of BIPB, there is potential safety hazard, also have considerable influence to reaction yield, product purity；
(4) di-tert-butyl peroxide as solvent is a kind of organic peroxide in itself, unstable to strong acid and high temperature, and easily produces electrostatic, and the reaction dissolvent for using it as synthesizing BIPB has potential safety hazard.Therefore, the method that this large amount of sulfuric acid catalysis synthetic methods can only prepare a small amount of BIPB products as laboratory, is not suitable for commercial production.
The preparation method (CN101544587A) of the patent bis(t-butylperoxy)diisopropylbenzene of Hunan Yixiang Chemical Industrial Co., Ltd., disclose and catalyst is done using the phosphorus heteropoly tungstic acid containing water of crystallization, with hexamethylene, di-tert-butyl peroxide or dichloromethane as solvent, by 80%TBHP, (aqueous 20%) carries out reaction 15 to 25 hours with DC, it is 1/5～1 that the consumption of heteropoly acid is DC mass, reaction temperature is 0～50 DEG C, reaction yield 50%～66%, does not describe regeneration and recycling method and effect that phosphorus heteropoly tungstic acid makees catalyst in embodiment.
The BIPB preparation methoies are suffered from the drawback that：
(1) phosphorus heteropoly tungstic acid has very strong hygroscopicity, stores and using all inconvenient；
(2) phosphorus heteropoly tungstic acid is expensive, and consumption is very big, and cost of material is higher, used heteropolyacid catalyst, due to having adsorbed large quantity of moisture and peroxide, when thermal dehydration is activated, the easy decomposition explosion of peroxide of residual, reclaiming are difficult, are also just difficult to recycle；
(3) response time be 15 to 25 hours react, due to anti-overlong time, reaction efficiency is very low；
(4) use and the same amount of heteropolyacid catalyst of DC weight, react 16 hours at 45 DEG C, the BIPB yields for obtaining only have 50.8% (embodiment 2)；Reaction yield is low, illustrates that its reaction conversion ratio and selectivity be not high.
The preparation method of above-mentioned BIPB, as catalyst amount is big, response speed is excessively slow, and reaction yield is low, can only not apply to and industrialized production for preparing a small amount of product in laboratory.
In patent CN102796035, disclose an inter-species, the synthetic method of double (t-butylperoxyisopropyl) benzene of para-position mixing, with two (2- hydroxyl -2- propyl group) benzene and tert-butyl hydroperoxide as initiation material, with the perchloric acid that concentration is 50%～52% as catalyst, with 6#Solvent naphtha is solvent, and each material proportion is：Two (2- hydroxyl -2- propyl group) benzene：Tert-butyl hydroperoxide (mol ratio) 1:2.30～2.90；Two (2- hydroxyl -2- propyl group) benzene：6#Solvent naphtha (weight ratio)：100:250～410,39～56 DEG C of controlling reaction temperature, control 0～-0.056Mpa of reaction pressure, carry out " decompression, nitrogen bubble " dehydration backflow condensation reaction, when reaction is reached home, plus alkali terminating reaction, reactant liquor Jing alkali cleanings, condensation liquid is washed to obtain, condensation liquid concentration is obtained into double (t-butylperoxyisopropyl) benzene.With easy control of reaction system, condensation reaction time is short, side-product is few, high income the characteristics of.
The synthetic method has the disadvantage that：
(1) consumption of tert-butyl hydroperoxide is more, and production cost is higher；
(2) response time is long, and side reaction is more, and reaction yield and product purity be not high；
(3) as the mol ratio of (2- hydroxyl -2- propyl group) benzene two in 1～embodiment of embodiment 3 and tert-butyl hydroperoxide is about 1:1, understand according to following reaction scheme, reaction primary product is that -3 (4)-(2- hydroxyisopropyls) benzene of 1- (tert-butylperoxyiso-propyl) and a small amount of BIPB, BIPB yield can not possibly reach more than 95%.
The content of the invention
It is an object of the invention to overcome the defect of prior art, a kind of production method of double (t-butylperoxyisopropyl) benzene is provided, the production method is with two-(2- hydroxyisopropyls) benzene and tert-butyl hydroperoxide aqueous solution as raw material, high chloro acid solution is catalyst, toluene is solvent, condensation dehydration is carried out under condition of negative pressure, the loss, the condensation reaction speed that reduce tert-butyl hydroperoxide are fast, side reaction is few, improve feed stock conversion, obtained yield and BIPB products that purity is higher, reduce production cost.
The present invention is achieved by the following technical solutions：
A kind of production method of double (t-butylperoxyisopropyl) benzene, with two-(2- hydroxyisopropyls) benzene and tert-butyl hydroperoxide aqueous solution as raw material, high chloro acid solution is catalyst, and toluene is solvent, is comprised the steps：
(1) toluene is added in a kettle., stir and add the tert-butyl hydroperoxide aqueous solution, stratification eliminating water；
(2) two-(2- hydroxyisopropyls) benzene and the high chloro acid solution are added, nitrogen bubble, carry out condensation reaction, isolated toluene reactor is back to after vapor condensation in condensation reaction, as 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content≤1.5wt%, alkali liquor terminating reaction is added；
(3) add alkali liquor or/and water to be washed, obtain double (t-butylperoxyisopropyl) benzene condensation liquids；
(4) double (t-butylperoxyisopropyl) benzene condensation liquid Jing concentration, flaking and double (t-butylperoxyisopropyl) benzene of dry acquisition.
Two in aforementioned production method step (2)-(2- hydroxyisopropyls) benzene without drying be directly used in condensation reaction.
In aforementioned production method step (2) as single peroxide intermediate 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content≤1.5wt%, alkali liquor terminating reaction is added, is conducive to the raising of double (t-butylperoxyisopropyl) benzaldehyde product yields and content.
Reacted to synthesize a para-position mixing BIPB with mixing DC and excess TBHP, mix DC be between, the mixture of para-isomer, its interposition DC (m-DC)：The ratio of para-position DC (p-DC) is 2：1, the process of condensation reaction is tracked with gas chromatogram, per the composition of sample analysis condensation liquid every other hour.Can clearly be seen that from chromatographic determination result, between intermediate, the absworption peak of para-position mixing MP (- 3 (4)-(2- hydroxyisopropyls) benzene of 1- (tert-butylperoxyiso-propyl)), p-MP (1- (tert-butylperoxyiso-propyl) -4- (2- hydroxyisopropyls) benzene) content now is far longer than m-MP (1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene), illustrates that p-MP generating rates are more than m-MP.Continue observation discovery and p-BIPB, and the m-BIPB occurred after the absworption peak is far longer than occur, illustrate initial reaction stage, intermediate p-MP reactions generate p-BIPB speed and are far longer than the m-BIPB that m-MP reactions are generated.It is continuously increased as reaction carries out m-MP absworption peaks, p-MP absworption peaks reduce quickly and disappear, meanwhile, m-BIPB contents gradually increase, and are slowly increased along with the absworption peak for OP by-products occur, and absworption peak.
For the production of double (t-butylperoxyisopropyl) benzene, the concentration of tert-butyl hydroperoxide aqueous solution does not have special requirement, can be 65wt%～85wt%, such as 70wt%, 85wt%；The concentration of high chloro acid solution does not have special requirement yet, can be 50wt%～70wt%, such as 50wt%～52wt%, 70wt%.
Preferably, each material proportion is as follows：
Two-(2- hydroxyisopropyls) benzene is 1 with the mol ratio of tert-butyl hydroperoxide：2.20～2.40, more preferably 1：2.25-2.35；
Two-(2- hydroxyisopropyls) benzene is 100 with the weight ratio of perchloric acid：0.38～0.75, more preferably 100：0.40～0.60；
Two-(2- hydroxyisopropyls) benzene is 100 with the weight ratio of toluene：200～600, more preferably 100：250～400.
The weight ratio of above-mentioned two-(2- hydroxyisopropyls) benzene and perchloric acid refers to the weight ratio of the solute perchloric acid in two-(2- hydroxyisopropyls) benzene and high chloro acid solution, i.e., pure perchloric acid.
Preferably, aforementioned production method also meets following arbitrary one group of condition：
A) between described two-(2- hydroxyisopropyls) benzene are, para-isomer mixing, described double (t-butylperoxyisopropyl) benzene be between, para-isomer mixing, the meta-isomer of described two-(2- hydroxyisopropyls) benzene is 1.5～3.0 with the ratio of the para-isomer of two-(2- hydroxyisopropyls) benzene：1, more excellent ratio is 2.0：1；
B) described two-(2- hydroxyisopropyls) benzene are meta-isomer, and described double (t-butylperoxyisopropyl) benzene are meta-isomer.
Preferably, the temperature of step (1) is 20～30 DEG C.
Preferably, the setting-up point of step (2) is 38～48 DEG C, and relative pressure is -0.05～-0.08MPa.It is furthermore preferred that before alkali liquor terminating reaction is added by temperature control below 40 DEG C.
Addition alkali liquor terminating reaction in the step (2) is conventional method, such as embodiment, adds the sodium hydrate aqueous solution that mass concentration is 3%～8% to carry out terminating reaction.Addition alkali liquor or/and water in the step (3) carries out washing for conventional method, such as embodiment, and alkali liquid washing is：Washed with the sodium hydrate aqueous solution that mass concentration is 3%～8%, carried out alkali cleaning, stirred, stood, arranged alkali liquor, caustic times are for more than once or twice；Water washing is：Washed with water, be then shut off water intaking valve, stirred, stood, draining, washing times are for more than once or twice.
Preferably, the concentration in the step (4) is：Double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration device, concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique.
Preferably, the concentration in the step (4) point adds tap water for 2～3 times, and the addition of the whole process tap water of one-pot concentration is not more than concentration liquid total amount 13%.During BIPB condensation liquid concentration, the purpose for adding water for the first time is using the feasible constant boiling mixture into boiling point ratio original low 25 DEG C (85 DEG C of toluene and water azeotropic temperature) of solvent and water, overwhelming majority solvents to be steamed in decompression and less than 80 DEG C；The purpose for adding water for the second time is in order to using water and toluene and the feasible properties into low boiling constant boiling mixture of TBHP, the solvent and denier TBHP of residual are brought out, to eliminate the BIPB sharp aromas caused because of TBHP, inertia vapor improves can also the safety in distillation later stage.
Preferably, the production method of above-mentioned double (t-butylperoxyisopropyl) benzene, is additionally added solid sodium sulfate in the step (1), the tert-butyl hydroperoxide aqueous solution is 100 with the weight ratio of the solid sodium sulfate：2.0～6.0.A small amount of solid sodium sulfate is added during TBHP extraction dehydrations, the excess that can reduce TBHP in condensation charge ratio is found surprisingly that, is reduced production cost.TBHP containing about 12wt% in water phase obtained by toluene extraction TBHP aqueous solutions (65wt%～85wt%)；During toluene extraction TBHP aqueous solutions (content 65wt%～85wt%), the solid sodium sulfate of TBHP weight 2wt%～6wt%, the TBHP in the water phase isolated containing only 2wt%～3wt% are added.
Preferably, the production method of above-mentioned double (t-butylperoxyisopropyl) benzene, is additionally added the water with the weight such as high chloro acid solution in the step (2).By perchloric acid with etc. weight tap water dilution after add reactor, and by controlling perchloric acid catalysis agent consumption, it is possible to reduce condensation reaction side reaction, be conducive to the raising of double (t-butylperoxyisopropyl) benzaldehyde product yields and content.
Preferably, the production method of above-mentioned double (t-butylperoxyisopropyl) benzene, in the step (2) simultaneously as the total content≤2.2wt% of by-product 1- (tert-butylperoxyiso-propyl) -3- isopropenylbenzenes and 1- (tert-butylperoxyiso-propyl) -4- isopropenylbenzenes, reaction terminates.
Between the production method of double (t-butylperoxyisopropyl) benzene of the present invention is applied to, the production of double (t-butylperoxyisopropyl) benzene of para-position mixing or double (t-butylperoxyisopropyl) benzene of meta.Due to pair (t-butylperoxyisopropyl) benzaldehyde product contents height, color substantial white that production method of the present invention is obtained, recrystallization operation is eliminated, production procedure is shortened, production cost is greatly reduced.
The present invention one of at least has the advantages that：
1st, side reaction is reduced, and BIPB yields reach more than 90% and reach more than 96wt% with content；
2nd, reduce the unit consumption of tert-butyl hydroperoxide；
3rd, double (t-butylperoxyisopropyl) benzaldehyde product content/purities are high, color substantial white, can directly provide client, be not required to carry out recrystallization purification again, shorten production procedure, greatly reduce production cost.
4th, catalyst amount scope make that condensation reaction carries out more thoroughly, can avoid occurring because of the fortuitous event that DC causes condensation reaction to slow containing micro alkaline matter or midway stops；
5th, toluene is conducive to the carrying out of condensation reaction for solvent, and response speed is fast, and the response time is short, and dehydrating effect is good, and solvent loss is few, is conducive to the raising of double (t-butylperoxyisopropyl) benzaldehyde product yields and content；Toluene not only can be used as the solvent of DC recrystallization, and when toluene is used as condensation reaction solvent, recrystallization DC need to be only centrifuged, and without drying, can be directly used for condensation reaction, eliminate DC drying processes.
Specific embodiment
Embodiments of the present invention are illustrated below by way of specific instantiation, the content that those skilled in the art can be by disclosed by this specification understands other advantages and effect of the present invention easily.The present invention can also be carried out or be applied by specific embodiments different in addition, and without departing from the spirit of the present invention the every details in this specification can also carry out various modifications and changes based on different viewpoints and application.
It should be clear that the not concrete process equipment for indicating or device adopt conventional equipment in the art or device in the following example.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel and can also exist additive method step before and after the combination step or additive method step can also be inserted between the step of these specifically mention, unless otherwise stated；It will also be understood that, combination annexation between one or more the equipment/devices mentioned in the present invention, do not repel and can also there is other equipment/device before and after the unit equipment/device or other equipment/device can also be inserted between these two equipment/devices for specifically mentioning, unless otherwise stated.And, unless otherwise stated, the numbering of various method steps only differentiates the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting enforceable scope of the invention, its relativeness is altered or modified, in the case of without essence change technology contents, when being also considered as enforceable category of the invention.
Embodiment 1
(1) 1200 kilograms of toluene are put in condensation reaction kettle, starts stirring.624 kilograms of 70wt%TBHP aqueous solutions are put in condensation kettle, temperature are controlled for 25 DEG C, are stirred 20 minutes, quiescent settling 20 minutes, point sub-cloud water phase (about 160kg).
(2) in 20 DEG C or so of kettle temperature, 400 kilograms of essences DC (97.5%), 3.2 kilograms of 50wt% high chloro acid solutions and 3.2 kilograms originally aqueous mixtures are put into toward condensation reaction kettle, wherein DC be between, para-isomer mixing, the ratio of the para-isomer of the meta-isomer of two-(2- hydroxyisopropyls) benzene and two-(2- hydroxyisopropyls) benzene is 1.8:1, by the temperature control chuck hot water bath temperature for adjusting chuck hot water flow and high-temperature-hot-water groove, while opening valve before and after condensation kettle inner coil pipe cooling water inlet regulating valve, being smoothly warming up to 40 DEG C or so of kettle temperature.When temperature rises to about 40 DEG C, valve on the nitrogen displacement pipe of condensation kettle top is closed, start condensation vacuum pump, after system vacuum is stable, carry out nitrogen bubble, needle valve controls N after adjusting effusion meter2Flow.The backflow situation of solvent in condensation reaction is kept a close eye on, and by condensation vacuum buffer tank governor valve control condensation kettle reaction pressure being adjusted in -0.06～-0.08MPa, to control setting-up point at 38～48 DEG C or so, can produce normal reflux dewatering.In course of reaction, solvent is separated to oil water separator after condensing with the condensed device of water, and solvent constantly returns condensation kettle.Own " solvent refluxing " rises and is calculated as condensation reaction and starts, and after reaction 2 hours, sample analysis BIPB and single peroxide content were sampled every 0.5 to 1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, the time for reaching condensation reaction terminal is calculated according to sample analysis data, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content is 1.0wt%, reaction terminates, and makes condensation kettle pressure be normal pressure.It is after being cooled to 35～40 DEG C, slow to open alkali addition valve on condensation kettle, the sodium hydrate aqueous solution 100kg terminating reactions of 5wt%, condensation reaction time about 6.5 hours are added into kettle.
(3) the sodium hydrate aqueous solution 300Kg for adding 5wt% carries out alkali cleaning, after stirring 20 minutes, stops stirring, after standing 20 minutes, opens bottom to the valve between residual liquid groove, alkali liquor is put to residual liquid groove.400Kg5wt% sodium hydrate aqueous solutions are added, second alkali cleaning is carried out.It is that the temperature for making following water washing operations is not less than 25 DEG C during alkali cleaning, in alkaline cleaning procedure, answers suitable control temperature.Condensation kettle washing tap water water intaking valve is opened, by water intaking valve is closed after gauge table metering water quantity 600Kg, after stirring 20 minutes, is stopped stirring, after standing 20 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, obtain 1692Kg condensation liquids, condensation liquid is neutral in PH, near colorless.
(4) double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration devices, concentration condensation liquid Jing concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid gross weight 13%, divides 2～3 times in concentration process and adds tap water.Open concentration feed well bottom to discharge to the valve of concentration device, a certain amount of condensation liquid is put into into concentration device using liquid level difference, measuring tank is closed to the valve between concentration device.Operating procedure is pressed again, concentration feed well is fed by several times, in case concentration feed supplement is used.Concentration device jacket high temperature hot water entrance's valve is opened, is heated up at ambient pressure, and is opened concentration device top nitrogen bubble valve, carry out nitrogen bubble.65 DEG C or so are to slowly warm up to, concentration device top nitrogen bubbling valve are closed, is stopped nitrogen bubble.By the atmospheric valve control and regulation of surge tank, vacuum is stepped up, to prevent slug；The control of concentration liquidus temperature, can be adjusted by the temperature of regulation concentration device jacket high temperature hot water flow and high-temperature-hot-water groove, to control concentration device liquidus temperature at 75～90 DEG C.After concentration terminates, continue nitrogen bubble, be cooled to 60～70 DEG C.The extraction valve that concentration two is cooled to concentration vacuum buffer tank is closed, by the N for blasting2Let out to normal pressure and close nitrogen bubble valve；Stop concentration vacuum system by vacuum pump operating standard, the dense vacuum buffer tank atmospheric valve of dispersing and elevation lets out vacuum-pumping system to normal pressure.And contact with product handling system hilllock in time, concentration liquid (product in the middle of BIPB) is discharged to concentration liquid discharging kettle.Concentration liquid is evacuated to into concentration liquid discharging kettle, the BIPB of 612Kg is obtained Jing after flaking is dried, reaction yield is 90%, colours white, its BIPB content of Jing gas chromatographic analysiss is 97.3wt%, wherein being 62.6wt% containing m-BIPB, p-BIPB contents are 34.7wt%；M-MP contents are 1.0wt%；M-OP and p-OP are 1.7wt% altogether.
Embodiment 2
(1) 1000 kilograms of toluene are put in condensation reaction kettle, starts stirring.572 kilograms of 70wt%TBHP aqueous solutions are put in condensation kettle, 16Kg powdery sodium sulfate is added, and temperature are controlled for 25 DEG C, are stirred 20 minutes, quiescent settling 20 minutes, point sub-cloud water phase (about 154Kg).
(2) in 20 DEG C or so of kettle temperature, 400 kilograms of essences DC (98%), 3.5 kilograms of 50wt% high chloro acid solutions and 3.5 kilograms originally aqueous mixtures are put into toward condensation reaction kettle, wherein DC be between, para-isomer mixing, the ratio of the meta-isomer and para-isomer of two-(2- hydroxyisopropyls) benzene is 2:1, by the temperature control chuck hot water bath temperature for adjusting chuck hot water flow and high-temperature-hot-water groove, while opening valve before and after condensation kettle inner coil pipe cooling water inlet regulating valve, being smoothly warming up to 40 DEG C or so of kettle temperature.When temperature rises to about 40 DEG C, valve on the nitrogen displacement pipe of condensation kettle top is closed, start condensation vacuum pump, after system vacuum is stable, carry out nitrogen bubble, needle valve controls N after adjusting effusion meter2Flow.The backflow situation of solvent in condensation reaction is kept a close eye on, and by condensation vacuum buffer tank governor valve control condensation kettle reaction pressure being adjusted in -0.06～-0.08MPa, to control setting-up point at 38～48 DEG C or so, can produce normal reflux dewatering.In course of reaction, solvent is separated to oil water separator after condensing with the condensed device of water, and solvent constantly returns condensation kettle.Own " solvent refluxing " rises and is calculated as condensation reaction and starts, and after reaction 2 hours, sample analysis BIPB and single peroxide content were sampled every 0.5 to 1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, calculates the time for reaching condensation reaction terminal according to sample analysis data, and when meta list peroxide intermediate (m-MP) content is 1.5wt%, reaction terminates, and makes condensation kettle pressure be normal pressure.It is after being cooled to 35～40 DEG C, slow to open alkali addition valve on condensation kettle, the sodium hydrate aqueous solution 100Kg terminating reactions of 5wt% are added into kettle, condensation reaction time is 6.2 hours.
(3) the sodium hydrate aqueous solution 250Kg for adding 5wt% carries out alkali cleaning, after stirring 20 minutes, stops stirring, after standing 20 minutes, opens bottom to the valve between residual liquid groove, alkali liquor is put to residual liquid groove.350Kg5wt% sodium hydrate aqueous solutions are added, second alkali cleaning is carried out.It is that the temperature for making following water washing operations is not less than 25 DEG C during alkali cleaning, in alkaline cleaning procedure, answers suitable control temperature.Condensation kettle washing tap water water intaking valve is opened, by water intaking valve is closed after gauge table metering water quantity 520Kg, after stirring 20 minutes, is stopped stirring, after standing 20 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, and obtains 1515Kg condensation liquids, condensation liquid is neutral in PH, near colorless.
(4) condensation liquid concentration：Per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid gross weight 13%, divides 2～3 times in concentration process and add tap water.Open concentration feed well bottom to discharge to the valve of concentration device, a certain amount of condensation liquid is put into into concentration device using liquid level difference, measuring tank is closed to the valve between concentration device.Operating procedure is pressed again, concentration feed well is fed by several times, in case concentration feed supplement is used.Concentration device jacket high temperature hot water entrance's valve is opened, is heated up at ambient pressure, and is opened concentration device top nitrogen bubble valve, carry out nitrogen bubble.65 DEG C or so are to slowly warm up to, concentration device top nitrogen bubbling valve are closed, is stopped nitrogen bubble.By the atmospheric valve control and regulation of surge tank, vacuum is stepped up, to prevent slug；The control of concentration liquidus temperature, can be adjusted by the temperature of regulation concentration device jacket high temperature hot water flow and high-temperature-hot-water groove, to control concentration device liquidus temperature at 75～90 DEG C.After concentration terminates, continue nitrogen bubble, be cooled to 60～70 DEG C.The extraction valve that concentration two is cooled to concentration vacuum buffer tank is closed, by the N for blasting2Let out to normal pressure and close nitrogen bubble valve；Stop concentration vacuum system by vacuum pump operating standard, the dense vacuum buffer tank atmospheric valve of dispersing and elevation lets out vacuum-pumping system to normal pressure.And contact with product handling system hilllock in time, concentration liquid (product in the middle of BIPB) is discharged to concentration liquid discharging kettle.Concentration liquid is evacuated to into concentration liquid discharging kettle, the BIPB of 615Kg is obtained Jing after flaking is dried, reaction yield is 90%, colours white, its BIPB content of Jing gas chromatographic analysiss is 97wt%, wherein being 65wt% containing m-BIPB, p-BIPB contents are 32wt%；M-MP contents are 1.0wt%；M-OP and p-OP are 2.0wt% altogether.
Embodiment 3
(1) 1575Kg toluene is sucked in condensation reaction kettle, starts stirring.648Kg70wt%TBHP aqueous solutions are put in condensation kettle, 26Kg powdery sodium sulfate is added, and temperature are controlled for 22 DEG C, are stirred 25 minutes, quiescent settling 20 minutes, point sub-cloud water phase (about 178Kg).
(2) according to formula in 20 DEG C or so of kettle temperature, 450Kg essences DC (98wt%) is put into toward condensation reaction kettle, it is subsequently adding 4.5Kg50% high chloro acid solutions and 4.5Kg originally aqueous mixtures, wherein DC be between, para-isomer mixing, the ratio of the para-isomer of the meta-isomer of two-(2- hydroxyisopropyls) benzene and two-(2- hydroxyisopropyls) benzene is 1.75:1, condensation kettle chuck hot water entrance's valve is opened, by controlling chuck hot water bath temperature, kettle temperature～40 DEG C or so is smoothly warming up to.When temperature rises to about 40 DEG C, valve on the nitrogen displacement pipe of condensation kettle top is closed, start condensation vacuum pump, after system vacuum is stable, strict control N before bubbling2Surge tank P<After 0.12MPa, after adjusting effusion meter, needle valve controls N2Flow.The backflow situation of solvent in condensation reaction is kept a close eye on, and according to the backflow situation of solvent, control condensation kettle reaction pressure setting-up point is controlled at 38～48 DEG C or so, can produce normal reflux dewatering in -0.06～-0.08MPa.In course of reaction, solvent is separated to oil water separator after condensing with the condensed device of water, and solvent constantly returns condensation kettle.Own " solvent refluxing " rises and is calculated as condensation reaction and starts, and after reaction 2 hours, sample analysis BIPB and single peroxide content were sampled every 0.5 to 1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, the time for reaching condensation reaction terminal is calculated according to sample analysis data, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content content is 0.8wt%, reaction terminates, gradually reduce the vacuum of system, chuck hot water inlet valve is closed, by vacuum pump operating standard termination of pumping.By adjusting condensation kettle top nitrogen displacement tube valve open degree, condensation kettle pressure is made to be normal pressure.It is after being cooled to less than 40 DEG C, slow to open alkali addition valve on condensation kettle, 5% sodium hydrate aqueous solution 100Kg terminating reactions are added into kettle, condensation reaction time is 6 hours.
(3) after condensation reaction terminates, 35～40 DEG C are cooled to, add 5% sodium hydrate aqueous solution 310Kg to carry out alkali cleaning, after stirring 25 minutes, stop stirring, after standing 25 minutes, bottom is opened to the valve between residual liquid groove, alkali liquor is put to residual liquid groove.As above the sodium hydrate aqueous solution of 410Kg5% is added, second alkali cleaning is carried out.It is that the temperature for making following water washing operations is not less than 25 DEG C during alkali cleaning, in alkaline cleaning procedure, answers suitable control temperature.Condensation kettle washing tap water water intaking valve is opened, and by water intaking valve being closed after gauge table metering water 610Kg, after stirring 20～30 minutes, is stopped stirring, after standing 20～30 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, obtain 2117Kg condensation liquids, condensation liquid is neutral in PH, near colorless.
(4) double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration devices, concentration condensation liquid Jing concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid gross weight 10%, divides 2～3 times in concentration process and adds tap water.Open concentration feed well bottom to discharge to the valve of concentration device, a certain amount of condensation liquid is put into into concentration device using liquid level difference, measuring tank is closed to the valve between concentration device.Operating procedure is pressed again, concentration feed well is fed by several times, in case concentration feed supplement is used.Concentration device jacket high temperature hot water entrance's valve is opened, is heated up at ambient pressure, and is opened concentration device top nitrogen bubble valve, carry out nitrogen bubble.65 DEG C or so are to slowly warm up to, concentration device top nitrogen bubbling valve are closed, is stopped nitrogen bubble.By the atmospheric valve control and regulation of surge tank, vacuum is stepped up, to prevent slug；The control of concentration liquidus temperature, can be adjusted by the temperature of regulation concentration device jacket high temperature hot water flow and high-temperature-hot-water groove, to control concentration device liquidus temperature at 75～90 DEG C.After concentration terminates, continue nitrogen bubble, be cooled to 60～70 DEG C.The extraction valve that concentration two is cooled to concentration vacuum buffer tank is closed, by the N for blasting2Let out to normal pressure and close nitrogen bubble valve；Stop concentration vacuum system by vacuum pump operating standard, the dense vacuum buffer tank atmospheric valve of dispersing and elevation lets out vacuum-pumping system to normal pressure.Then 700KgBIPB products, colours white are obtained after carrying out flaking and drying, reaction yield is that its BIPB content of 91%, Jing gas chromatographic analysiss is 97.5wt%, wherein being 63.2wt% containing m-BIPB, p-BIPB is 34.3wt%；M-MP contents are 0.8wt%；M-OP and p-OP contents are 1.7wt%.
Embodiment 4
(1) 2115Kg toluene input is furnished with 5 cubes of condensation reaction kettles of oil water separator, starts stirring.700Kg70wt%TBHP is put in condensation kettle, 35Kg powdery sodium sulfate is added, and temperature is controlled for 22 DEG C, is stirred 25 minutes, quiescent settling 20 minutes, point sub-cloud water phase (about 190Kg).
(2) according to formula in 21 DEG C or so of kettle temperature, 470Kg essences DC (98.5wt%) is put into toward condensation reaction kettle, it is subsequently adding 6.6Kg50wt% perchloric acid and 6.6Kg originally aqueous mixtures, wherein DC be between, para-isomer mixing, the ratio of the para-isomer of the meta-isomer of two-(2- hydroxyisopropyls) benzene and two-(2- hydroxyisopropyls) benzene is 2.1:1, condensation kettle chuck hot water entrance's valve is opened, and by the temperature of chuck hot water flow and high-temperature-hot-water groove being adjusted to control chuck hot water bath temperature, is smoothly warming up to kettle temperature～40 DEG C or so.When temperature rises to about 40 DEG C, valve on the nitrogen displacement pipe of condensation kettle top is closed, start condensation vacuum pump, after system vacuum is stable, carry out nitrogen bubble, needle valve controls N after adjusting effusion meter2Flow.The backflow situation of solvent in condensation reaction is kept a close eye on, and according to the backflow situation of solvent, control condensation kettle reaction pressure setting-up point is controlled at 38～48 DEG C or so, can produce normal reflux dewatering in -0.06～-0.08MPa.In course of reaction, solvent is separated to oil water separator after condensing with the condensed device of water, and solvent constantly returns condensation kettle.Own " solvent refluxing " rises and is calculated as condensation reaction and starts, and after reaction 2 hours, sample analysis BIPB and single peroxide content were sampled every 0.5～1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, the time for reaching condensation reaction terminal is calculated according to sample analysis data, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content is 0.7wt%, reaction terminates, gradually reduce the vacuum of system, chuck hot water inlet valve is closed, by vacuum pump operating standard termination of pumping.By adjusting condensation kettle top nitrogen displacement tube valve open degree, condensation kettle pressure is made to be normal pressure.It is after being cooled to less than 40 DEG C, slow to open alkali addition valve on condensation kettle, the sodium hydrate aqueous solution 100Kg terminating reactions of 5wt%, condensation reaction time 5.8 hours are added into kettle.
(3) after condensation reaction terminates, continue through condensation kettle inner coil pipe cooling water inlet regulating valve and be cooled to 35～40 DEG C, the sodium hydrate aqueous solution 340Kg for adding 5% carries out alkali cleaning, after stirring 30 minutes, stop stirring, after standing 30 minutes, bottom is opened to the valve between residual liquid groove, peony water layer is put to residual liquid groove.The sodium hydrate aqueous solution of 440Kg5wt% is added, second alkali cleaning is carried out, is divided and is removed light red water layer.It is that the temperature for making following water washing operations is not less than 20 DEG C during alkali cleaning, in alkaline cleaning procedure, answers suitable control temperature.Condensation kettle washing tap water water intaking valve is opened, by water intaking valve is closed after gauge table metering water quantity 660Kg, after stirring 20 minutes, is stopped stirring, after standing 25 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, obtain 2645Kg condensation liquids, condensation liquid is neutral in PH, near colorless.
(4) double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration devices, concentration condensation liquid Jing concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid gross weight 10%, divides 2～3 times in concentration process and adds tap water.Open concentration feed well bottom to discharge to the valve of concentration device, a certain amount of condensation liquid is put into into concentration device using liquid level difference, measuring tank is closed to the valve between concentration device.Operating procedure is pressed again, concentration feed well is fed by several times, in case concentration feed supplement is used.Concentration device jacket high temperature hot water entrance's valve is opened, is heated up at ambient pressure, and is opened concentration device top nitrogen bubble valve, carry out nitrogen bubble.65 DEG C or so are to slowly warm up to, concentration device top nitrogen bubbling valve are closed, is stopped nitrogen bubble.By the atmospheric valve control and regulation of surge tank, vacuum is stepped up, to prevent slug；The control of concentration liquidus temperature, can be adjusted by the temperature of regulation concentration device jacket high temperature hot water flow and high-temperature-hot-water groove, to control concentration device liquidus temperature at 75～90 DEG C.After concentration terminates, continue nitrogen bubble, be cooled to 60～70 DEG C.The extraction valve that concentration two is cooled to concentration vacuum buffer tank is closed, by the N for blasting2Let out to normal pressure and close nitrogen bubble valve；Stop concentration vacuum system by vacuum pump operating standard, the dense vacuum buffer tank atmospheric valve of dispersing and elevation lets out vacuum-pumping system to normal pressure.Then 742Kg BIPB products, colours white are obtained after carrying out flaking and drying, reaction yield is that its BIPB content of 92%, Jing gas chromatographic analysiss is 98.0wt%, wherein being 65.0wt% containing m-BIPB, it is 33.0wt% that p-BIPB contains；M-MP contents are 0.7wt%；M-OP and p-OP contents are 1.3wt%.
Embodiment 5
(1) 900Kg toluene is sucked in condensation reaction kettle, starts stirring.648Kg70wt%TBHP aqueous solutions are put in condensation kettle, 13Kg powdery sodium sulfate is added, and temperature are controlled for 22 DEG C, are stirred 25 minutes, quiescent settling 20 minutes, point sub-cloud water phase (about 165Kg).
(2) according to formula in 20 DEG C or so of kettle temperature, 450Kg essences DC (98wt%) is put into toward condensation reaction kettle, it is subsequently adding 3.4Kg50wt% high chloro acid solutions and 3.4Kg originally aqueous mixtures, wherein DC be between, para-isomer mixing, the ratio of the para-isomer of the meta-isomer of two-(2- hydroxyisopropyls) benzene and two-(2- hydroxyisopropyls) benzene is 2:1, condensation kettle chuck hot water entrance's valve is opened, by controlling chuck hot water bath temperature, about 40 DEG C or so of kettle temperature is smoothly warming up to.When temperature rises to about 40 DEG C, valve on the nitrogen displacement pipe of condensation kettle top is closed, start condensation vacuum pump, after system vacuum is stable, strict control N before bubbling2Surge tank P<After 0.12MPa, after adjusting effusion meter, needle valve controls N2Flow.The backflow situation of solvent in condensation reaction is kept a close eye on, and according to the backflow situation of solvent, control condensation kettle reaction pressure setting-up point is controlled at 38～48 DEG C or so, can produce normal reflux dewatering in -0.06～-0.08MPa.In course of reaction, solvent is separated to oil water separator after condensing with the condensed device of water, and solvent constantly returns condensation kettle.Own " solvent refluxing " rises and is calculated as condensation reaction and starts, and after reaction 2 hours, sample analysis BIPB and single peroxide content were sampled every 0.5 to 1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, the time for reaching condensation reaction terminal is calculated according to sample analysis data, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content is 1.0wt%, reaction terminates, gradually reduce the vacuum of system, chuck hot water inlet valve is closed, by vacuum pump operating standard termination of pumping.By adjusting condensation kettle top nitrogen displacement tube valve open degree, condensation kettle pressure is made to be normal pressure.It is after being cooled to less than 40 DEG C, slow to open alkali addition valve on condensation kettle, the sodium hydrate aqueous solution 100Kg terminating reactions of 5wt% are added into kettle, condensation reaction time is 6.5 hours.
(3) after condensation reaction terminates, 35～40 DEG C are cooled to, add the sodium hydrate aqueous solution 310Kg of 5wt% to carry out alkali cleaning, after stirring 25 minutes, stop stirring, after standing 25 minutes, bottom is opened to the valve between residual liquid groove, alkali liquor is put to residual liquid groove.As above the sodium hydrate aqueous solution of 410Kg5wt% is added, second alkali cleaning is carried out.It is that the temperature for making following water washing operations is not less than 25 DEG C during alkali cleaning, in alkaline cleaning procedure, answers suitable control temperature.Condensation kettle washing tap water water intaking valve is opened, by water intaking valve is closed after gauge table metering water quantity 610Kg, after stirring 20～30 minutes, is stopped stirring, after standing 20～30 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, obtain 1500Kg condensation liquids, condensation liquid is neutral in PH, near colorless.
(4) double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration devices, concentration condensation liquid Jing concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid gross weight 10wt%, divides 2～3 times in concentration process and adds tap water.Open concentration feed well bottom to discharge to the valve of concentration device, a certain amount of condensation liquid is put into into concentration device using liquid level difference, measuring tank is closed to the valve between concentration device.Operating procedure is pressed again, concentration feed well is fed by several times, in case concentration feed supplement is used.Concentration device jacket high temperature hot water entrance's valve is opened, is heated up at ambient pressure, and is opened concentration device top nitrogen bubble valve, carry out nitrogen bubble.65 DEG C or so are to slowly warm up to, concentration device top nitrogen bubbling valve are closed, is stopped nitrogen bubble.By the atmospheric valve control and regulation of surge tank, vacuum is stepped up, to prevent slug；The control of concentration liquidus temperature, can be adjusted by the temperature of regulation concentration device jacket high temperature hot water flow and high-temperature-hot-water groove, to control concentration device liquidus temperature at 75～90 DEG C.After concentration terminates, continue nitrogen bubble, be cooled to 60～70 DEG C.The extraction valve that concentration two is cooled to concentration vacuum buffer tank is closed, by the N for blasting2Let out to normal pressure and close nitrogen bubble valve；Stop concentration vacuum system by vacuum pump operating standard, the dense vacuum buffer tank atmospheric valve of dispersing and elevation lets out vacuum-pumping system to normal pressure.Then 691KgBIPB products, colours white are obtained after carrying out flaking and drying, reaction yield is that its BIPB content of 90%, Jing gas chromatographic analysiss is 97.3wt%, wherein being 63.1wt% containing m-BIPB, p-BIPB is 34.2wt%；M-MP contents are 1.0wt%；M-OP and p-OP contents are 1.7wt%.
Embodiment 6
(1) 2352 kilograms of toluene are put in condensation reaction kettle, starts stirring.574 kilograms of 70wt%TBHP aqueous solutions are put in condensation kettle, 34Kg powdery sodium sulfate is added, and temperature are controlled for 25 DEG C, are stirred 20 minutes, quiescent settling 20 minutes, point sub-cloud water phase (about 190Kg).
(2) according to formula in 20 DEG C or so of kettle temperature, 400 kilograms of essences DC (98wt%) are put into toward condensation reaction kettle, 6 kilograms of 50wt% high chloro acid solutions is subsequently adding and 6 kilograms of originally aqueous mixtures, wherein DC be between, para-isomer mixing, the ratio of the para-isomer of the meta-isomer of two-(2- hydroxyisopropyls) benzene and two-(2- hydroxyisopropyls) benzene is 2:1, by the temperature control chuck hot water bath temperature for adjusting chuck hot water flow and high-temperature-hot-water groove, while opening valve before and after condensation kettle inner coil pipe cooling water inlet regulating valve, being smoothly warming up to 40 DEG C or so of kettle temperature.When temperature rises to about 40 DEG C, valve on the nitrogen displacement pipe of condensation kettle top is closed, start condensation vacuum pump, after system vacuum is stable, carry out nitrogen bubble, needle valve controls N after adjusting effusion meter2Flow.The backflow situation of solvent in condensation reaction is kept a close eye on, and by condensation vacuum buffer tank governor valve control condensation kettle reaction pressure being adjusted in -0.06～-0.08MPa, to control setting-up point at 38～48 DEG C or so, can produce normal reflux dewatering.In course of reaction, solvent is separated to oil water separator after condensing with the condensed device of water, and solvent constantly returns condensation kettle.Own " solvent refluxing " rises and is calculated as condensation reaction and starts, and after reaction 2 hours, sample analysis BIPB and single peroxide content were sampled every 0.5 to 1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, the time for reaching condensation reaction terminal is calculated according to sample analysis data, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content is 0.6wt%, reaction terminates, and makes condensation kettle pressure be normal pressure.It is after being cooled to 35～40 DEG C, slow to open alkali addition valve on condensation kettle, the sodium hydrate aqueous solution 100Kg terminating reactions of 5wt% are added into kettle, condensation reaction time is 5.0 hours.
(3) the sodium hydrate aqueous solution 260Kg for adding 5wt% carries out alkali cleaning, after stirring 20 minutes, stops stirring, after standing 20 minutes, opens bottom to the valve between residual liquid groove, alkali liquor is put to residual liquid groove.360Kg5wt% sodium hydrate aqueous solutions are added, second alkali cleaning is carried out.It is that the temperature for making following water washing operations is not less than 25 DEG C during alkali cleaning, in alkaline cleaning procedure, answers suitable control temperature.Condensation kettle washing tap water water intaking valve is opened, by water intaking valve is closed after gauge table metering water quantity 540Kg, after stirring 20 minutes, is stopped stirring, after standing 20 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, obtain 2790Kg condensation liquids, condensation liquid is neutral in PH, near colorless.
(4) double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration devices, concentration condensation liquid Jing concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid gross weight 10wt%, divides 2～3 times in concentration process and adds tap water.Open concentration feed well bottom to discharge to the valve of concentration device, a certain amount of condensation liquid is put into into concentration device using liquid level difference, measuring tank is closed to the valve between concentration device.Operating procedure is pressed again, concentration feed well is fed by several times, in case concentration feed supplement is used.Concentration device jacket high temperature hot water entrance's valve is opened, is heated up at ambient pressure, and is opened concentration device top nitrogen bubble valve, carry out nitrogen bubble.65 DEG C or so are to slowly warm up to, concentration device top nitrogen bubbling valve are closed, is stopped nitrogen bubble.By the atmospheric valve control and regulation of surge tank, vacuum is stepped up, to prevent slug；The control of concentration liquidus temperature, can be adjusted by the temperature of regulation concentration device jacket high temperature hot water flow and high-temperature-hot-water groove, to control concentration device liquidus temperature at 75～90 DEG C.After concentration terminates, continue nitrogen bubble, be cooled to 60～70 DEG C.The extraction valve that concentration two is cooled to concentration vacuum buffer tank is closed, by the N for blasting2Let out to normal pressure and close nitrogen bubble valve；Stop concentration vacuum system by vacuum pump operating standard, the dense vacuum buffer tank atmospheric valve of dispersing and elevation lets out vacuum-pumping system to normal pressure.Then the BIPB of 635Kg, colours white are obtained after carrying out flaking and drying, reaction yield is that its BIPB content of 93%, Jing gas chromatographic analysiss is 98wt%, wherein being 64wt% containing m-BIPB, p-BIPB contents are 34wt%；M-MP contents are 0.6wt%；M-OP and p-OP are 1.4wt% altogether.
Embodiment 7
(1) in 20 liters of stainless steel cauldrons for being furnished with oil water separator and thermometer, the toluene solvant and 2060 grams of 70wt%TBHP aqueous solutions of 5460 grams of addition, add 82 grams of solid sodium sulfate powder, it is stirred at room temperature 15 minutes, stop stirring and stand 10 to 15 minutes, slowly branch vibration layer, water mutually weigh about 638 grams.
(2) stirring is started lower in reactor plus 1350 grams of pure metas essence DC (98wt%), 10 grams of 50wt% high chloro acid solutions are added with 10 grams of originally aqueous mixtures, with heating in water bath for reaction mixture to 38 DEG C, start water circulation vacuum pump, air or nitrogen bubble are carried out by being inserted into the capillary tube of bottom of bottle, it is that -0.06MPa arrives -0.08MPa to adjust vacuum, with heating in water bath to solvent refluxing, the temperature of heated water bath is 45 to 55 DEG C, and the temperature of reactant liquor is 40 DEG C to 48 DEG C.During back flow reaction, sampling is constituted with liquid-phase chromatographic analysis reactant liquor, reaction process is tracked by the content of monitoring intermediate list peroxide MP, condensation reaction takes No. 1 sample for two hours after starting, and takes within 3 hours No. 2 samples, takes within 4 hours No. 3 samples, the time for reaching condensation reaction terminal is calculated according to sample analysis data, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyisopropyls) benzene content is 0.85wt%, reaction terminates, and makes condensation kettle pressure be normal pressure.After being cooled to 35～40 DEG C, slowly 400 grams of 5wt% sodium hydrate aqueous solution terminating reactions are added into kettle, condensation reaction time is 6.5 hours.
(3) in the case where stirring is started, add 900 gram 5% of sodium hydroxide solution in the condensation liquid after cooling, stir 15 minutes, 10 to 15 minutes are stood, is divided and is removed peony water layer, add 1300 gram 5% of sodium hydroxide solution, stirring 15 minutes, stands 10 to 15 minutes, divides and removes light red water layer.In the case where stirring is started, in the condensation liquid after alkali cleaning add 1950 grams of water to be washed, stir 10 minutes, stand 10 minutes, again with 1950 grams of water washings once, the water layer for going to PH=6.5～7.5, washing is divided to terminate, 6192 grams of condensation liquids are obtained, condensation liquid is neutral in PH, near colorless.
(4) double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration devices, concentration condensation liquid Jing concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, per kettle before time concentration, appropriate tap water is sucked in concentration device first with the vacuum of upgrading system, first add 350 grams of tap waters in 20 liters of stainless steel cauldrons, the purpose for adding water is using the feasible constant boiling mixture into boiling point than low 25 DEG C originally of toluene and water, most solvents to be steamed below 80 DEG C, during decompression concentration, (every time 100 grams) add 300 grams of water in three times, later stage adds water can take the toluene of residual and micro TBHP azeotropic out of, inertia vapor strengthens can also the safety in distillation later stage.Heated water bath temperature is 65 DEG C to 90 DEG C, and vacuum is that -0.03MPa arrives -0.095Mpa, and concentration will be started in stirring to be carried out under lower or nitrogen bubble.Jing concentration, cooling and solidifying, after crushing and being dried, 2097 grams of pure meta BIPB products are obtained, reaction yield is 91%, colours white, and its BIPB content of Jing gas chromatographic analysiss is 97wt%, wherein being 96wt% containing m-BIPB, p-BIPB contents are 1.0wt%；M-MP contents are 0.85wt%；M-OP is 2.15wt%.
Comparative example 1
(1) 1200 kilograms of C6 solvent naphthas are put in condensation reaction kettle, starts stirring.636 kilograms of 70wt%TBHP aqueous solutions are put in condensation kettle, temperature are controlled for 23 DEG C, are stirred 25 minutes, quiescent settling 30 minutes, point sub-cloud water phase.
(2) in 20 DEG C or so of kettle temperature, 400 kilograms of essences DC (98wt%), 2.4 kilograms of 50wt% perchloric acid are put into toward condensation reaction kettle, two in wherein DC-ratio of the para-isomer of the meta-isomer and two-(2- hydroxyisopropyls) benzene of (2- hydroxyisopropyls) benzene is 2:1, the chuck hot water provided by high-temperature-hot-water groove Jing heat-exchanger pumps is heated up, and is opened condensation kettle chuck hot water and is heated up, and control kettle temperature is at 42 DEG C or so；Condensation vacuum pump evacuation is opened, reaction pressure is controlled in -0.052MPa, bottom nitrogen bubble is carried out from device nitrogen buffer tank, carry out " decompression, nitrogen bubble " reflux dewatering reaction；Jing after condensation condenser condensation, lime set enters oil water separator separation to condensation reaction gas phase, and 6 solvent naphtha of solvent C enters oil water separator separation from top overflow, and 6 solvent naphtha of solvent C flows back into condensation kettle；After reaction 3 hours, sample analysis BIPB and single peroxide content were sampled every 0.5 to 1 hour later, and the reaction later stage determines sampling interval time according to real reaction situation.Detection intermediate list peroxide content, calculates the time for reaching condensation reaction terminal according to sample analysis data, and when single peroxide intermediate (MP, meta and para-position) content is 2.3wt%, reaction terminates, and makes condensation kettle pressure be normal pressure.It is after being cooled to 35～40 DEG C, slow to open alkali addition valve on condensation kettle, the sodium hydrate aqueous solution 100Kg terminating reactions of 5wt% are added into kettle, condensation reaction time is 8 hours.
(3) the sodium hydrate aqueous solution 150Kg for adding 5wt% carries out alkali cleaning, after stirring 23 minutes, stops stirring, after standing 20 minutes, opens bottom to the valve between residual liquid groove, alkali liquor is put to residual liquid groove；Condensation kettle washing tap water water intaking valve is opened, by water intaking valve is closed after gauge table metering water quantity 400Kg, after stirring 20 minutes, is stopped stirring, after standing 20 minutes, is opened the valve of bottom to residual liquid groove, washess are put to residual liquid groove.Second washing is carried out by this, until washing water layer PH=6.5～7.5, washing terminates, obtain 1600Kg condensation liquids, condensation liquid PH is neutrality, near colorless.
(4) 1600Kg condensation liquid nitrogen is depressed in concentration device, the hot water provided by high-temperature-hot-water groove Jing heat-exchanger pumps enters chuck heating, concentration is carried out using azeotrope with water decompression desolventizing and decompression nitrogen bubble technique, concentration device liquidus temperature is at 50～80 DEG C, pressure -0.095MPa～normal pressure, during concentration, adds tap water in three times, the addition of the whole process tap water of one-pot concentration is not more than concentration liquid total amount 10%, and concentration liquid is discharged to concentration liquid discharging kettle.Concentration liquid is evacuated to into concentration liquid discharging kettle, the BIPB of 581Kg is obtained Jing after flaking is dried, reaction yield is 85%, and color is faint yellow, its BIPB content of Jing gas chromatographic analysiss is 95wt%, wherein being 63wt% containing m-BIPB, p-BIPB contents are 32wt%；M-MP contents are 2.3wt%；M-OP and p-OP are 2.7wt% altogether.
The above; only presently preferred embodiments of the present invention; not any formal and substantial to present invention restriction; it should be understood that; for those skilled in the art; on the premise of without departing from the inventive method, some improvement and supplement can be also made, these improve and supplement also should be regarded as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, when a little change, modification made using disclosed above technology contents and the equivalent variations for developing, are the Equivalent embodiments of the present invention；Meanwhile, change, modification and the differentiation of any equivalent variations that all substantial technologicals according to the present invention are made to above-described embodiment are still fallen within the range of technical scheme.
Claims (10)
1. the production method of a kind of double (t-butylperoxyisopropyl) benzene, with two-(2- hydroxyisopropyls) benzene and t-butyl peroxy
Change aqueous solution of hydrogen is raw material, and high chloro acid solution is catalyst, and toluene is solvent, is comprised the steps：
(1) toluene is added in a kettle., stir and add the tert-butyl hydroperoxide aqueous solution, stratification eliminating water；
(2) two-(2- hydroxyisopropyls) benzene and the high chloro acid solution, nitrogen bubble are added, carry out condensation reaction,
Isolated toluene reactor is back to after vapor condensation in condensation reaction, when 1- (tert-butylperoxyiso-propyl) -3- (2- hydroxyls
Base isopropyl) benzene content≤1.5wt% when, add alkali liquor terminating reaction；
(3) add alkali liquor or/and water to be washed, obtain double (t-butylperoxyisopropyl) benzene condensation liquids；
(4) double (t-butylperoxyisopropyl) benzene condensation liquid Jing concentration, flaking and the double (t-butyl peroxies of dry acquisition
Change isopropyl) benzene.
2. the production method of double (t-butylperoxyisopropyl) benzene according to claim 1, it is characterised in that each material is matched somebody with somebody
Than as follows：
Two-(2- hydroxyisopropyls) benzene is 1 with the mol ratio of tert-butyl hydroperoxide：2.20～2.40；
Two-(2- hydroxyisopropyls) benzene is 100 with the weight ratio of perchloric acid：0.38～0.75；
Two-(2- hydroxyisopropyls) benzene is 100 with the weight ratio of toluene：200～600.
3. the production method of double (t-butylperoxyisopropyl) benzene according to claim 1, it is characterised in that the production
Method also meets following arbitrary one group of condition：
A) between described two-(2- hydroxyisopropyls) benzene are, para-isomer mixing, described double (t-butylperoxyisopropyl) benzene
For, para-isomer mixing, the meta-isomer and two-(2- hydroxyisopropyls) of described two-(2- hydroxyisopropyls) benzene
The ratio of the para-isomer of benzene is 1.5～3.0：1；
B) described two-(2- hydroxyisopropyls) benzene are meta-isomer, and described double (t-butylperoxyisopropyl) benzene are that meta is different
Structure body.
4. the production method of double (t-butylperoxyisopropyl) benzene according to claim 1, it is characterised in that the step
(1) temperature is 20～30 DEG C.
5. the production method of double (t-butylperoxyisopropyl) benzene according to claim 1, it is characterised in that the step
(2) setting-up point is 38～48 DEG C, and relative pressure is -0.05～-0.08MPa.
6. the production method of double (t-butylperoxyisopropyl) benzene according to claim 1, it is characterised in that the step
(4) concentration in is：Double (t-butylperoxyisopropyl) benzene condensation liquids are added in concentration device, using azeotrope with water
Decompression desolventizing and decompression nitrogen bubble technique carry out concentration.
7. the production method of double (t-butylperoxyisopropyl) benzene according to claim 1, it is characterised in that the step
(4) concentration in point adds tap water 2～3 times, and the addition of the whole process tap water of one-pot concentration is not more than concentration liquid
Gross weight 13%.
8. the production method according to arbitrary described double (t-butylperoxyisopropyl) benzene of claim 1 to 7, it is characterised in that
It is additionally added solid sodium sulfate in the step (1), the weight ratio of the tert-butyl hydroperoxide aqueous solution and the solid sodium sulfate
For 100：2.0～6.0.
9. the production method according to arbitrary described double (t-butylperoxyisopropyl) benzene of claim 1 to 7, it is characterised in that
The water with the weight such as high chloro acid solution is additionally added in the step (2).
10. the production method according to arbitrary described double (t-butylperoxyisopropyl) benzene of claim 1 to 7, it is characterised in that
In the step (2), while working as by-product 1- (tert-butylperoxyiso-propyl) -3- isopropenylbenzenes and 1- (t-butyl peroxies
Isopropyl) -4- isopropenylbenzenes total content≤2.2wt% when, reaction terminates.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111100054A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | α' -dihydroxy-diisopropylbenzene, bis- (tert-butylperoxyisopropyl) benzene and epoxy compound synthesis method |
| CN113999151A (en) * | 2021-12-01 | 2022-02-01 | 广西东岚新材料有限公司 | Condensation reaction method for synthesizing meta-position and para-position 2- (tert-butyl peroxyisopropyl) benzene |
| CN114195692A (en) * | 2020-09-17 | 2022-03-18 | 中国石油化工股份有限公司 | 3- (2-hydroxy-2-propyl) cumene hydroperoxide and preparation method thereof |
| CN114920681A (en) * | 2022-05-27 | 2022-08-19 | 山东阳谷华泰化工股份有限公司 | Synthesis method of di (tert-butyl peroxy isopropyl) benzene |
| CN115583905A (en) * | 2022-11-04 | 2023-01-10 | 湖南方锐达科技有限公司 | Preparation method of m-di-tert-butylperoxydiisopropylbenzene |
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| CN103058908A (en) * | 2012-12-25 | 2013-04-24 | 宁波东来化工有限公司 | One-step synthetic method for bis(t-butylperoxyisopropyl)benzene |
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| CN102796035A (en) * | 2012-09-07 | 2012-11-28 | 金魏 | Condensation method of m-,p-mixed di-(tert-butyl isopropyl peroxide)benzene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111100054A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | α' -dihydroxy-diisopropylbenzene, bis- (tert-butylperoxyisopropyl) benzene and epoxy compound synthesis method |
| CN114195692A (en) * | 2020-09-17 | 2022-03-18 | 中国石油化工股份有限公司 | 3- (2-hydroxy-2-propyl) cumene hydroperoxide and preparation method thereof |
| CN114195692B (en) * | 2020-09-17 | 2024-01-30 | 中国石油化工股份有限公司 | 3- (2-hydroxy-2-propyl) cumene hydroperoxide and preparation method thereof |
| CN113999151A (en) * | 2021-12-01 | 2022-02-01 | 广西东岚新材料有限公司 | Condensation reaction method for synthesizing meta-position and para-position 2- (tert-butyl peroxyisopropyl) benzene |
| CN114920681A (en) * | 2022-05-27 | 2022-08-19 | 山东阳谷华泰化工股份有限公司 | Synthesis method of di (tert-butyl peroxy isopropyl) benzene |
| CN115583905A (en) * | 2022-11-04 | 2023-01-10 | 湖南方锐达科技有限公司 | Preparation method of m-di-tert-butylperoxydiisopropylbenzene |
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