CN107698479A - A kind of continuous stream synthesis technique of the ethylhexyl carbonate tert-butyl ester of peroxidating 2 of no enlarge-effect - Google Patents
A kind of continuous stream synthesis technique of the ethylhexyl carbonate tert-butyl ester of peroxidating 2 of no enlarge-effect Download PDFInfo
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Abstract
The present invention provides a kind of continuous stream synthesis technique of the ethylhexyl carbonate tert-butyl ester of peroxidating 2 of no enlarge-effect, described synthesis technique is with tertbutanol peroxide, alkali lye, the ethylhexyl of chloro-carbonic acid 2 is raw material, continuously successively through quaternization, esterification and cancellation step obtain the ethylhexyl carbonate tert-butyl ester of peroxidating 2, described synthesis technique is carried out in integrated continuous flow reactor, reaction raw materials tertbutanol peroxide is uninterruptedly added in the charging aperture of the integrated continuous flow reactor, alkali lye, the ethylhexyl of chloro-carbonic acid 2, the ethylhexyl carbonate tert-butyl ester of peroxidating 2 is uninterruptedly obtained in the integrated continuous flow reactor discharging opening, without enlarge-effect, reaction is no more than 180s at total time.Compared with traditional production technology, temperature is substantially improved, and reaction greatly shortens total time, no enlarge-effect, and product index is stable, favorable reproducibility.
Description
Technical field
The present invention relates to chemical field, and in particular to a kind of continuous stream of peroxidating -2- ethylhexyl carbonate tert-butyl esters is closed
Into technique.
Background technology
Peroxy esters are important organic peroxides, such as the peroxidating -2- ethylhexyl carbonate tert-butyl esters, peroxidating neodecanoic acid
Isopropyl phenyl ester, and peroxidating neodecanoic acid -1,1,3,3- tetramethyl butyl esters.Peroxy esters are that the low temperature of Raolical polymerizable triggers
Agent, it is widely used in polyethylene (LDPE), polyvinyl chloride (PVC), polystyrene (PS), styrol copolymer (e.g., ABS), poly- first
The production field such as base acrylate (PMMA) and polyvinyl acetate (PVAc).Meanwhile it is also that the high temperature of unsaturated polyester (UP) is consolidated
Agent.
Since Baeyer in 1901 and Villiger reports have produced first case peroxy esters so far, existing many peroxy esters are produced
Product come out, and the preparation from laboratory scale to industrially scalable has been reported that.At present, on the whole, most peroxy esters
Preparation is completed by acylated process (Acylation procedures).Its general principle is：By peroxide alcohol and acylation
Agent (includes the carbamyl chloride (Carbamyl of acyl chlorides, acid anhydrides, ketenes, chlorosulfuric acid, phosgene, chloroform, isocyanates
Chloride) etc.) reacted and prepared.Following reaction is the concrete form of the principle：
Peroxy esters are very active compounds, are extremely easy in decomposition free radical and oxygen for high reaction activity, meeting during being somebody's turn to do
The substantial amounts of heat of release even triggers blast.As organic peroxide, its key character be SADT (SADT,
Self Accelerating Decomposition Temperature), equal to or higher than under SADT, have
Machine peroxide decomposition reaction rate of heat release and function of environment heat emission speed are unbalance, i.e., system heat is constantly being accumulated, and now, has
Machine peroxide can cause the autoacceleration decomposition reaction of danger and the blast or on fire under adverse environment by thermal decomposition.With not
Compatible material contact and raising mechanical stress can cause equal to or less than the decomposition under SADT.
Organic peroxide can decompose in the presence of temperature, and this is due to that presence can be in about 84~184kJ/mol
Energy range △ H in open o-o bond, the energy range depend on the organic peroxide property.In other words
Different organic peroxides required energy when opening o-o bond of decomposing is different because of respective property.Therefore, no
Same organic peroxide, selfdecomposition accelerate temperature and heat endurance to have very big difference.Simultaneously because architectural difference, different organic
The synthetic route of peroxide and required raw material are all different, and the physics of raw material, chemical property also vary.This numerous difference
Cause the technical process in the absence of one so-called " general " that all organic peroxides, different organic peroxides can be applicable
Synthesis technique also can not mutually transplant and apply mechanically.The synthesis of each specific organic peroxide is required for being decomposed according to its autoacceleration
Temperature and heat endurance and using the physics of raw material, chemical property come the special applicable craft process for designing and developing personalization,
Condition and parameter.For example, it is 0 DEG C that the selfdecomposition of diisobutyryl peroxide (DIPB), which accelerates temperature (SADT), 10 hour half-life period
Corresponding temperature is 23 DEG C；It is 10 DEG C, 10 hours that the selfdecomposition of cumyl peroxyneodecanoate (CNP), which accelerates temperature (SADT),
Temperature corresponding to half-life period is 38 DEG C；It is 20 DEG C that the selfdecomposition of tert-Butyl peroxypivalate (TBPV), which accelerates temperature (SADT),
Temperature corresponding to 10 hour half-life period is 57 DEG C；And the selfdecomposition of the peroxidating 2- hexylacetic acids tert-butyl ester (TBPEH) accelerates temperature
(SADT) it is then 35 DEG C, temperature corresponding to 10 hour half-life period is 72 DEG C；For tertbutanol peroxide (TBHP), its selfdecomposition adds
Fast temperature (SADT) is more up to 80 DEG C, and temperature corresponding to 10 hour half-life period is 98 DEG C.
Peroxidating -2- ethylhexyl carbonate the tert-butyl esters, are abbreviated as TBEC, are mainly used in：The polymerization of styrene, it can use
In the polymerisation of styrene and the EVA of styrene, polymeric reaction temperature scope is 100-130 DEG C.In polymerisation in bulk,
It is advantageous to increase reaction rate., can be with using the peroxidating -2- ethylhexyl carbonates tert-butyl ester in aqueous suspension polymerization technique
Reduce the residual quantity of reaction final stage styrene monomer；The polymerization of acrylate and methacrylate, can be used for propylene
The polymerisation of acid esters or methacrylate, polymeric reaction temperature are 100-170 DEG C；The solidification of thermosetting resin, available for fat
The solidification of fat race unsaturated polyester (UP) at high temperature；And curing agent (SMC, BMC, ZMC that UP resin hot compression moldings technique is preferred
Deng), temperature range is 120-170 DEG C, product better tolerance, safety and environmental protection.Peroxidating -2- ethylhexyl carbonate the tert-butyl esters from
Accelerated decomposition temperature (SADT) is 60 DEG C, and temperature corresponding to 10 hour half-life period is 98 DEG C.
TBEC synthesis material is tertbutanol peroxide, sodium hydroxide or potassium hydroxide and chloro-carbonic acid 2- ethylhexyls, its
Reaction equation is as follows.At present, produced more using batch technology, reaction temperature generally below 50 DEG C, yield be 90% with
On, storage temperature is generally below 40 DEG C.
Batch technology (batch process) is to wait certain time (including each step after adding raw materials into reactor
Time of reaction, temperature fall time, heating-up time, soaking time and interval stand-by period for respectively operating etc.), reaction reaches one
After provisioning request, product is once drawn off, i.e. the mode of production of product is partitioned into batch, and can only produce per batch limited
The product of fixed qty (its quantity depends on the size of reactor volume).Refer to the reaction total time of batch technology from raw material to
The total time of product is made, includes the feed time of each step, in the reaction time, the discharge time, turns to expect the time, temperature fall time,
Heating-up time, soaking time and interval stand-by period for respectively operating etc..Material (bag in reactor in batch technology operating process
Include intermediate product, final product) composition, the state parameter such as temperature can change over time, be transient, production process and
Product quality has a very big uncertainty, and the quality for directly resulting in downstream product is unstable, it is difficult to controls.
The most important feature of batch technology has at 2 points, when during " stop " or " interruption " be present, second, production
It is spaced apart, i.e., product has batch and a batch production can only obtain the product of fixed qty.It is, for every
A batch of production, the raw material of fixed qty are reacted according to the order of reactions steps, finally give limited fixed qty
Product (product)；Then the raw material of fixed qty is put into again, the reaction of next batch is carried out according to same step, and being made has
The product of the fixed qty of limit.
The mode that batch technology is realized has two kinds：1) realized respectively with multiple reactors (for example, flask, reactor etc.),
Carried out per single step reaction in a reactor；2) realized with a reactor (for example, flask, reactor etc.), in the reaction
Every step reaction is sequentially completed in device, needs to add multiple raw materials successively according to reaction process in course of reaction, that is, each step
After reaction, just have " stop ", wait the raw material of further addition subsequent reactions.Some documents are also mode 2) it is referred to as continuously
(continuous), its substantially and interval because during " stop " be present, need to wait for feeding, or need to be next
Suitable temperature (for example, heating, cooling or insulation) is arrived in step reaction regulation.
Current synthesis technique uses intermittent reaction mostly.It is primarily present problems with：
1st, interval batch operation is inefficient, and the reaction time is very long.Need first to be slowly added dropwise alkali lye to tertbutanol peroxide
Synthesizing tertiary butyl sodium peroxide (potassium), during to control temperature, then chloro-carbonic acid 2- ethylhexyls are slowly added dropwise and continue to react.
2nd, the either reaction of tertbutanol peroxide and alkali lye, or the esterification of second step and chloro-carbonic acid 2- ethylhexyls
Journey is all exothermic reaction, it is necessary to reactor has good heat exchange property, ensures reaction not temperature runaway.Moreover, temperature is too high, production
Product can decompose, and reduce yield.And the heat exchange efficiency of reactor is poor, it is therefore desirable to control the rate of addition of reaction very
Slowly.Intermittent reaction security is to be improved.
The problem of although existing a small amount of continuous process exploitation for preparing TBEC comes out, and existing technique is present is：One
It is enlarge-effect unavoidably be present, this is that further industrial applications bring many uncertainties, for example, because amplification is imitated
Should have uncertain and be influenceed very big by production-scale, the technical process with enlarge-effect is amplified to industrialization
When, it is necessary to repeatedly amplify step by step, each amplification process will readjust Optimizing Technical and parameter, for example, according to production
When needing to adjust output, amplification process will be related to, the regulation of each output is required for readjusting optimization work
Skill condition and parameter, this can greatly consume manpower and materials and project development time；Because enlarge-effect is by production-scale
Influence is very big, can change with the change of output and without regularity, in industrialized production, even if process conditions and ginseng
Number is adjusted in place, if changing production scale, it is also desirable to readjusts Optimizing Technical and parameter, production process lacks
Flexibility；Significantly uncertain enlarge-effect can influence the stability and reliability of technique simultaneously, process conditions and parameter
Minor fluctuations all may greatly influence product quality so that unstable product quality, it is difficult to control；In addition, this can also give life
Production process brings potential security risk.
Second, can not react complete in some continuous processing short time, it is necessary to the longer reaction time improves conversion ratio, make
Decline into production efficiency.
Third, being to have used stirred reactor in some continuous processings, largely organic peroxy is based on wherein still containing
The reactant mixture of thing, despite the presence of the device for dissipative reaction heat, but the reactant mixture can still result in possible put
The danger of thermal response (such as decomposition).
Enlarge-effect (Scaling-Up Effect), refer to carry out chemical process (i.e. small-scale) in fact using mini-plant
The result of study that (such as laboratory scale) is drawn is tested, (such as is industrialized with large production equipment under the same operating conditions
Scale) result that draws often has very big difference.Influence about these difference is referred to as enlarge-effect.Its reason is mainly small rule
Temperature, concentration, residence time of material distribution in the experimental facilities of mould and the difference in large-scale equipment.It is that is, identical
Operating condition under, the results of study of small scale experiments can not be repeated completely on industrially scalable；To in industrially scalable
On obtain identical with small scale experiments or approximate as a result, it is desirable to by optimizing and revising, change technological parameter and operating condition.It is right
For chemical process, enlarge-effect is a problem of difficulty is larger and in the urgent need to address.If do not solved, can cause
Production process and product quality have very big uncertainty, first, the quality for directly resulting in downstream product is unstable, it is difficult to control
System；Second, uncertainty can bring production process technology parameter fluctuation, and then lead to not effectively control production process so that raw
Production security can not be guaranteed, and many potential safety hazards are buried for production process.
The A of Chinese patent CN 101287704 describe can synthesize peroxidating -2- ethylhexyl carbon by micro-reacting tcchnology
The method of tert-butyl acrylate, is related to a kind of under the auxiliary of at least one static micro-mixer, and it is organic efficiently and safely to synthesize this
The method of peroxide and the device for implementing this method.The patent explicitly points out organic peroxide equal to or higher than autoacceleration
Under decomposition temperature (SADT), the autoacceleration decomposition reaction of danger can be caused by thermal decomposition, and explodes or rises under adverse environment
Fire.That is, organic peroxide can even explode or rise equal to or higher than that can be in extreme danger under SADT
Fire.Correspondingly, the patent clearly proposes organic peroxide in preparing experience have shown that desired reaction temperature is less than above-mentioned SADT
Scope.TBEC SADTs are 60 DEG C, and the patent is made under the conditions of 55 DEG C (i.e. below its SADT)
For TBEC, reaction total time was at 3 to 6 minutes.
Chinese patent CN 101479239A describe continuously to be prepared using the plate type heat exchanger with high heat-exchange capacity
The method of organic peroxide.It is unstable and thermo-responsive compound that the patent, which mentions organic peroxide, i.e., in temperature
The lower compound decomposed of effect, therefore needs limit reached maximum temperature in synthesis.By different in plate type heat exchanger
Position (plate) introduces different reactants to control the maximum temperature so that can continuously prepare at a given temperature selected
Peroxide.Its temperature given value is such temperature, and organic peroxide becomes thermo-responsive during higher than the temperature, that is, synthesizes
In reaction temperature will be below the thermo-responsive temperature range of the relatively low organic peroxide.Compare batch technology,
Yield is close or more preferable but reaction temperature is higher.The synthesising reacting time of this method is in the model that laboratory scale is 1 second to 45 seconds
In enclosing, and it is up to 2 minutes to 3 minutes at industrial scale.Compared to batch technology, the continuous preparation method in production efficiency and
It is with the obvious advantage in security.Simply the commercial scale reaction time is 2 times~180 times of laboratory scale, is not existed very significantly not
It is determined that the enlarge-effect of (extension of 2~180 times of pole wide scopes of reaction time), adds industrialized difficulty.Simply by the presence of putting
Big effect, no matter amplitude size, whether determine, it is many unfavorable all to be brought to the industrial applications in technique future, for example, by
Existing uncertain in enlarge-effect and enlarge-effect be present, when amplifying to industrialization, can only take what is repeatedly amplified step by step
Method, and in order to obtain the result with laboratory scale uniformity, each amplification process will readjust optimize technique bar
Part and parameter, this can greatly consume manpower and materials and project development time；Even if using repeatedly amplifying step by step, because amplification is imitated
Should not know, amplitude of variation it is too big, it is also possible to be unable to reach the good result of laboratory scale after ultimately resulting in amplification；Due to amplification
Effect is very big by production-scale influence, can change with the change of output and without regularity, in industrialized production
In, even if process conditions and parameter adjustment are in place, if changing production scale, it is also desirable to readjust Optimizing Technical
And parameter, production process lack flexibility；Significantly uncertain enlarge-effect can influence the stability of technique and reliable simultaneously
Property, cause unstable product quality, it is difficult to control；In addition, this can also bring potential security risk to production process.
Chinese patent CN 101631772, CN 101641326 and document Chem.Eng.Process.2013,70,217-
221 report available for the continuation method for preparing TBEC, and these continuation methods all employ or part has used stirring reaction
Device, this causes：First, the stirred reactor used still carries the feature of batch equipment, thus enlarge-effect all be present.Second, by
In this " interval " factor being present, during have " stop ", technical process is still transient, is not continuous stream work
Skill, produce (synthesis) process and product quality and fluctuation and uncertainty still be present.Third, reactor is still containing substantial amounts of
Reactant mixture based on organic peroxide, despite the presence of the device for dissipative reaction heat, but the reactant mixture is still
The danger of possible exothermic reaction (such as decomposition) can be caused.Fourth, usually used mechanical agitator may not provide each reaction
The optimal mixing of phase, it is even more so when especially these are mutually unmixing.
From the prior art as can be seen that the synthesis technique of the existing peroxidating -2- ethylhexyl carbonate tert-butyl esters is deposited
In different degrees of enlarge-effect, cause that when to industrialization amplifying a large amount of manpower and materials can be consumed and many uncertainties be present；
Reliability of technology causes unstable product quality there is also problem after amplification, it is difficult to controls；Production process lacks flexibility simultaneously
And have potential security risk；It is low additionally, due to reaction temperature, cause reaction total time long, and yield is not high, reduces
Production efficiency, each of which increases industrialized difficulty.Large-scale production can not be realized, limits its application.Therefore, need
Find it is a kind of without enlarge-effect, it is simple to operate, efficiently, be easy to the tertiary fourth of peroxidating -2- ethylhexyl carbonates of large-scale production
The continuous stream synthesis technique of ester.
The content of the invention
It is deficiency for prior art, the technical problem to be solved by the invention is to provide one kind without enlarge-effect, operation
Simply, efficiently, it is easy to the continuous stream synthesis technique of the peroxidating -2- ethylhexyl carbonate tert-butyl esters of large-scale production.
Continuous synthesis technique (continuous processing, continuous process) refers to that production system respectively produces in production process
It is mutually linked between step, ensures continuous service on the whole, but allow to stop in each step and wait.Continuous stream synthesis technique
The one kind of (continuous flow process, continuous-flow process) as continuous processing, is a kind of whole process rapidly and efficiently
Continuous processing, there is short used time, efficiency high, easy to operate, during uninterruptedly add raw material, it is continuous uninterrupted
Ground production be made product, during material (reactant mixture for including raw material, intermediate, product, solvent etc.) be continuous
Flowing, it is not interrupted, does not stop wait, be i.e. product is continuously produced, and is a kind of change of " streamline " formula
Work production process.When technological operation reaches stationary state, the state parameter such as the composition of material, temperature is not on any position in reactor
Time to time change, it is steady-state process, thus production process and product quality are all stable.Including the work of multistep reaction
In skill, if wherein certain several step is continuous or simply simply connects each step in original batch technology,
The technique is properly termed as half-continuous process；And it is to connect in whole technical process that only all steps, which are all continuous and materials,
What afterflow was moved, that is, raw material is continuously added to, continuously draws product, continuous flow process (or whole process continuous processing) could be referred to as.
To solve the technical problem of the present invention, the present invention innovatively provides a kind of peroxidating -2- of no enlarge-effect
The continuous stream synthesis technique of the ethylhexyl carbonate tert-butyl ester, described synthesis technique is with tertbutanol peroxide, alkali lye, chloro-carbonic acid 2-
Ethylhexyl is raw material, continuously obtains peroxidating -2- ethylhexyl carbon through quaternization, esterification and cancellation step successively
Tert-butyl acrylate, described synthesis technique are carried out in integrated continuous flow reactor, in the integrated continuous flow reactor
Charging aperture uninterruptedly adds reaction raw materials tertbutanol peroxide, alkali lye, chloro-carbonic acid 2- ethylhexyls, in the integrated continuous flow
Reactor discharging opening uninterruptedly obtains the peroxidating -2- ethylhexyl carbonate tert-butyl esters, and described synthesis technique is without enlarge-effect.
Combination of the invention by integrated reaction technique and reactor, solves the technical problem of enlarge-effect.Due to this
Enlarge-effect is not present in the solution of invention, significantly reduces the difficulty of industrial applications, when amplifying to industrialization, nothing
Repeatedly amplifying and process conditions, the adjusting and optimizing of parameter step by step for very complicated need to be undergone, you can required for being once amplified to
Production scale, manpower and materials and project development time are greatly saved；In industrialized production, flexibly changing production
Scale, without readjusting Optimizing Technical and parameter, production process flexibility is good；Without enlarge-effect so that production process is steady
Fixed reliable, the fluctuation of process conditions and parameter does not interfere with product quality yet, and product quality is easily controllable；This is also greatly lifted
The security of production process.The production technology of the present invention can be completed to prepare peroxidating -2- second rapidly, continuously at high temperature
The two-step reaction of base hexyl t-butyl carbonate (TBEC), the selfdecomposition that described high temperature even can be far above TBEC accelerate temperature
(can be reacted more than 80 DEG C), production efficiency is greatly improved.It can be seen that production technology of the invention breaches prior art
Limitation, harshness that prior art can not be realized, it is dangerous under conditions of, the high efficiency for realizing TBEC that succeeded, high quality
Synthesis ((reaction, yield >=97% can be completed in 180s), and enlarge-effect is not present, industrialized production is especially suitable for,
It is an important breakthrough of this area.
The reaction scheme of the present invention is as follows：
Further, reaction total time≤180s of the synthesis technique, it is preferred that described reaction total time be 20~
180s；Preferably, described reaction total time is 40~90s；Preferably, described reaction total time is 20~150s, preferably
, described reaction total time is 20~110s；It is furthermore preferred that described reaction total time is 20~90s；It is furthermore preferred that institute
The reaction total time stated is 20~70s；It is furthermore preferred that described reaction total time is 20~60s, it is furthermore preferred that described is anti-
Should it be 30~50s total times；It is furthermore preferred that described reaction total time is 30~40s.Described reaction total time refers to from original
Material enters the time needed for reactor to output of products reactor, and the residence time is also referred to as in continuous flow process
(residence time).Reaction mother liquor can obtain industrial products peroxidating -2- ethyls by stratification, washing and after drying
Hexyl t-butyl carbonate.
Further, yield >=97% of the peroxidating -2- ethylhexyl carbonate tert-butyl esters；Preferably, the peroxide
Yield >=98% of the change -2- ethylhexyl carbonate tert-butyl esters；It is furthermore preferred that peroxidating -2- ethylhexyl carbonate the tert-butyl esters
Yield >=99%.
Further, content >=93% of the peroxidating -2- ethylhexyl carbonate tert-butyl esters；Preferably, the peroxide
Content >=96% of the change -2- ethylhexyl carbonate tert-butyl esters.
Further, temperature >=50 DEG C of the esterification, preferable temperature >=80 DEG C, preferable temperature are 50~90
DEG C, preferable temperature be 70~85 DEG C, preferable temperature be 50~100 DEG C, preferable temperature be 60~90 DEG C, more preferably temperature be 65~
85 DEG C, more preferably temperature is 70~80 DEG C.
Further, the temperature of the quaternization is 5~35 DEG C, preferably 5~30 DEG C, more preferably 5~20 DEG C, more preferably
5~18 DEG C, more preferably 5~13 DEG C, more preferably 6~11 DEG C, more preferably 7~9 DEG C.
Further, the temperature of described cancellation step is 15~45 DEG C, preferably 25~40 DEG C.
Further, the alkali lye is selected from the aqueous solution of potassium hydroxide or sodium hydroxide.
Further, the concentration of the alkali lye is 5%~45%, preferably 15%~35%, more preferably 20%~30%.
Further, the concentration of the tertbutanol peroxide is 60%~85%, preferably 65%~80%, more preferably 70%
~75%.
Further, the mol ratio of the alkali and tertbutanol peroxide is 1.0~1.5:1, preferably 1.10~1.25:1, more
Preferably 1.20:1.
Further, the mol ratio of chloro-carbonic acid 2- ethylhexyls and tertbutanol peroxide is 0.7~1.0:1, preferably 0.8~
1.0:1, more preferably 0.85:1.
To meet the condition of continuous flow process of the present invention, the present invention develops special integrated reactor.Described is anti-
It can be modular structure, it is necessary to design the organizational form of module, quantity to answer device, the module that each warm area includes, it is also necessary to open
Targetedly process conditions and parameter to be sent out, includes division and the temperature setting of each warm area, any of the above factor acts synergistically,
So that this continuous flow process is achieved.Each temperature and material concentration, material proportion and material can also further be combined
Flow velocity, it is allowed to match with reaction process, obtains more preferable reaction effect.Described material includes each raw material, course of reaction
Each intermediate product, described material concentration include concentration, the concentration of each intermediate product of each raw material, and described material proportion includes
The matching of each raw material, the concentration of each intermediate product, described material flow include flow velocity, the stream of each intermediate product of each raw material
Speed.
Further, to match with peroxidating -2- ethylhexyl carbonate tert-butyl ester continuous stream synthesis techniques, the one
Change continuous flow reactor and use having unit structure, including alkalize and unit, esterification unit and be quenched unit.Wherein：Described alkalization
Unit is used for tertbutanol peroxide t-butyl peroxy salt corresponding with alkali reaction generation and is transported to esterification unit；Described
Esterification unit is used for the reaction generation tertiary fourth of peroxidating -2- ethylhexyl carbonates of t-butyl peroxy salt and chloro-carbonic acid 2- ethylhexyls
Ester (TBEC) is simultaneously transported to unit is quenched；Simultaneously output-response mother liquor is quenched for reaction in the described unit that is quenched.
Further, temperature >=50 DEG C of the esterification unit, preferable temperature >=80 DEG C, preferable temperature are 50~90
DEG C, preferable temperature be 70~85 DEG C, preferable temperature be 50~100 DEG C, preferable temperature be 60~90 DEG C, more preferably temperature be 65~
85 DEG C, more preferably temperature is 70~80 DEG C.
Further, the temperature of the alkalization unit is 5~35 DEG C, preferably 5~30 DEG C, more preferably 5~20 DEG C, more preferably
5~18 DEG C, more preferably 5~13 DEG C, more preferably 6~11 DEG C, more preferably 7~9 DEG C.
Further, the described temperature that unit is quenched is 15~45 DEG C, preferably 25~40 DEG C.
Further, to match with peroxidating -2- ethylhexyl carbonate tert-butyl ester continuous stream synthesis techniques, the one
Change continuous flow reactor and use having unit structure, described each unit is independently comprising more than one reactor module or anti-
Device module group is answered, wherein reactor module group is made up of multiple reactor module serial or parallel connections, is serially connected between each unit.
Further, to match with peroxidating -2- ethylhexyl carbonate tert-butyl ester continuous stream synthesis techniques, the one
Change continuous flow reactor and use having unit structure, the corresponding warm area of described each unit, each warm area independently includes one
Reactor module or reactor module group more than individual, wherein reactor module group is by multiple reactor module serial or parallel connection groups
Into being serially connected between each warm area.
Further, buffer is further comprised between described unit.
The quantity of the integrated continuous flow reactor feed mouth is one or more, the integrated continuous flow reactor
The quantity of discharging opening is one or more.
The invention provides an efficient TBEC continuous streams synthetic schemes without enlarge-effect, i.e. three kinds of reactants are not
In disconnected ground input reactor, and continuously collecting reaction product.The integrated continuous flow reactor used includes three function lists
Member：Alkalization unit, esterification unit and it is quenched unit.By means of the division of functional unit warm area and the optimization of temperature setting and three
The synergy of functional unit, just can fully it be reacted in the short time, reaction foreshortens in 3 minutes total time, greatly improves
The efficiency of technique.Especially can be under higher temperature (being higher than 80 DEG C) more than the SADT for substantially exceeding TBEC
Esterification is completed, greatly accelerates reaction process, without delay lie within a short period of time (being typically in 3 minutes)
Obtain more than 97% in high yield so that TBEC production realizes high quality, high efficiency, stabilized large-scale production.
In continuous flow process stability and good reliability, thus product quality is stable, favorable reproducibility；Technique does not amplify effect
Should, also solve the problems, such as that the industrialization of TBEC continuous flow process has enlarge-effect；Simultaneously the integrated continuous flow reactor by
In without delay lie, small volume, floor space is small, has greatly saved factory building land used.
Further, described reactor module is optionally that any one can realize the reactor of continuous flow process, described
Reactor be selected from microreactor (Microreactor), series connection coil reactor (Tandem loop reactor), tubular type is anti-
Answer device (Tubular reactor) any one or it is any a variety of.Described microreactor, also known as micro-structured reactor or micro-
Channel reactor, be it is a kind of wherein chemical reaction occur in universal lateral dimensions setting in 1mm and following finite region
Standby, this kind of most typical form of finite region is miniature sizes passage.Series connection coil reactor, i.e., reacted coil pipe with pipeline
Device is together in series the reactor of composition, and wherein coil reactor is that tubular reactor is made to the form of coil pipe.Tubular reactor
Be occur the middle of last century it is a kind of in a tubular form, the very big continuous manipulation reactor of draw ratio.This reactor can be very long；
Can also multitube parallel with single tube；It can be managed with blank pipe or filling.
Further, described reactor can be one or more.
Further, the material of the channel of reactor is monocrystalline silicon, special glass, ceramics, scribbles corrosion resistant coating not
Become rusty steel or metal alloy, polytetrafluoroethylene (PTFE).
Further, between described reactor module, between reactor module group, reactor module and reactor module
It is respectively serial or parallel connection between group.
Further, the alkalization unit corresponds to warm area 1, and the esterification unit corresponds to warm area 2, and the unit that is quenched corresponds to
Warm area 3.
Further, described continuous stream synthesis technique is carried out in the integrated continuous flow reactor comprising 3 warm areas.
Further, described continuous stream synthesis technique comprises the following steps：
(a) tertbutanol peroxide and alkali lye are conveyed into warm area 1, flows through warm area 1 and react, generate the tertiary fourth of intermediate
Base peroxy salt；
(b) reaction solution of outflow warm area 1 enters warm area 2 after being mixed with chloro-carbonic acid 2- ethylhexyls, flows through warm area 2, until
Reaction is complete.
(c) reaction solution for flowing out warm area 2 enters the cooling of warm area 3 reaction is quenched, and obtains peroxidating -2- ethylhexyl carbonates
The tert-butyl ester.
Further, the temperature of the warm area 1 is 5~35 DEG C, preferably 5~30 DEG C, more preferably 5~20 DEG C, more preferably 5~
18 DEG C, more preferably 5~13 DEG C, more preferably 6~11 DEG C, more preferably 7~9 DEG C.
Further, temperature >=50 DEG C of the warm area 2, preferable temperature >=80 DEG C, preferable temperature are 50~90 DEG C,
Preferable temperature is 70~85 DEG C, and preferable temperature is 50~100 DEG C, and preferable temperature is 60~90 DEG C, and more preferably temperature is 65~85
DEG C, more preferably temperature is 70~80 DEG C.
Further, the temperature of the warm area 3 is 15~45 DEG C, preferably 25~40 DEG C.
Further, step (a) alkali lye is selected from the aqueous solution of potassium hydroxide or sodium hydroxide.
Further, the concentration of lye is 5%~45%, preferably 15%~35%, more preferably 20%~30%.
Further, step (a) the tertbutanol peroxide concentration is 60%~85%, preferably 65%~80%, more excellent
Select 70%~75%.
Further, the mol ratio of alkali and tertbutanol peroxide is 1.0~1.5:1, preferably 1.10~1.25:1, more preferably
For 1.20:1.
Further, the mol ratio of chloro-carbonic acid 2- ethylhexyls and tertbutanol peroxide is 0.7~1.1:1, preferably 0.8~
1.0:1, more preferably 0.85:1.
Further, yield >=97% of the peroxidating -2- ethylhexyl carbonate tert-butyl esters；Preferably, the peroxide
Yield >=98% of the change -2- ethylhexyl carbonate tert-butyl esters；It is furthermore preferred that peroxidating -2- ethylhexyl carbonate the tert-butyl esters
Yield >=99%.
Further, content >=93% of the peroxidating -2- ethylhexyl carbonate tert-butyl esters；Preferably, the peroxide
Content >=96% of the change -2- ethylhexyl carbonate tert-butyl esters.
It should be noted that the peroxidating uncle in actual synthesis used in (including in laboratory, pilot scale, actual production process)
Butanol concentration has the deviation of ± 3 percentage points of mass concentration；Concentration of lye has the inclined of ± 3 percentage points of mass concentration
Difference；Warm area temperature has ± 5 DEG C of deviation；Reaction has ± 5s deviation total time.
Second object of the present invention is to provide a kind of peroxidating -2- ethyls for being exclusively used in any form as previously described
The integrated continuous flow reactor of the continuous stream synthesis technique of hexyl t-butyl carbonate, described integrated continuous flow reactor are adopted
With having unit structure, including alkalization unit, esterification unit and unit is quenched, wherein：Described alkalization unit is used for peroxidating uncle
Butanol t-butyl peroxy salt corresponding with alkali reaction generation is simultaneously transported to esterification unit；Described esterification unit is used for tertiary fourth
The reaction of base peroxy salt and chloro-carbonic acid 2- ethylhexyls, which generates the peroxidating -2- ethylhexyl carbonates tert-butyl ester and is transported to, quenches
Go out unit；Simultaneously output-response mother liquor is quenched for reaction in the described unit that is quenched.
Third object of the present invention is to provide a kind of peroxidating -2- ethyls for being exclusively used in any form as previously described
The integrated continuous flow reactor of the continuous stream synthesis technique of hexyl t-butyl carbonate, the integrated continuous flow reactor use
Having unit structure, described each unit independently includes more than one reactor module or reactor module group, wherein instead
Answer device module group to be made up of multiple reactor module serial or parallel connections, be serially connected between each unit.
Fourth object of the present invention is to provide a kind of peroxidating for being exclusively used in any form as previously described new last of the ten Heavenly stems
The integrated continuous flow reactor of the continuous stream synthesis technique of tert-butyl acrylate, described integrated continuous flow reactor use unit
Change structure, each described unit corresponds at least one warm area, and each warm area independently includes more than one reactor module
Or reactor module group, wherein reactor module group are made up of multiple reactor module serial or parallel connections, between each warm area mutually
Series connection.
Three of the above continuous flow reactor can be further：
Further, buffer (Buffer vessel), described buffer are further comprised between described unit
For the container with a constant volume, it is mainly used in pressure oscillation and the balance flow difference of buffer system, makes system work more flat
Surely.
Further, the quantity of the integrated continuous flow reactor feed mouth is one or more, and the integration is continuous
The quantity of flow reactor discharging opening is one or more.
Further, described reactor module is optionally that any one can realize the reactor of continuous flow process, described
Reactor be selected from microreactor (Microreactor), series connection coil reactor (Tandem loop reactor), tubular type is anti-
Answer device (Tubular reactor) any one or it is any a variety of.Described microreactor, also known as micro-structured reactor or micro-
Channel reactor, be it is a kind of wherein chemical reaction occur in universal lateral dimensions setting in 1mm and following finite region
Standby, this kind of most typical form of finite region is miniature sizes passage.Series connection coil reactor, i.e., reacted coil pipe with pipeline
Device is together in series the reactor of composition, and wherein coil reactor is that tubular reactor is made to the form of coil pipe.Tubular reactor
Be occur the middle of last century it is a kind of in a tubular form, the very big continuous manipulation reactor of draw ratio.This reactor can be very long；
Can also multitube parallel with single tube；It can be managed with blank pipe or filling.
Further, described reactor can be one or more.
Further, between described reactor module, between reactor module group, reactor module and reactor module
It is respectively serial or parallel connection between group.
Further, the material of the channel of reactor is monocrystalline silicon, special glass, ceramics, scribbles corrosion resistant coating not
Become rusty steel or metal alloy, polytetrafluoroethylene (PTFE).
Further, described integrated continuous flow reactor includes 3 warm areas.
Further, the alkalization unit corresponds to warm area 1, and the esterification unit corresponds to warm area 2, and the unit that is quenched corresponds to
Warm area 3.
Further, the temperature of the warm area 1 is 5~35 DEG C, preferably 5~30 DEG C, more preferably 5~20 DEG C, more preferably 5~
18 DEG C, more preferably 5~13 DEG C, more preferably 6~11 DEG C, more preferably 7~9 DEG C.
Further, temperature >=50 DEG C of the warm area 2, preferable temperature >=80 DEG C, preferable temperature are 50~90 DEG C,
Preferable temperature is 70~85 DEG C, and preferable temperature is 50~100 DEG C, and preferable temperature is 60~90 DEG C, and more preferably temperature is 65~85
DEG C, more preferably temperature is 70~80 DEG C.
Further, the temperature of the warm area 3 is 15~45 DEG C, preferably 25~40 DEG C.
The present invention compared with the prior art, has the beneficial effect that：
1st, the efficient continuous stream synthesis of TBEC is realized on integrated continuous flow reactor.That is, three kinds of reactants are continuous
In ground input reactor, and continuously collecting reaction product.It is short by means of the division of functional unit warm area and the optimization of temperature setting
It just can fully be reacted in time, greatly improve the efficiency of technique.It is at most 3 minutes to react total time.
2nd, process safety significant increase, the relatively small liquid holdup of continuous flow reactor and excellent heat-transfer character, add
The shorter reaction time (in 3 minutes) cause the technical process it is safer.Wherein described reactor liquid holdup refers to work as
When operation reaches stationary state, the cumulative volume for the reaction mass having in any instant reactor.
3rd, TBEC SADT is 60 DEG C, and esterification reaction temperature is set in compared with low temperature in some continuous flow process
When spending (55 DEG C), in order to reach appropriate yield, it is necessary to extend the reaction time, and this obviously can reduce the efficiency of successive reaction.
And this technical process, esterification is still very steady at a temperature of 80 DEG C of even more highs in esterification unit is carried out, and observation is not
To significant decomposing phenomenon.With the raising of temperature, the yield of reaction significantly improves, i.e. available more than 97% in the short time
In high yield, so that the reaction time greatly shortens, it can react complete in typically 3 minutes, production is highly efficient.
4th, the physics according to TBEC SADT and heat endurance and using raw material, chemical property, one
Three functional units are devised in body continuous flow reactor.The unit that wherein alkalizes is used for tertbutanol peroxide and generated with alkali reaction
Corresponding t-butyl peroxy salt is simultaneously transported to esterification unit；Esterification unit is used for t-butyl peroxy salt and chloro-carbonic acid 2- ethyls
The reaction of own ester, which generates the peroxidating -2- ethylhexyl carbonates tert-butyl ester (TBEC) and is transported to, is quenched unit；Unit is quenched
Simultaneously output-response mother liquor is quenched for reacting.Acted synergistically by three functional units so that reaction can be in 3 minutes fully
Complete.
5th, in integrated continuous flow reactor, due to flow speed stability, stable production process, thus product quality it is stable,
Favorable reproducibility.
6th, the technique still completed reaction, product content and yield and laboratory rule on industrially scalable in 3 minutes
It is essentially identical during mould, enlarge-effect is not found, solves the problems, such as the industrialization amplification of TBEC continuous flow process.
7th, the integrated continuous flow reactor is because without delay lie, small volume, floor space is small, greatly saves
Factory building land used.
Brief description of the drawings
The continuous synthesis technique artwork of Fig. 1 embodiment of the present invention 1.
Wherein, T1 is the temperature of warm area 1；T2 is the temperature of warm area 2；T3 is the temperature of warm area 3.
Fig. 2 is the schematic diagram of integrated reactor of the present invention.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of instruction of the present invention has been read, this area skill
Art personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims institute
The scope of restriction.
Concentration in the embodiment of the present invention is mass concentration, and the content of product is examined using high performance liquid chromatography (HPLC)
Survey.
Embodiment 1
As depicted in figs. 1 and 2, it is raw material 1 (tertbutanol peroxide) and raw material 2 (potassium hydroxide aqueous solution) is defeated with constant flow pump
It is sent into warm area 1, flows through warm area 1 and react, generates intermediate tert-butyl hydroperoxide potassium.Using constant flow pump by the (chloromethane of raw material 3
Sour 2- ethylhexyls) convey into warm area 2, warm area 2 is flowed through, reaction is complete.The reaction solution of outflow warm area 2 cools into warm area 3
Reaction is quenched, reaction mother liquor is collected.Mother liquor is layered, washing etc., you can obtain the peroxidating -2- ethylhexyl carbonate tert-butyl esters.
Each response parameter and result are as follows：
Table 1：Material flow, warm area temperature, reaction time, content and yield
Embodiment 2-19
Using the operating method of embodiment 1, preparation peroxidating -2- ethylhexyl carbonate uncles under differential responses parameter have been investigated
Reaction time, content and the yield of butyl ester, each Parameter Conditions and result are as shown in table 2 below and 3.
Table 2：Embodiment 2-19 material concentration and flow
| Temperature T1c(℃) | Temperature T2c(℃) | Temperature T3c(℃) | React total timed | Content (%) | Yield (%) | |
| 2 | 5 | 50 | 35 | 180s | 93.0 | 97.1 |
| 3 | 20 | 70 | 20 | 50s | 93.5 | 97.3 |
| 4 | 11 | 55 | 15 | 150s | 92.9 | 97.7 |
| 5 | 25 | 65 | 40 | 20s | 95.5 | 97.0 |
| 6 | 30 | 60 | 30 | 110s | 96.0 | 97.8 |
| 7 | 13 | 80 | 45 | 80s | 95.2 | 97.2 |
| 8 | 9 | 78 | 23 | 100s | 93.7 | 97.6 |
| 9 | 9 | 78 | 23 | 100s | 93.7 | 97.6 |
| 10 | 7 | 90 | 31 | 30s | 94.2 | 97.4 |
| 11 | 18 | 79 | 28 | 120s | 94.6 | 98.0 |
| 12 | 18 | 79 | 28 | 120s | 94.6 | 98.0 |
| 13 | 35 | 82 | 29 | 70s | 95.0 | 97.5 |
| 14 | 35 | 82 | 29 | 70s | 95.0 | 97.5 |
| 15 | 6 | 85 | 32 | 60s | 93.3 | 98.8 |
| 16 | 8 | 81 | 17 | 40s | 94.0 | 98.6 |
| 17 | 10 | 83 | 33 | 90s | 94.5 | 98.3 |
| 18 | 5 | 50 | 35 | 150s | 94.3 | 99.0 |
| 19 | 8 | 100 | 25 | 60s | 93.8 | 99.5 |
Tertbutanol peroxide concentration used has ± 3 percentage points of matter with concentration listed in table in the actual synthesis of a
Measure the deviation of concentration.
Concentration listed in concentration of lye and table used has ± 3 percentage points of mass concentration in the actual synthesis of b
Deviation.
Listed temperature has ± 5 DEG C of deviation in warm area temperature and table in the actual synthesis of c.
The listed deviation for having ± 5s reaction total times in reaction total time and table in the actual synthesis of d.
Comparative example 8 and 9, embodiment 11 and 12, embodiment 13 and 14 understand that iodine scale is not to product
Content and yield have an impact, i.e., this technique and enlarge-effect is not present；From embodiment 2, even in relatively low 50 DEG C
Esterification is carried out, reaction remains to complete in 3 minutes, and obtains 93.0% product content and 97.1% product yield.
This all shows that this technique has the characteristics of stable, reliable, efficiently and suitable for industrialization to amplify.
Claims (11)
- A kind of 1. continuous stream synthesis technique of the peroxidating -2- ethylhexyl carbonate tert-butyl esters of no enlarge-effect, it is characterised in that： Described synthesis technique using tertbutanol peroxide, alkali lye, chloro-carbonic acid 2- ethylhexyls as raw material, continuously successively through quaternization, Esterification and cancellation step obtain the peroxidating -2- ethylhexyl carbonate tert-butyl esters, and described synthesis technique connects in integration Carried out in afterflow reactor, the tertiary fourth of reaction raw materials peroxidating is uninterruptedly added in the charging aperture of the integrated continuous flow reactor Alcohol, alkali lye, chloro-carbonic acid 2- ethylhexyls, peroxidating -2- second is uninterruptedly obtained in the integrated continuous flow reactor discharging opening Base hexyl t-butyl carbonate, described synthesis technique is without enlarge-effect.
- 2. continuous stream synthesis technique according to claim 1, it is characterised in that：The reaction total time of the synthesis technique≤ 180s, it is preferred that described reaction total time is 20~180s；Preferably, described reaction total time is 40~90s；It is preferred that , described reaction total time is 20~150s, it is preferred that described reaction total time is 20~110s；It is it is furthermore preferred that described Reaction total time be 20~90s；It is furthermore preferred that described reaction total time is 20~70s；It is furthermore preferred that described reaction Total time is 20~60s, it is furthermore preferred that described reaction total time is 30~50s；It is furthermore preferred that described reaction total time For 30~40s.
- 3. continuous stream synthesis technique according to claim 1 or 2, it is characterised in that：The integrated continuous flow reactor Using having unit structure, including alkalization unit, esterification unit and unit is quenched, wherein：Described alkalization unit is used for peroxidating Tert-butyl alcohol t-butyl peroxy salt corresponding with alkali reaction generation is simultaneously transported to esterification unit；Described esterification unit is used for uncle The reaction of butyl peroxy salt and chloro-carbonic acid 2- ethylhexyls generates the peroxidating -2- ethylhexyl carbonates tert-butyl ester and is transported to Unit is quenched；Simultaneously output-response mother liquor is quenched for reaction in the described unit that is quenched.
- 4. continuous stream synthesis technique according to claim 1 or 2, it is characterised in that：The integrated continuous flow reactor Using having unit structure, described each unit independently includes more than one reactor module or reactor module group, its Middle reactor module group is made up of multiple reactor module serial or parallel connections, is serially connected between each unit.
- 5. continuous stream synthesis technique according to claim 1 or 2, it is characterised in that：Described each unit is corresponding one Warm area, each warm area independently include more than one reactor module or reactor module group, wherein reactor module group by Multiple reactor module serial or parallel connections form, and are serially connected between each warm area.
- 6. according to the continuous stream synthesis technique described in claim any one of 1-5, it is characterised in that：Described continuous stream synthesis work Skill is carried out in the integrated continuous flow reactor comprising 3 warm areas.
- 7. according to the continuous stream synthesis technique described in claim any one of 3-5, it is characterised in that：The corresponding temperature of alkalization unit Area 1, the esterification unit correspond to warm area 2, and the unit that is quenched corresponds to warm area 3.
- 8. the continuous stream synthesis technique according to claim 6 or 7, it is characterised in that：Described continuous stream synthesis technique bag Include following steps：（a）Tertbutanol peroxide and alkali lye are conveyed into warm area 1, warm area 1 is flowed through and reacts, generates intermediate tert-butyl group mistake Oxonium salt；（b）The reaction solution of outflow warm area 1 enters warm area 2 after being mixed with chloro-carbonic acid 2- ethylhexyls, flows through warm area 2, until reaction Completely；（c）The reaction solution of outflow warm area 2 enters warm area 3 and cooled reaction is quenched, and obtains the tertiary fourth of peroxidating -2- ethylhexyl carbonates Ester.
- A kind of 9. continuous stream synthesis work of peroxidating -2- ethylhexyl carbonate tert-butyl esters for being exclusively used in any one of claim 1-8 The integrated continuous flow reactor of skill, it is characterised in that：Described integrated continuous flow reactor uses having unit structure, including Unit, esterification unit and unit is quenched in alkalization, wherein：Described alkalization unit is used for tertbutanol peroxide and reacts generation phase with alkali The t-butyl peroxy salt answered simultaneously is transported to esterification unit；Described esterification unit is used for t-butyl peroxy salt and chloro-carbonic acid 2- The reaction of ethylhexyl, which generates the peroxidating -2- ethylhexyl carbonates tert-butyl ester and is transported to, is quenched unit；Described is quenched Unit is quenched for reaction and output-response mother liquor.
- A kind of 10. continuous stream synthesis work of peroxidating -2- ethylhexyl carbonate tert-butyl esters for being exclusively used in any one of claim 1-8 The integrated continuous flow reactor of skill, it is characterised in that：The integrated continuous flow reactor uses having unit structure, described Each unit independently includes more than one reactor module or reactor module group, and wherein reactor module group is by multiple anti- Answer device block coupled in series or compose in parallel, be serially connected between each unit.
- 11. according to the integrated continuous flow reactor described in claim any one of 1-8, it is characterised in that：Described each list The corresponding warm area of member, each warm area independently includes more than one reactor module or reactor module group, wherein reacting Device module group is made up of multiple reactor module serial or parallel connections, is serially connected between each warm area.
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| CN108794522A (en) * | 2018-05-07 | 2018-11-13 | 浙江万盛股份有限公司 | A kind of tricresyl phosphate（The chloro- 2- propyl of 1-）The Total continuity stream production technology of ester |
| WO2019034004A1 (en) * | 2017-08-12 | 2019-02-21 | 上海惠和化德生物科技有限公司 | Online full continuous flow production process for directly preparing organic peroxide with hydrogen peroxide as raw material |
| CN109553560A (en) * | 2017-08-12 | 2019-04-02 | 上海惠和化德生物科技有限公司 | A kind of online Total continuity stream production technology directly preparing organic peroxide by alcohol or alkane |
| US10947189B2 (en) | 2017-08-12 | 2021-03-16 | Shanghai Hybrid-Chem Technologies | Online continuous flow process for the synthesis of organic peroxides using hydrogen peroxide as raw material |
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| CN116178234A (en) * | 2023-03-07 | 2023-05-30 | 淄博正华助剂股份有限公司 | Preparation method of solvent type peroxy-2-ethylhexyl tert-butyl carbonate |
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| CN101287704A (en) * | 2005-10-14 | 2008-10-15 | 埃尔费尔德微技术Bts有限责任公司 | Method for the production of organic peroxides by means of a microreaction technique |
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