CN108047042A - A kind of method using high-gravity technology synthesis 2,3,5- trimethylhydroquinone diester - Google Patents
A kind of method using high-gravity technology synthesis 2,3,5- trimethylhydroquinone diester Download PDFInfo
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Abstract
The invention discloses it is a kind of using high-gravity technology synthesize 2,3,5 trimethylhydroquinone diester method, including：(1) acylating agent and acidic catalyst are mixedly configured into solution A；(2) ketoisophorone solution is B solution；(3) solution A and B solution are passed through supergravity reactor to react.This method reduces the generation of 3,4,5 trimethyl pyrocatechol of by-product to reduce reaction temperature, is finally reached the purpose for improving 2,3,5 trimethylhydroquinone diester purity of product by using high-gravity technology mass transfer enhancement efficiency.
Description
Technical field
The present invention relates to a kind of method for synthesizing 1,4-diacetoxy-2,3,5-trimethylbenzene more particularly to one kind in hypergravity condition
Under, in the presence of acidic catalyst, by ketoisophorone and anhydride reaction, prepare the side of 1,4-diacetoxy-2,3,5-trimethylbenzene
Method.
Background technology
1,4-diacetoxy-2,3,5-trimethylbenzene is the important intermediate for preparing vitamin E, can pass through condensation with different vegetable alcohol
Reaction generation Vitwas E, also reacts generation vitamin E with different vegetable alcohol after hydrolyzable.Synthesis 2,3,5- front threes at present
The method of base hydroquinone di-esters has very much, but there are it is certain the defects of.
It is disclosed in DE2149159, US5955628, CN1420859A and EP0850912 using Bronsted acid or Louis
The method that acid prepares DA-TMHQ for catalyst KIP with acetic anhydride.The defects of such method is due to reactor, catalysis
Agent consumption is big, temperature drift, and by-product is mostly generated with a small amount of pernicious gas such as sulfur dioxide simultaneously.
CN104387269A discloses a kind of preparation method of two alkanoic acid ester of 2,3,5-trimethylhydroquinone (TMHQ-DA),
Preparation method is：In the presence of magnetic solid acid catalyst, by 2,6,6-trimethylcyclohex-2-ene-1,4-dione (KIP) with
Acylating agent rearrangement reaction and realize.This method catalyst preparation is complicated, and cost of manufacture is high, and environment easy to pollute.
CN102180793A is reported using α-isophorone as raw material, it is made to be reacted in the presence of a catalyst with acylating agent
To the enol isomers carboxylate of isophorone；Solvent DMSO and heteropllyacids catalyst are added in enol isomers carboxylate
And alkali, air is blasted, the mono-esterification product of ketoisophorone is obtained by the reaction；The solvent in the mono-esterification product is recycled,
Then 2,3,5- trimethylhydroquinone diester is obtained by the reaction in the presence of carboxylic acid anhydrides and catalyst.The invention should needed for step compared with
It is more, and product purity is generally relatively low after crystallization.
CN101607896A is catalyst using acidic ion liquid, under -20 DEG C~130 DEG C of reaction temperature, makes oxygen
Acylated preparation 2,3,5- trimethylhydroquine dialkanoates are reset for isophorone.The invention solvent loss is big, and ionic liquid valency
Lattice are expensive, and temperature is high, and side reaction is more, is not easy to realize industrialized production.
High-gravity technology is a kind of typical chemical process reinforcement technique, it can increase substantially reaction selectivity and turn
Rate is a kind of multinomial quick for needing to strengthen interphase mass transfer, heat transfer and molecular mixing under Elevated Gravity
The preferable reinforcement technique of reaction process has great importance for the miniaturization or even micromation of chemical process.Using overweight
Power reactor simulation Elevated Gravity can strengthen transmission and reaction process, and then transmission is significantly increased and is imitated with reaction process
Rate can be reduced significantly the volume of reaction and separator.Its principle is explained by taking rotary packed bed as an example：Fluid is in centrifugal force field
Be torn into tiny drop, brin or liquid film under environment, generate substantial amounts of quick newer surface area, strengthen significantly mass transfer and
Mixed process, the transmission especially limited by mass transfer and mixing and reaction process.High-gravity technology there is no to apply 2,3 at present,
The preparation of 5- trimethylhydroquinone diester.
The content of the invention
In order to solve in the preparation process of 1,4-diacetoxy-2,3,5-trimethylbenzene, there are 3,4,5- trimethyl coke catechu of by-product
The higher problem of two ester content of phenol uses high-gravity technology mass transfer enhancement efficiency so as to reduce by-product 3 the present invention provides a kind of,
The generation of 4,5- trimethyl pyrocatechols is to obtain the technical solution of high-purity 2,3,5- trimethylhydroquinone diester.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of method using high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, this method include：
(1) acylating agent and acidic catalyst are mixedly configured into solution A；
(2) ketoisophorone solution is B solution；
(3) solution A and B solution are passed through supergravity reactor to react.
Further, the acidic catalyst is the catalyst commonly used in the prior art for this reaction.Can be matter
The one or more of sub- acid catalyst or lewis acid catalyst；The Bronsted acid can use inorganic acid (such as sulfuric acid, salt
Acid, phosphoric acid, fluoboric acid and hydrofluoric acid), organic acid (such as sulfonic acid such as P-TOLUENE SULFO ACID 99, benzene sulfonic acid, Loprazolam, trifluoromethane sulfonic acid
And ethane sulfonic acid；Halogenated carboxylic acid or halogen-containing carboxylic acid such as monoxone, trichloroacetic acid and trifluoroacetic acid；Picric acid) and
Hammentt Acidity function Hs0Super acids (such as H less than -11.932SO4-SO3、HF-NbF5、SbF5、HF-Sb5、Sb5-FSO3H、
FSO3H-TaF5、SbF5-CF3SO3H), preferably hydrochloric acid, sulfuric acid, H2SO4-SO3；BF can be used in the lewis acid3、BF3OEt2、
AlCl3、FeCl3、ZnCl2、TiCl4、SnCl2、InCl3Deng preferably FeCl3、ZnCl2.The acidic catalyst can also be ion
Liquid (such as acidic ion liquid, degradation property).Above-mentioned acidic catalyst can also be loaded on one or more loads
On body or porous carrier.Above-mentioned acidic catalyst (including support type) is that can promote ketoisophorone weight in the prior art
The catalyst of the acylated generation 1,4-diacetoxy-2,3,5-trimethylbenzene of row, can refer to patent CN1113851C, DE2149159,
US5955628, CN1420859A, DE19627977, CN1886361A, CN101607896A, CN104529761A etc.；It is wherein excellent
The catalyst of choosing at least has the advantages that following a kind of：Pollution is less, cheap, preparation is simple, catalytic activity is good, to equipment requirement
It is low, suitable for Elevated Gravity.In Elevated Gravity, catalyst generally selects liquid form, directly liquid can be selected to urge
Agent can also make catalyst dissolving or lo-tionized；If solid catalyst, solid catalysis that intensity can be selected larger
Agent should either be urged using the methods of catalyst is fixed on supergravity reactor or catalyst is supported on filler to reduce
Agent wear and caused by catalyst loss, reduce the negative consequences such as catalytic efficiency.
Further, the acylating agent is the one or more in carboxylic acid anhydrides or carboxylic acid halides.The carboxylic acid anhydrides is excellent
Select C2-C10Aliphatic series, cyclic aliphatic and aromatic series carboxylic acid anhydride (such as acetic anhydride, propionic andydride, butyric anhydride, isobutyric anhydride, hexamethylene acid anhydrides, benzene
Formic anhydride etc.)；The carboxylic acid halides can be the corresponding carboxylic acid halides of carboxylic acid anhydride being previously mentioned.
Further, acidic catalyst and ketoisophorone molar ratio are 1:10~200, preferably 1:20~50；Oxo
The molar ratio of isophorone and acylating agent is 1:2.5~5, preferably 1:3~4.
In the present invention, solution A and B solution each lead into supergravity reactor and are reacted, and B solution is passed through rate by surpassing
Gravity reactor size determines that the addition rate of solution A is determined by ingredient proportion.
Further, the reaction temperature of the reaction can change between -10~60 DEG C, preferably 0~30 DEG C；High temperature energy
Make direction offset of the reaction towards 3,4,5- trimethyl pyrocatechol diester of generation, select relatively low temperature so that side reaction is dropped significantly
It is low；In the prior art, using ketoisophorone synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene reaction temperature generally 40 DEG C with
Upper even as high as 130 DEG C, excessively high temperature can cause the purity of product inadequate, when will react carry out at low temperature when, reaction
Time is again comparatively very long, when the inventory of especially reaction mass is larger (being usually more than 40h)；The technical program
Using high-gravity technology so that the reaction time can be significantly reduced while the reaction carries out at low temperature again, reach in the short time
The technique effect of interior efficient output high-purity 2,3,5- trimethylhydroquinone diester.
Further, the rotating speed of the supergravity reactor is 400~2000r/min, preferably 800~1600r/min.It can
According to actual process needs, to consider input and output, the rotating speed for adjusting supergravity reactor carrys out the big of the adults field of force
Small and material residence time in super gravity field is optimal to achieve the effect that.
By above-mentioned reaction, the conversion ratio of ketoisophorone can reach more than 95%, it is preferred that will be above-mentioned anti-
Reaction solution after answering, then be passed through in reactor and carry out further reaction so that remaining unreacted ketoisophorone thoroughly to be converted
Into 1,4-diacetoxy-2,3,5-trimethylbenzene, the reactor is supergravity reactor or interior recycle super-gravity reactor；It can also
It is the reactor existing in the prior art such as reaction kettle or flask, this reaction is preferably passed through in supergravity reactor again to be carried out, optimal
It gates and is carried out in interior recycle super-gravity reactor.Reaction temperature is -10~100 DEG C, preferably 30~60 DEG C；Due in reaction solution
Unreacted ketoisophorone is less, final choice is influenced smaller, and reaction process afterwards can be slow, can be with
Preferentially making choice higher temperature according to actual process situation, thoroughly the reaction was complete so that aoxidizing isophorone, when reaction exists
It when being carried out in supergravity reactor or interior recycle super-gravity reactor, is preferred with 30~60 DEG C, when reaction is not reacted in hypergravity
When being carried out in device, then 60 DEG C are at least wanted.
Above-mentioned two-step reaction carries out in continuous or discontinuous manner.
Supergravity reactor in above-mentioned two-step reaction can be same, may not be same；When not being same
When a, the pattern of reactor can it is identical can not also be identical.
Specifically：
After the completion of first step reaction, reaction solution collection is passed through or is passed directly into and reacts identical or different with the first step
The prior arts such as supergravity reactor or reaction kettle, flask conventional reactor carries out second step reaction；Preferably, the first step is anti-
Answer continuous feed react after be passed through immediately in the supergravity reactor (except interior recycle super-gravity reactor) of second step, due to
The residence time is shorter in supergravity reactor, and generally 1~2s, two-step reaction are almost carried out at the same time；It is furthermore preferred that second step is anti-
It should preferably be carried out in a discontinuous manner in interior recycle super-gravity reactor；Although remaining unreacted ketoisophorone is simultaneously
Seldom, but the direction progress being difficult to generation 1,4-diacetoxy-2,3,5-trimethylbenzene is compared in reaction；In common reactor into
Row still needs long time more than when small (at least 6), if (interior recycle super-gravity reactor removes in supergravity reactor
In outside), although the reaction time is very short, reaction not exclusively thorough situation can be had at a lower temperature by reacting, and second
Recycle super-gravity reactor contributes in the short period at a lower temperature (1~3h) by the different Fo Er of remaining oxo in step reaction
Thoroughly the reaction was complete for ketone.
Further, on supergravity reactor coupling ultrasonic ripple, microwave, magnetic field etc. strengthen means one or more,
Further strengthen mixing and the mass transfer effect in revolving bed.
Further, unreacted acid anhydrides is recycled by being evaporated under reduced pressure, then described 2 is purified by crystallizing, 3,5- tri-
Methylnaphthohydroquinone diester.
Preferred crystallization temperature is 0~30 DEG C.
General before crystallization first to add in n-hexane and water progress liquid separation, obtained n-hexane is mutually crystallized.
The supergravity reactor can be it is vertical can also be horizontal；Can be that rotary packed bed hypergravity is anti-
Answer device, deflector type supergravity reactor, helical duct supergravity reactor, rotating compact disc formula supergravity reactor or fixed-rotor
Any supergravity reactor in the prior art such as formula supergravity reactor.It is preferred that rotary packed bed hypergravity reacts
Device.
Corresponding transformation, which is made, in the internal structure of supergravity reactor can obtain interior recycle super-gravity reactor.
Compared with the existing technology, the invention has the advantages that：
1st, due to being reacted in supergravity reactor, the mass transfer effect in reaction process is greatly enhanced so that
While low-temp reaction is kept, the process of reaction is substantially accelerated, and greatly reduces the reaction time, so that the place of reactor
Reason efficiency is significantly promoted, and the size of equipment greatly reduces, reduces energy consumption, the investment for reducing equipment and industrial cost；
2nd, after high-gravity technology is handled, the conversion ratio and selectivity of ketoisophorone are greatly improved, and make
The purity for the 2,3,5- trimethylhydroquinone diester that must be generated increases；
3rd, by reaction solution is further reacted, the yield of ketoisophorone is further improved.
Specific embodiment
The present invention synthesizes target product 1,4-diacetoxy-2,3,5-trimethylbenzene using following methods, but the invention is not restricted to listed
The embodiment gone out should also be included in other any well known changes in interest field of the presently claimed invention.
Comparative example 1
By 408g (4mol) aceticanhydride, 5.07g (0.05mol, mass fraction 36%) HCl/water solution, 1.625g (0.01mol)
FeCl3It is added to (152.95g, content 99.5%, 1mol) ketoisophorone liquid in 1000mL three-neck flasks, 50 DEG C are stirred
Mix reaction for 24 hours, sampling gas chromatographic analysis KIP conversion ratios are that 85.0%, DA-TMHQ selectivity is 93.0%, 3,4,5- front threes
Base pyrocatechol is 4.0%.
Embodiment 1
By 4900g (48mol) aceticanhydride, 60.8g (0.6mol, mass fraction 36%) HCl/water solution and 19.5g
(0.12mol)FeCl3Be mixedly configured into solution A, B solution for ketoisophorone liquid (1835g, content 99.5%,
12mol).Solution A is entered by revolving bed inlet liquid distributor in revolving bed 1 with B solution, and solution A feed rate is
83.0g/min, B solution feed rate are 30.6g/min, and 1 rotating speed of revolving bed is 1200r/min, and reaction temperature is 20 DEG C, reaction
Liquid enters 2 liquid-inlet of revolving bed from 1 liquid outlet of revolving bed, and 2 rotating speed of revolving bed is 1200r/min, and reaction temperature is 50 DEG C,
Reaction solution enters reaction solution collecting tank from 2 liquid outlet of revolving bed, samples gas chromatographic analysis, KIP conversion ratios up to 99.5%,
DA-TMHQ is 1.1% selectively up to 98.1%, 3,4,5- trimethyl pyrocatechol.
Note：Revolving bed is supergravity reactor
Embodiment 2-20
Note：In embodiment 2-18, acid anhydrides is acetic anhydride；In embodiment 19, acid anhydrides is hexamethylene acid anhydrides；In embodiment 20, acid
Acid anhydride is benzoyl oxide；HCl/ZnCl in each embodiment2Or HCl/FeCl3It is 5 that ratio, which is,:1 (molar ratio).
Embodiment 21
By 4900g (48mol) aceticanhydride, 60.8g (0.6mol, mass fraction 36%) HCl/water solution and 19.5g
(0.12mol)FeCl3Be mixedly configured into solution A, B solution for ketoisophorone liquid (1835g, content 99.5%,
12mol).Solution A is entered by revolving bed inlet liquid distributor in revolving bed 1 with B solution, and solution A feed rate is
83.0g/min, B solution feed rate are 30.6g/min, and 1 rotating speed of revolving bed is 1200r/min, and reaction temperature is 20 DEG C, reaction
Liquid enters revolving bed 2 (revolving bed 2 is interior circulation rotating bed) liquid-inlet from 1 liquid outlet of revolving bed, and 2 rotating speed of revolving bed is
1200r/min, reaction temperature are 50 DEG C, residence time 3h, and reaction solution enters reaction solution collecting tank from 2 liquid outlet of revolving bed,
Gas chromatographic analysis is sampled, KIP conversion ratios are selective up to 98.1%, 3,4,5- trimethyl pyrocatechol up to 99.9%, DA-TMHQ
For 1.1%.
Embodiment 22
By reaction solution in embodiment 21 be transferred to 10L recycling kettle be recovered under reduced pressure to 145 DEG C, add in 2400g n-hexanes with
After 240g water extracting and demixings, 20 DEG C of recrystallizations are cooled to.Crystallization drying is precipitated in filtering, can obtain filter cake 2594.0g, purity is
99.8%, yield 93.20%.
Claims (10)
- A kind of 1. method using high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, which is characterized in that including：(1) acylating agent and acidic catalyst are mixedly configured into solution A；(2) using ketoisophorone liquid as B solution；(3) solution A and B solution are passed through in supergravity reactor and reacted.
- 2. as described in claim 1 using the method for high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, feature exists In the acidic catalyst is the one or more of bronsted acid catalyst or lewis acid catalyst；The acylating agent is One or more in carboxylic acid anhydrides or carboxylic acid halides.
- 3. as claimed in claim 2 using the method for high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, feature exists In the acidic catalyst is HCl, H2SO4、H2SO4-SO3、FeCl3、ZnCl2One or more；The acylating agent is Acetic anhydride, propionic andydride, butyric anhydride, isobutyric anhydride, hexamethylene acid anhydrides, benzoyl oxide and one kind in the corresponding carboxylic acid halides of the acid anhydrides or It is a variety of.
- 4. as described in claim 1 using the method for high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, feature exists In acidic catalyst is 1 with ketoisophorone molar ratio:10~200；The molar ratio of ketoisophorone and acylating agent is 1: 2.5~5；The reaction temperature of the reaction is -10~60 DEG C；The rotating speed of the supergravity reactor is 400~2000r/min；Preferably, the acidic catalyst is 1 with ketoisophorone molar ratio:20~50；Ketoisophorone and acyl The molar ratio of agent is 1:3~4；The reaction temperature of the reaction is 0~30 DEG C；The rotating speed of the supergravity reactor is 800 ~1600r/min.
- 5. the method that such as claim 1-4 any one of them synthesizes 1,4-diacetoxy-2,3,5-trimethylbenzene using high-gravity technology, It is characterized in that, by the reaction solution after the reaction, it is passed through in reactor is further reacted again；Wherein, the reaction temperature further reacted is -10~100 DEG C, the reactor for supergravity reactor or Interior recycle super-gravity reactor or reaction kettle or flask.
- 6. as claimed in claim 5 using the method for high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, feature exists In the reaction temperature further reacted is 30~60 DEG C；The reactor is super for supergravity reactor or interior Xun Huan Gravity reactor.
- 7. as claimed in claim 5 using the method for high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene, feature exists In two-step reaction carries out in continuous or discontinuous manner.
- 8. the method using high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene as described in claim 1 or 6, feature It is, the one or more in coupling ultrasonic ripple or microwave or magnetic field on supergravity reactor.
- 9. the method using high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene as described in claim 1 or 6, feature It is, unreacted acid anhydrides is recycled by being evaporated under reduced pressure, then by crystallizing come purified product, the crystallization temperature is 0~30 ℃。
- 10. the method using high-gravity technology synthesis 1,4-diacetoxy-2,3,5-trimethylbenzene as described in claim 1 or 6, special Sign is that the supergravity reactor is vertical or horizontal rotary packed bed supergravity reactor, deflector type hypergravity is anti- Answer device, helical duct supergravity reactor, rotating compact disc formula supergravity reactor or fixed-rotator type supergravity reactor.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970553A (en) * | 2019-04-03 | 2019-07-05 | 万华化学集团股份有限公司 | A method of preparing 2,3,5- trimethylhydroquinone diester |
| CN111675612A (en) * | 2020-06-16 | 2020-09-18 | 万华化学集团股份有限公司 | Method for preparing 2,3, 5-trimethylhydroquinone diester |
| CN113416433A (en) * | 2021-03-29 | 2021-09-21 | 北京化工大学 | Preparation method of amorphous chromium hydroxide dispersoid |
| CN113649076A (en) * | 2021-09-17 | 2021-11-16 | 万华化学(四川)有限公司 | Method for synthesizing trimethylhydroquinone diester through bimetal oxidation catalysis |
| CN115260224A (en) * | 2022-08-04 | 2022-11-01 | 浙江锦华新材料股份有限公司 | Method for producing vinyl tributyrinoxime silane by supergravity method |
| CN115260029A (en) * | 2022-06-29 | 2022-11-01 | 万华化学集团股份有限公司 | Method for producing 2,3,5-trimethylhydroquinone diester by using bubble column reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109970553A (en) * | 2019-04-03 | 2019-07-05 | 万华化学集团股份有限公司 | A method of preparing 2,3,5- trimethylhydroquinone diester |
| CN109970553B (en) * | 2019-04-03 | 2021-09-03 | 万华化学集团股份有限公司 | Method for preparing 2,3, 5-trimethylhydroquinone diester |
| CN111675612A (en) * | 2020-06-16 | 2020-09-18 | 万华化学集团股份有限公司 | Method for preparing 2,3, 5-trimethylhydroquinone diester |
| CN111675612B (en) * | 2020-06-16 | 2023-03-03 | 万华化学集团股份有限公司 | Method for preparing 2,3,5-trimethylhydroquinone diester |
| CN113416433A (en) * | 2021-03-29 | 2021-09-21 | 北京化工大学 | Preparation method of amorphous chromium hydroxide dispersoid |
| CN113649076A (en) * | 2021-09-17 | 2021-11-16 | 万华化学(四川)有限公司 | Method for synthesizing trimethylhydroquinone diester through bimetal oxidation catalysis |
| CN113649076B (en) * | 2021-09-17 | 2022-08-05 | 万华化学(四川)有限公司 | Method for synthesizing trimethylhydroquinone diester through bimetal oxidation catalysis |
| CN115260029A (en) * | 2022-06-29 | 2022-11-01 | 万华化学集团股份有限公司 | Method for producing 2,3,5-trimethylhydroquinone diester by using bubble column reactor |
| CN115260029B (en) * | 2022-06-29 | 2024-04-09 | 万华化学集团股份有限公司 | Method for producing 2,3, 5-trimethylhydroquinone diester by using bubble column reactor |
| CN115260224A (en) * | 2022-08-04 | 2022-11-01 | 浙江锦华新材料股份有限公司 | Method for producing vinyl tributyrinoxime silane by supergravity method |
| CN115260224B (en) * | 2022-08-04 | 2024-04-02 | 浙江锦华新材料股份有限公司 | Method for producing vinyl tributyl ketoximino silane by supergravity method |
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