CN109851498A - A kind of New Type of Ethylene ketone ester is combined to the preparation method of IPA - Google Patents
A kind of New Type of Ethylene ketone ester is combined to the preparation method of IPA Download PDFInfo
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- CN109851498A CN109851498A CN201910080025.XA CN201910080025A CN109851498A CN 109851498 A CN109851498 A CN 109851498A CN 201910080025 A CN201910080025 A CN 201910080025A CN 109851498 A CN109851498 A CN 109851498A
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- ipa
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Abstract
A kind of New Type of Ethylene ketone ester is combined to the preparation method of IPA, comprising the following steps: (1) ketenes is continuously fed into the reaction kettle of the esterification equipped with acetone soln, while putting into S2O8 ‑/ZrO2‑TiO2Microspheres with solid catalyst, is stirred；(2) crude product refining for obtaining step (1), crystallisation by cooling, finally drying obtains IPA product.Preparation method of the present invention is compared with other methods, and catalytic efficiency is greatly promoted, and has many advantages, such as that reaction process is simple, the reaction time is short, the operation and special equipment without any complexity.In addition, the method that the present invention uses is nearly free from the three wastes, the environmentally protective of industrial production technology is realized.
Description
Technical field
The invention belongs to field the field of chemical synthesis, and in particular to a kind of New Type of Ethylene ketone ester is combined to the preparation side of IPA
Method.
Background technique
Methylvinyl acetate (isopropenyl acetate, IPA) is a kind of colourless, transparency liquid, flash-point: 18 DEG C, fusing point :-
92.9 DEG C, boiling point: 92-94 DEG C, density: 0.913g/cm3, it is miscible in alcohol, ether, ketone etc., property is stablized.Industrial main use
In synthesis acetylacetone,2,4-pentanedione, analytical reagent is also served as；The refining solvent of fluocinolone acetonide series of products is mainly used as in medicine.
Inorganic liquid acid is that IPA prepares most important early stage catalyst, and, process flow more since there are side reactions is long, sets
Standby corrosivity is big, post-processing is difficult, easily cause the problems such as environmental pollution and gradually by more environmentally-friendly efficient new catalyst institute
Replace.
Catalytic esterification is most commonly seen with molecular sieve, solid super-strong acid and cation exchange resin, molecular sieve and solid
Superacid catalysis esterification, catalytic activity is low under low temperature, and poor selectivity under high temperature still has gap from industrial application；And ion
Although exchanger resin has preferable catalytic activity at low temperature, the presence of water has very big shadow to resin catalysis activity in reaction
It rings, is easy to cause resin catalysis is active to reduce even complete deactivation.
Summary of the invention
The purpose of the present invention is to solve the shortcomings of the prior art and providing the system that a kind of New Type of Ethylene ketone ester is combined to IPA
Preparation Method improves esterification yield and is realized synthesis IPA intermediate work using novel catalyst ketenes esterification
Industry production technology it is environmentally protective, do not generate the three wastes substantially.
A kind of New Type of Ethylene ketone ester is combined to the preparation method of IPA, comprising the following steps: (1) by ketenes continuous feed
Into the reaction kettle of the esterification equipped with acetone soln, while putting into S2O8 -/ZrO2-TiO2Microspheres with solid catalyst, is stirred；(2)
The crude product refining that step (1) is obtained, crystallisation by cooling, finally drying obtains IPA product.
Preferably, the esterification temperature in the reaction kettle of the esterification is 55-75 DEG C；
Preferably, the S2O8 -/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 5%-10% of acetone quality.
Further, the S2O8 -/ZrO2-TiO2Microspheres with solid catalyst the preparation method comprises the following steps: (1) by isopropyl titanate and/
Or titanium tetrachloride and/or titanium sesquisulfate, zirconium oxychloride are stirred；(2) basic solvent is added and is greater than 9 to PH, the reaction was continued 1-
3h is aged 2-5h；(3) product of generation is washed repeatedly to neutrality and removes Cl-；(4) by products therefrom in (NH4)2S2O8It is molten
24-48h is impregnated in liquid, grinds to obtain powder after dry；(5) by gained powder be transferred in high-temperature high-pressure reaction kettle carry out hydro-thermal it is anti-
It answers；(6) it is cooled to room temperature, washing filtering is dried in vacuo at 45-75 DEG C；(7) dried product exhibited is forged in air atmosphere
It burns, obtains S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
Preferably, isopropyl titanate and/or titanium tetrachloride and/or titanium sesquisulfate, two class object of zirconium oxychloride in the step (1)
For matter in terms of Zr and Ti, the molar ratio of Zr and Ti are 0.1-10:100.
Further, the isopropyl titanate and/or titanium tetrachloride and/or titanium sesquisulfate, zirconium oxychloride use surface-active
Agent carries out pre-treatment.
Preferably, the surfactant is one of cetylamine, octadecylamine or dodecyl sodium sulfate or a variety of.
Preferably, step (2) the neutral and alkali solvent is ammonium hydroxide.
Preferably, in the step (5) hydro-thermal reaction condition are as follows: heat 12-24h at 120-185 DEG C.
Preferably, calcination temperature is 400-600 DEG C in the step (7), calcination time 30-100min.
Preferably, the partial size of the microspheres with solid catalyst of preparation is at 1-8 μm.
The medicine have the advantages that
With ZrO2For active component, in ZrO2Ti is introduced in microstructure is remarkably improved catalyst surface acid strength；Use over cure
Acid ion impregnates solid catalyst, forms the stronger acid site Lewis, further improves the acid of solid catalyst
Property；
S made from hydro-thermal method2O8 -/ZrO2-TiO2Microspheres with solid catalyst has mesoporous and spherical structure uniform, has biggish
Specific surface area effectively improves the catalytic efficiency of ketenes lactate synthesis IPA；
Preparation method of the present invention is compared with other methods, and has that reaction process is simple, the reaction time is short, is not necessarily to any complexity
Operation and special equipment the advantages that；In addition, the method that the present invention uses is nearly free from the three wastes, industrial production skill is realized
Art it is environmentally protective.
Specific embodiment
Embodiment 1
At room temperature, it is proportionally added into zirconium oxychloride and titanium tetrachloride, is added cetylamine solution (1wt%), so that Zr and Ti in solution
Molar ratio be 1:100, after being stirred 30s, solution left standstill settle 18h.Product and solution are washed with deionized water and ethyl alcohol
3 times are washed, drying and grinding.Ammonium hydroxide is added into gained powder to PH in the section 9-10, reaction time 2h, then is aged 3h.By institute
Obtaining product and being washed repeatedly to PH is neutrality, and uses AgNO3Detection guarantees without Cl-, then by product 1.5mol/L (NH4)2S2O8It is impregnated in solution for 24 hours, vacuum drying grinding.
Product is transferred in high-temperature high-pressure reaction kettle, second alcohol and water is added, hydro-thermal reaction 18h, is cooled at 160 DEG C
It is washed respectively 3 times after room temperature with deionized water and ethyl alcohol, filters, be dried in vacuo at 60 DEG C, by dry product in air gas
120min is calcined at 500 DEG C in atmosphere.Obtain S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
Ketenes is continuously fed into the reaction kettle of the esterification equipped with fixed acetone soln, S is put into2O8 -/ZrO2-TiO2Gu
Body microspherical catalyst, S2O8 -/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 8% of acetone quality, and adjusting temperature is 60
DEG C, it is stirred；By gained crude product refining, crystallisation by cooling, filtering drying obtains IPA product.
Embodiment 2
At room temperature, it is proportionally added into zirconium oxychloride and titanium tetrachloride, is added octadecylamine solution (1wt%), so that Zr and Ti in solution
Molar ratio be 10:100, after being stirred 30s, solution left standstill settle 12h.Product and solution are washed with deionized water and ethyl alcohol
3 times are washed, drying and grinding.Ammonium hydroxide is added into gained powder to PH in the section 10-11, reaction time 1h, then is aged 2h.By institute
Obtaining product and being washed repeatedly to PH is neutrality, and uses AgNO3Detection guarantees without Cl-, then by product 1.5mol/L (NH4)2S2O832h, vacuum drying grinding are impregnated in solution.
Product is transferred in high-temperature high-pressure reaction kettle, second alcohol and water is added, hydro-thermal reaction 18h, is cooled at 160 DEG C
It is washed respectively 3 times after room temperature with deionized water and ethyl alcohol, filters, be dried in vacuo at 50 DEG C, by dry product in air gas
120min is calcined at 550 DEG C in atmosphere.Obtain S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
Ketenes is continuously fed into the reaction kettle of the esterification equipped with fixed acetone soln, S is put into2O8 -/ZrO2-TiO2Gu
Body microspherical catalyst, S2O8 -/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 5% of acetone quality, and adjusting temperature is 70
DEG C, it is stirred；By gained crude product refining, crystallisation by cooling, filtering drying obtains IPA product.
Embodiment 3
At room temperature, it is proportionally added into zirconium oxychloride and titanium tetrachloride, is added sodium dodecyl sulfate solution (1wt%), so that solution
The molar ratio of middle Zr and Ti is 0.1:100, and after being stirred 30s, solution left standstill settles 14h.By product and solution deionization
Water and ethanol washing 3 times, drying and grinding.Ammonium hydroxide is added into gained powder to PH in the section 10-11, reaction time 3h, then
It is aged 5h.Products therefrom is washed repeatedly to PH is neutrality, and uses AgNO3Detection guarantees without Cl-, then by product in 1.5mol/
(the NH of L4)2S2O848h, vacuum drying grinding are impregnated in solution.
Product is transferred in high-temperature high-pressure reaction kettle, second alcohol and water is added, hydro-thermal reaction 14h, is cooled at 180 DEG C
It is washed respectively 3 times after room temperature with deionized water and ethyl alcohol, filters, be dried in vacuo at 75 DEG C, by dry product in air gas
60min is calcined at 600 DEG C in atmosphere.Obtain S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
Ketenes is continuously fed into the reaction kettle of the esterification equipped with fixed acetone soln, S is put into2O8 -/ZrO2-TiO2Gu
Body microspherical catalyst, S2O8 -/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 10% of acetone quality, and adjusting temperature is 75
DEG C, it is stirred；By gained crude product refining, crystallisation by cooling, filtering drying obtains IPA product.
Embodiment 4
At room temperature, it is proportionally added into zirconium oxychloride and titanium tetrachloride, is added cetylamine solution (1wt%), so that Zr and Ti in solution
Molar ratio be 0.5:100, after being stirred 30s, solution left standstill settle 16h.By product and solution deionized water and ethyl alcohol
Washing 3 times, drying and grinding.Ammonium hydroxide is added into gained powder to PH in the section 11-12, reaction time 2h, then is aged 3h.It will
It is neutrality that products therefrom, which is washed repeatedly to PH, and uses AgNO3Detection guarantees without Cl-, then by product 1.5mol/L (NH4)2S2O8It is impregnated in solution for 24 hours, vacuum drying grinding.
Product is transferred in high-temperature high-pressure reaction kettle, second alcohol and water is added, hydro-thermal reaction 14h, is cooled at 180 DEG C
It is washed respectively 3 times after room temperature with deionized water and ethyl alcohol, filters, be dried in vacuo at 60 DEG C, by dry product in air gas
90min is calcined at 500 DEG C in atmosphere.Obtain S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
Ketenes is continuously fed into the reaction kettle of the esterification equipped with fixed acetone soln, S is put into2O8 -/ZrO2-TiO2Gu
Body microspherical catalyst, S2O8 -/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 5% of acetone quality, and adjusting temperature is 60
DEG C, it is stirred；By gained crude product refining, crystallisation by cooling, filtering drying obtains IPA product.
Embodiment 5
At room temperature, it is proportionally added into zirconium oxychloride and titanium tetrachloride, is added cetylamine solution (1wt%), so that Zr and Ti in solution
Molar ratio be 4:100, after being stirred 30s, solution left standstill settle 20h.Product and solution are washed with deionized water and ethyl alcohol
3 times are washed, drying and grinding.Ammonium hydroxide is added into gained powder to PH in the section 9-10, reaction time 2h, then is aged 3h.By institute
Obtaining product and being washed repeatedly to PH is neutrality, and uses AgNO3Detection guarantees without Cl-, then by product 1.5mol/L (NH4)2S2O830h, vacuum drying grinding are impregnated in solution.
Product is transferred in high-temperature high-pressure reaction kettle, second alcohol and water is added, hydro-thermal reaction 14h, is cooled at 180 DEG C
It is washed respectively 3 times after room temperature with deionized water and ethyl alcohol, filters, be dried in vacuo at 60 DEG C, by dry product in air gas
90min is calcined at 500 DEG C in atmosphere.Obtain S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
Ketenes is continuously fed into the reaction kettle of the esterification equipped with fixed acetone soln, S is put into2O8 -/ZrO2-TiO2Gu
Body microspherical catalyst, S2O8 -/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 6% of acetone quality, and adjusting temperature is 60
DEG C, it is stirred；By gained crude product refining, crystallisation by cooling, filtering drying obtains IPA product.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. the preparation method that a kind of New Type of Ethylene ketone ester is combined to IPA, which comprises the following steps: (1) by ketenes
It is continuously fed into the reaction kettle of the esterification equipped with acetone soln, while putting into S2O8 -/ZrO2-TiO2Microspheres with solid catalyst, stirring
Mixing；(2) crude product refining for obtaining step (1), crystallisation by cooling, finally drying obtains IPA product.
2. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 1 is combined to IPA, which is characterized in that described
S2O8 -/ZrO2-TiO2Microspheres with solid catalyst the preparation method comprises the following steps: (1) is sub- by isopropyl titanate and/or titanium tetrachloride and/or sulfuric acid
Titanium, zirconium oxychloride are stirred；(2) basic solvent is added and is greater than 9, the reaction was continued 1-3h to pH, is aged 2-5h；(3) by step
(2) product generated washs repeatedly to neutrality and removes Cl-；(4) by step (3) products therefrom in (NH4)2S2O8It is impregnated in solution
24-48h grinds to obtain powder after dry；(5) powder obtained by step (4) is transferred in high-temperature high-pressure reaction kettle to carry out hydro-thermal anti-
It answers；(6) it is cooled to room temperature, washing filtering is dried in vacuo at 45-75 DEG C；(7) by step (6) dried product exhibited in air gas
It is calcined in atmosphere, obtains S2O8 -/ZrO2-TiO2Microspheres with solid catalyst.
3. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 2 is combined to IPA, which is characterized in that described
Isopropyl titanate and/or titanium tetrachloride and/or titanium sesquisulfate in step (1), two substance of zirconium oxychloride is in terms of Zr and Ti, Zr and Ti
Molar ratio be 0.1-10:100.
4. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 3 is combined to IPA, which is characterized in that described
Isopropyl titanate and/or titanium tetrachloride and/or titanium sesquisulfate, zirconium oxychloride carry out pre-treatment with surfactant.
5. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 4 is combined to IPA, which is characterized in that described
Surfactant is one of cetylamine, octadecylamine or dodecyl sodium sulfate or a variety of.
6. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 2 is combined to IPA, which is characterized in that described
Step (2) neutral and alkali solvent is ammonium hydroxide.
7. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 2 is combined to IPA, which is characterized in that described
The condition of hydro-thermal reaction in step (5) are as follows: heat 12-24h at 120-185 DEG C.
8. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 2 is combined to IPA, which is characterized in that described
Calcination temperature is 400-600 DEG C in step (7), calcination time 30-100min.
9. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 1 is combined to IPA, which is characterized in that described
Esterification temperature in reaction kettle of the esterification is 55-75 DEG C.
10. the preparation method that a kind of New Type of Ethylene ketone ester according to claim 9 is combined to IPA, which is characterized in that described
S2O8-/ZrO2-TiO2The additional amount of microspheres with solid catalyst is the 5%-10% of acetone quality.
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