CN107698480A - A kind of continuous stream synthesis technique of the new peroxide tert-butyl caprate of no enlarge-effect - Google Patents
A kind of continuous stream synthesis technique of the new peroxide tert-butyl caprate of no enlarge-effect Download PDFInfo
- Publication number
- CN107698480A CN107698480A CN201710688986.XA CN201710688986A CN107698480A CN 107698480 A CN107698480 A CN 107698480A CN 201710688986 A CN201710688986 A CN 201710688986A CN 107698480 A CN107698480 A CN 107698480A
- Authority
- CN
- China
- Prior art keywords
- unit
- reaction
- reactor
- synthesis technique
- warm area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
Abstract
The present invention provides a kind of continuous stream synthesis technique of the new peroxide tert-butyl caprate of no enlarge-effect, described synthesis technique is with tertbutanol peroxide, alkali lye, new decanoyl chloride is raw material, continuously successively through quaternization, esterification and cancellation step obtain new peroxide tert-butyl caprate, 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, new decanoyl chloride, new peroxide tert-butyl caprate is uninterruptedly obtained in the integrated continuous flow reactor discharging opening, without enlarge-effect, react total time≤180s.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 synthesis technique of new peroxide tert-butyl caprate.
Background technology
Peroxy esters are important organic peroxide, such as new peroxide tert-butyl caprate, cumyl peroxyneodecanoate,
With peroxidating neodecanoic acid -1,1,3,3- tetramethyl butyl esters.Peroxy esters are the low temperature initiators of Raolical polymerizable, are widely used in
Polyethylene (LDPE), polyvinyl chloride (PVC), polystyrene (PS), styrol copolymer (e.g., ABS), polymethacrylates
And the production field such as polyvinyl acetate (PVAc) (PMMA).Meanwhile it is also the high-temperature curing agent of unsaturated polyester (UP).
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 is SADT (SADT),
Equal to or higher than under SADT, organic peroxide decomposition reaction rate of heat release is unbalance with function of environment heat emission speed
, i.e., system heat is constantly being accumulated, and now, organic peroxide can cause the autoacceleration decomposition reaction of danger by thermal decomposition
With the blast under adverse environment or on fire.Contacting and improve mechanical stress with incompatible material can cause be equal to or low
Decomposition under SADT.
Different organic peroxides, selfdecomposition accelerate temperature and heat endurance to have very big difference.Simultaneously because structure is poor
Different, the synthetic route of different organic peroxides and required raw material are all different, the physics of raw material, chemical property also thousand poor ten thousand
Not.This numerous difference causes the technical process in the absence of one so-called " general " to be applicable all organic peroxides, different
The synthesis technique of organic peroxide also can not mutually transplant and apply mechanically.The synthesis of each specific organic peroxide is required for root
Special to design and develop personalization according to its SADT and heat endurance and using the physics of raw material, chemical property
Applicable craft process, condition and parameter.For example, it is 0 DEG C, 10 hours that the selfdecomposition of diisobutyryl peroxide, which accelerates temperature (SADT),
Temperature corresponding to half-life period is 23 DEG C；It is 10 DEG C that the selfdecomposition of cumyl peroxyneodecanoate, which accelerates temperature (SADT), and 10 is small
When temperature corresponding to half-life period be 38 DEG C；It is 20 DEG C that the selfdecomposition of tert-Butyl peroxypivalate, which accelerates temperature (SADT), and 10 is small
When temperature corresponding to half-life period be 57 DEG C；And it is then 35 that the selfdecomposition of the peroxidating 2- hexylacetic acid tert-butyl esters, which accelerates temperature (SADT),
DEG C, temperature corresponding to 10 hour half-life period is 72 DEG C；For tertbutanol peroxide (TBHP), its selfdecomposition accelerates temperature (SADT)
More up to 80 DEG C, temperature corresponding to 10 hour half-life period is 98 DEG C.
New peroxide tert-butyl caprate, BNP is abbreviated as, the superior low-temperature for being mainly used in polyethylene from high pressure process (LDPE) triggers
Agent, it is used for tubular process, can be with the initiator peroxidating pivalic acid tert-butyl ester, the peroxidating -2- ethyl acids tert-butyl ester, peroxide
Change t-butyl perbenzoate etc. and collectively constitute composite initiator system, polymerization effect is more preferable.It is the high-temperature curing agent of unsaturated polyester (UP).
Available for vinyl chloride, the polymerization of the copolymer polymerization initiator and methacrylate, vinylacetate of styrene or styrene
Initiator, the SADT (SADT) of new peroxide tert-butyl caprate is 20 DEG C, temperature corresponding to 10 hour half-life period
For 46 DEG C.
BNP synthesis material is tertbutanol peroxide, sodium hydroxide or potassium hydroxide and new decanoyl chloride.At present, it is to use more
Batch technology produces, and for reaction temperature generally below 20 DEG C, yield is more than 90%, and storage temperature will typically be less than -10 DEG C.
Reaction equation is as follows：
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.
Synthesis BNP technique is mostly using batch technology at present.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 new decanoyl chloride is slowly added dropwise and continues to react.
2nd, the either reaction of tertbutanol peroxide and alkali lye, or the esterification process of second step and new decanoyl chloride, all it is
, it is necessary to which reactor has good heat exchange property, not temperature runaway is reacted in guarantee for exothermic reaction.Moreover, temperature is too high, product can occur
Decompose, reduce yield.And the heat exchange efficiency of reactor is poor, it is therefore desirable to control the rate of addition of reaction very it is slow.
Batch technology security is to be improved.
Although existing a small amount of continuous flow process develops, problem be present：Unavoidably enlarge-effect be present, this
Many uncertainties are brought for further industrial applications；In some continuous flow process short time reaction not enough completely, it is necessary to
Reaction time is increased to improve conversion ratio by delay lie, causes production efficiency to decline.
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.
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, by introducing different reactants in plate type heat exchanger diverse location (plate), in given temperature
The selected peroxide of the lower continuous preparation of degree.Its temperature given value is such temperature, i.e., higher than the temperature when organic peroxy
Thing becomes thermo-responsive, and final preferable range of reaction temperature is 5-60 DEG C.The synthesising reacting time of this method is in laboratory scale
In the range of 1 second to 45 seconds, and it is up to 2 minutes to 3 minutes at industrial scale.Compared to batch technology, the continuous preparation
Method has certain advantage in production efficiency and security, but due to being inevitably present enlarge-effect, its industry
The scale reaction time is 2~180 times of laboratory scale, exists and does not know (2~180 times of pole wide scopes of reaction time significantly
Extension) enlarge-effect, considerably increase industrialized difficulty.Significantly uncertain enlarge-effect can give the work of the technique
It is many unfavorable that industry application is brought, for example, when amplifying to industrialization, can only take the method repeatedly amplified step by step, and be
Acquisition and the result of laboratory scale uniformity, each amplification process will readjust Optimizing Technical and parameter, this
The time of manpower and materials and project development can greatly be consumed；Even if using repeatedly amplifying step by step, because enlarge-effect changes width
Degree is too big, it is also possible to ultimately results in the good result that laboratory scale is unable to reach after amplifying；Significantly uncertain amplification simultaneously
Effect can influence the stability and reliability of technique, cause unstable product quality, it is difficult to control；In addition, this can also give production
Process brings potential security risk.
Chinese patent CN 104592080A describe a kind of method that continuous stream prepares BNP, and its course of reaction is in micro- reaction
Carried out in device, then have to pass through delay lie and further fully react and cool down, collect product.Obtained under the conditions of 15~35 DEG C
Obtain more than 98% yield.Compared to batch technology, although being carried to a certain extent in the advantage of mass-and heat-transfer using microreactor
The high reaction temperature of esterification, shortens the reaction time, but still suffer from many deficiencies：First, esterification reaction temperature is still inclined
Low (15~35 DEG C), cause reaction not abundant enough；Second, in order to further fully react and cool down, it is necessary to Cai use delay lie
The purpose of reaction can be reached.Delay lie is as a kind of tubular reactor, when amplifying to industrially scalable still inevitably
Enlarge-effect be present.I.e. the program fails to avoid enlarge-effect problem existing for batch technology completely, and the amplification for increasing technique is difficult
Degree so that process reliability, product quality stability and production security are problematic in that；Three be due to that reaction is not filled
Point, delay lie has been used, has caused reaction total time partially long, typically at least wants more than 5 minutes, even up to 20 minutes, cause
Production efficiency is relatively low.In addition, the tubular reactor that delay lie needs needs to occupy certain space, space waste is caused.
From the prior art as can be seen that the synthesis technique of existing new peroxide tert-butyl caprate is present in various degree
Enlarge-effect, because reaction temperature is low, cause to react that total time is long, and yield is not high, adds industrialized difficulty.Nothing
Method realizes large-scale production, limits its application.It is, thus, sought for it is a kind of without enlarge-effect, it is simple to operate, efficiently, it is easy to
The continuous stream synthesis technique of the new peroxide tert-butyl caprate of large-scale production.
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 new peroxide tert-butyl caprate 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 (partly) continuous processing；And only all steps are all continuous and materials is in whole technical process
Continuously flow, that is, be continuously added to raw material, continuously draw product, continuous flow process (or the continuous work of whole process could be referred to as
Skill).
To solve the technical problem of the present invention, the present invention provides a kind of continuous stream synthesis work of new peroxide tert-butyl caprate
Skill, using tertbutanol peroxide, alkali lye, new decanoyl chloride as raw material, continuously successively through quaternization, esterification and cancellation step
New peroxide tert-butyl caprate is obtained, reaction scheme is as follows：
The present invention innovatively provides a kind of continuous stream synthesis technique of new peroxide tert-butyl caprate (BNP), its feature
It is：Described synthesis technique is using tertbutanol peroxide, alkali lye, new decanoyl chloride as raw material, continuously successively through quaternization, esterification
Reaction and cancellation step obtain new peroxide tert-butyl caprate, and described synthesis technique enters in integrated continuous flow reactor
OK, reaction raw materials tertbutanol peroxide, alkali lye, new caprinoyl are uninterruptedly added in the charging aperture of the integrated continuous flow reactor
Chlorine, new peroxide tert-butyl caprate, described synthesis technique are uninterruptedly obtained in the integrated continuous flow reactor discharging opening
Without enlarge-effect.
The invention provides an efficient BNP continuous streams synthetic schemes without enlarge-effect, i.e. three kinds of reactants are continuous
In ground input reactor, and continuously collecting reaction product.The advantage of integrated reaction technique of the present invention and reactor, utilizes function
Unit warm area divides and the optimization of temperature setting and the synergy of functional unit, just can be abundant without increasing delay lie
Reaction, reaction can be foreshortened in 3 minutes total time, greatly improve the efficiency of technique, and synthesis technique is without enlarge-effect.Especially
It is can to complete esterification under higher temperature (more than 50 DEG C, even as high as more than 60 DEG C), greatly accelerates reaction
Process, without delay lie within a short period of time (generally within 180 seconds) i.e. it is available more than 98% (or even up to
More than 99.5%) the defects of in high yield, overcoming prior art, BNP high efficiency, high quality, large-scale production are realized.
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 BNP continuous flow process has enlarge-effect；Simultaneously the integrated continuous flow reactor due to
It is small without delay lie, small volume, floor space, greatly save factory building land used.
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, 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；It is preferred that
, 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)。
Further, yield >=98% of the new peroxide tert-butyl caprate；Preferably, the peroxidating neodecanoic acid uncle
Yield >=99% of butyl ester；It is furthermore preferred that yield >=99.5% of the new peroxide tert-butyl caprate
Further, content >=89.4% of the new peroxide tert-butyl caprate；Preferably, the peroxidating neodecanoic acid
Content >=90% of the tert-butyl ester；Content >=92% of the new peroxide tert-butyl caprate.
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 the esterification is 15~65 DEG C, preferably 35~60 DEG C, more preferably 35~55 DEG C, more
It is preferred that 35~45 DEG C, more preferably 50~60 DEG C.
Further, the temperature of the cancellation step is 5~35 DEG C, preferably 10~30 DEG C.
Further, the 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, the tertbutanol peroxide concentration be 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 1.18:1.
Further, the mol ratio of the new decanoyl chloride and tertbutanol peroxide is 0.6~1.1:1, preferably 0.7~0.9:
1, more preferably 0.75:1.
Further, to match with new peroxide tert-butyl caprate continuous stream synthesis technique, the integrated continuous flow
Reactor uses having unit structure, including alkalization unit, esterification unit and unit is quenched.Wherein：Described alkalization unit is used for
Tertbutanol peroxide t-butyl peroxy salt corresponding with alkali reaction generation is simultaneously transported to esterification unit；Described esterification unit
Reaction for t-butyl peroxy salt and new decanoyl chloride, which generates new peroxide tert-butyl caprate (BNP) and is transported to, is quenched list
Member；It is described be quenched unit be used for react be quenched and export the reaction mother liquor containing new peroxide tert-butyl caprate.
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 temperature of the esterification unit is 15~65 DEG C, preferably 35~60 DEG C, more preferably 35~55 DEG C, more
It is preferred that 35~45 DEG C, more preferably 50~60 DEG C.
Further, the temperature that unit is quenched is 5~35 DEG C, preferably 10~30 DEG C.
Further, to match with new peroxide tert-butyl caprate continuous stream synthesis technique, the integrated continuous flow
Reactor uses having unit structure, and each described unit 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, are serially connected between each unit.
Further, to match with new peroxide tert-butyl caprate continuous stream synthesis technique, the integrated continuous flow
Reactor uses having unit structure, and each described unit correspond at least one warm area, each warm area independently include one with
On reactor module or reactor module group, wherein reactor module group be made up of multiple reactor module serial or parallel connections,
It is serially connected between each warm area.
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, 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 peroxide salt；
(b) reaction solution of outflow warm area 1 enters warm area 2 after being mixed with new decanoyl chloride, 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 output contains the tertiary fourth of peroxidating neodecanoic acid
The reaction mother liquor of 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, the temperature of the warm area 2 is 15~65 DEG C, preferably 35~60 DEG C, more preferably 35~55 DEG C, more preferably
35~45 DEG C, more preferably 50~60 DEG C.
Further, the temperature of the warm area 3 is 5~35 DEG C, preferably 10~30 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 1.18:1.
Further, the mol ratio of new decanoyl chloride and tertbutanol peroxide is 0.6~1.1:1, preferably 0.7~0.9:1, more
Preferably 0.75:1.
Further, yield >=98% of the new peroxide tert-butyl caprate；Preferably, the peroxidating neodecanoic acid uncle
Yield >=99% of butyl ester；It is furthermore preferred that yield >=99.5% of the new peroxide tert-butyl caprate.
Further, content >=89.4% of the new peroxide tert-butyl caprate；Preferably, the peroxidating neodecanoic acid
Content >=90% of the tert-butyl ester；Content >=92% of the new peroxide tert-butyl caprate.
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 neodecanoic acid for being exclusively used in any form as previously described
The integrated continuous flow reactor of the continuous stream synthesis technique of the tert-butyl ester, described integrated continuous flow reactor use blocking
Unit, esterification unit and unit is quenched in structure, including alkalization, wherein：Described alkalization unit is used for tertbutanol peroxide and alkali
Reaction generates corresponding t-butyl peroxy salt and is transported to esterification unit；Described esterification unit is used for t-butyl peroxy salt
Reaction with new decanoyl chloride generates new peroxide tert-butyl caprate, and is transported to and unit is quenched；Described is quenched unit use
It is quenched in reaction and exports the reaction mother liquor containing new peroxide tert-butyl caprate.
Third 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 independently includes more than one reactor module or reactor module group, wherein reactor
Module group is made up of multiple reactor module serial or parallel connections, is 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, 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, the temperature of the warm area 2 is 15~65 DEG C, preferably 35~60 DEG C, more preferably 35~55 DEG C, more preferably
35~45 DEG C.
Further, the temperature of the warm area 3 is 5~35 DEG C, preferably 10~30 DEG C.
The present invention compared with the prior art, has the beneficial effect that：
1st, the efficient continuous stream synthesis of BNP is realized on integrated continuous flow reactor.That is, three kinds of reactants are constantly
In input reactor, and continuously collecting reaction product.The optimization with temperature setting is divided by means of functional unit warm area, without
Increase delay lie just can fully react, and greatly improve the efficiency of technique.It is at most 180 seconds 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 (within 180 seconds) cause the technical process it is safer.Wherein described reactor liquid holdup refers to
When operation reaches stationary state, the cumulative volume for the reaction mass having in any instant reactor.
3rd, BNP SADT is 20 DEG C, and esterification reaction temperature is set in compared with low temperature in some continuous flow process
When spending (15~35 DEG C), in order to reach appropriate yield, it is necessary to extend the reaction time using delay lie, and this obviously can drop
The efficiency of low successive reaction.And this technical process, esterification is still non-at a temperature of 55 DEG C of even more highs in esterification unit
Chang Pingwen is carried out, and does not observe significant decomposing phenomenon.With the raising of temperature, the yield of reaction significantly improves, without delay
Pipeline i.e. available 98% in high yield, so that the reaction time greatly shortens, can react complete in typically 3 minutes, produce
It is highly efficient.
4th, the physics according to BNP SADT and heat endurance and using raw material, chemical property, in one
Change in continuous flow reactor and devise three functional units, unit, the esterification unit of alkalizing and unit is quenched, wherein alkalization unit is used
In tertbutanol peroxide tert-butyl hydroperoxide sodium (potassium) corresponding with alkali reaction generation and it is transported to esterification unit；Esterification is single
Member is used for the reaction generation new peroxide tert-butyl caprate (BNP) of tert-butyl hydroperoxide sodium (potassium) and new decanoyl chloride and is conveyed
To unit is quenched；Be quenched unit be used for react be quenched and export the reaction mother liquor containing new peroxide tert-butyl caprate.Pass through three
Individual functional unit synergy, especially can complete ester under higher temperature (more than 50 DEG C, even as high as more than 60 DEG C)
Change reaction, greatly accelerate reaction process, can obtain (generally within 180 seconds) within a short period of time without delay lie
More than 98% (or even up to more than 99.5%) in high yield, the defects of overcoming prior art, realizes the efficient of BNP
Rate, high quality, large-scale production.
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 BNP 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, without delay lie in reactor.
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 new last of the ten Heavenly stems of raw material 3
Acyl chlorides) convey into warm area 2, warm area 2 is flowed through, reaction is complete.The reaction solution of outflow warm area 2 enters warm area 3 and cooled to be quenched instead
Should, collect reaction mother liquor.Mother liquor is layered, washing etc., you can obtain new peroxide tert-butyl caprate.Each response parameter and result are such as
Under：
Table 1：Material flow, warm area temperature, reaction time, content and yield
Embodiment 2-19
Using the operating method of embodiment 1, investigate and the anti-of new peroxide tert-butyl caprate is prepared under differential responses parameter
Between seasonable, content and yield, each Parameter Conditions and result are as shown in table 2 below and 3.
Table 2：Embodiment 2-19 material concentration and flow
Table 3：Temperature, reaction time, content and the yield of each warm areas of embodiment 2-19
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.
By embodiment 8 and 9, embodiment 11 and 12, embodiment 13 and 14 is understood, iodine scale is not to product
Content and yield have an impact, i.e., this technique and enlarge-effect are not present；From embodiment 16, enter even in relatively low 15 DEG C
Row esterification, without delay lie, reaction remains to complete at 3 minutes, and obtains 90.3% product content and 98.6%
Product yield；And under higher temperature (more than 50 DEG C, even as high as more than 60 DEG C), reaction can be completed in shorter time.
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 new peroxide tert-butyl caprate of no enlarge-effect, it is characterised in that：Described conjunction Into technique using tertbutanol peroxide, alkali lye, new decanoyl chloride as raw material, continuously through quaternization, esterification and it is quenched successively Step obtains new peroxide tert-butyl caprate, and described synthesis technique is carried out in integrated continuous flow reactor, described one The charging aperture of body continuous flow reactor uninterruptedly adds reaction raw materials tertbutanol peroxide, alkali lye, new decanoyl chloride, described one Body continuous flow reactor discharging opening uninterruptedly obtains new peroxide tert-butyl caprate, and 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；Preferably, 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 generation new peroxide tert-butyl caprate of butyl peroxy salt and new decanoyl chloride, and be transported to and unit is quenched；Described Be quenched unit be used for react be quenched and export the reaction mother liquor containing new peroxide tert-butyl caprate.
- 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, each described 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：The integrated continuous flow reactor Using having unit structure, each described unit corresponds at least one warm area, and each warm area is independently comprising more than one anti- Device module or reactor module group are answered, wherein reactor module group is made up of multiple reactor module serial or parallel connections, each warm area Between be serially connected.
- 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 Saline oxide；（b）The reaction solution of outflow warm area 1 enters warm area 2 after being mixed with new decanoyl chloride, flows through warm area 2, until reaction is complete；（c）The reaction solution of outflow warm area 2 enters warm area 3 and cooled reaction is quenched, and exports containing new peroxide tert-butyl caprate Reaction mother liquor.
- 9. the one of a kind of continuous stream synthesis technique for being exclusively used in the new peroxide tert-butyl caprate described in claim any one of 1-8 Body continuous flow reactor, it is characterised in that：Described integrated continuous flow reactor uses having unit structure, including alkalization list Member, esterification unit and unit is quenched, wherein：Described alkalization unit is used for tertbutanol peroxide and reacts the corresponding uncle of generation with alkali Butyl peroxy salt is simultaneously transported to esterification unit；Described esterification unit is used for the reaction of t-butyl peroxy salt and new decanoyl chloride New peroxide tert-butyl caprate is generated, and is transported to and unit is quenched；The described unit that is quenched is quenched and exported for reaction Reaction mother liquor containing new peroxide tert-butyl caprate.
- 10. a kind of continuous stream synthesis technique for being exclusively used in the new peroxide tert-butyl caprate described in claim any one of 1-8 Integrated continuous flow reactor, it is characterised in that：Described integrated continuous flow reactor uses having unit structure, each described Unit independently include more than one reactor module or reactor module group, wherein reactor module group is by multiple reactions Device block coupled in series composes in parallel, and is serially connected between each unit.
- 11. a kind of continuous stream synthesis technique for being exclusively used in the new peroxide tert-butyl caprate described in claim any one of 1-8 Integrated continuous flow reactor, it is characterised in that：Each described unit corresponds at least one warm area, and each warm area independently wraps Containing more than one reactor module or reactor module group, wherein reactor module group is connected or simultaneously by multiple reactor modules Connection forms, and is serially connected between each warm area.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610668327 | 2016-08-13 | ||
| CN2016106683275 | 2016-08-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107698480A true CN107698480A (en) | 2018-02-16 |
| CN107698480B CN107698480B (en) | 2020-09-11 |
Family
ID=61170878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710688986.XA Active CN107698480B (en) | 2016-08-13 | 2017-08-13 | Continuous flow synthesis process of tert-butyl peroxyneodecanoate without amplification effect |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107698480B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892616A (en) * | 2018-08-31 | 2018-11-27 | 凯莱英生命科学技术(天津)有限公司 | Prepare continuous device and its application of benzaldehydes intermediate |
| 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 |
| CN112892436A (en) * | 2020-12-30 | 2021-06-04 | 杭州新本立医药有限公司 | Full continuous flow production process of 1-alkyl-5-hydroxypyrazole |
| CN115385838A (en) * | 2022-07-28 | 2022-11-25 | 鄂尔多斯市瀚博科技有限公司 | Preparation method of cumyl peroxyneodecanoate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05307102A (en) * | 1992-04-30 | 1993-11-19 | Kureha Chem Ind Co Ltd | Optical lens |
| 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 |
| CN101479239A (en) * | 2006-04-27 | 2009-07-08 | 阿克马法国公司 | Process for synthesizing selected organic peroxides |
| CN104592080A (en) * | 2014-11-26 | 2015-05-06 | 淄博正华助剂股份有限公司 | Method for preparing tert-butyl peroxyneodecanoate (BNP) through continuous flow |
-
2017
- 2017-08-13 CN CN201710688986.XA patent/CN107698480B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05307102A (en) * | 1992-04-30 | 1993-11-19 | Kureha Chem Ind Co Ltd | Optical lens |
| 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 |
| CN101479239A (en) * | 2006-04-27 | 2009-07-08 | 阿克马法国公司 | Process for synthesizing selected organic peroxides |
| CN104592080A (en) * | 2014-11-26 | 2015-05-06 | 淄博正华助剂股份有限公司 | Method for preparing tert-butyl peroxyneodecanoate (BNP) through continuous flow |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108892616A (en) * | 2018-08-31 | 2018-11-27 | 凯莱英生命科学技术(天津)有限公司 | Prepare continuous device and its application of benzaldehydes intermediate |
| CN112892436A (en) * | 2020-12-30 | 2021-06-04 | 杭州新本立医药有限公司 | Full continuous flow production process of 1-alkyl-5-hydroxypyrazole |
| CN115385838A (en) * | 2022-07-28 | 2022-11-25 | 鄂尔多斯市瀚博科技有限公司 | Preparation method of cumyl peroxyneodecanoate |
| CN115385838B (en) * | 2022-07-28 | 2024-03-08 | 鄂尔多斯市瀚博科技有限公司 | Preparation method of cumyl peroxyneodecanoate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107698480B (en) | 2020-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107698480A (en) | A kind of continuous stream synthesis technique of the new peroxide tert-butyl caprate of no enlarge-effect | |
| CN107698479A (en) | A kind of continuous stream synthesis technique of the ethylhexyl carbonate tert-butyl ester of peroxidating 2 of no enlarge-effect | |
| US10947189B2 (en) | Online continuous flow process for the synthesis of organic peroxides using hydrogen peroxide as raw material | |
| CN1757654B (en) | Apparatus for continuous polymerization and method for continuous polymerizing using the same | |
| CN103992443B (en) | The method that room temperature batch mixing method prepares polycarboxylate water-reducer | |
| US6252016B1 (en) | Continuous polymerization in a non-cylindrical channel with temperature control | |
| Roberge et al. | Development of an industrial multi‐injection microreactor for fast and exothermic reactions–part II | |
| CN104262196B (en) | A kind of Ammoximation reaction and separation coupling technique and device | |
| CN108295782B (en) | Microchannel reactor and three acetylation reactions method in microchannel reactor | |
| US9624176B2 (en) | Method for preparing caprolactam by using a microreactor under lewis acid catalysis | |
| CN109876747A (en) | Pillar flow reactor and pillar continuous reaction system | |
| CN109553560A (en) | A kind of online Total continuity stream production technology directly preparing organic peroxide by alcohol or alkane | |
| CN107253913B (en) | Method for preparing chloroenyne by using microchannel reactor | |
| JPH11240904A (en) | Continuous production of polymer | |
| CN103055792A (en) | Oscillation tube type reactor for liquid phase oxidization of cyclohexane and application method thereof | |
| CN208275392U (en) | A kind of continuous neutralization device | |
| CN104650010A (en) | Method for preparing hexafluoropropylene oxide | |
| US9550731B2 (en) | Method for phase transfer synthesis of organic peroxides | |
| EP1174184A3 (en) | Sequential reaction system | |
| CN104470883B (en) | The alcohol radical hypohalogenous acids oxidation of quick catalysis | |
| WO2019034006A1 (en) | Online fully continuous flow production process for directly preparing organic peroxide from alcohol or alkane | |
| CN204365250U (en) | A kind of feeding device of the suspension polymerization preparation method for polyvinyl chloride | |
| CN212758544U (en) | Dichlorvos microchannel apparatus for producing | |
| CN110256320A (en) | The synthetic method of dicetyl peroxydicarbonate two (2- ethylhexyl) ester | |
| CN114933527B (en) | Method for continuously synthesizing o-methylbenzoyl chloride in micro-channel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |