CN113444058B - Continuous preparation method of alicyclic epoxy compound - Google Patents
Continuous preparation method of alicyclic epoxy compound Download PDFInfo
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- CN113444058B CN113444058B CN202010225333.XA CN202010225333A CN113444058B CN 113444058 B CN113444058 B CN 113444058B CN 202010225333 A CN202010225333 A CN 202010225333A CN 113444058 B CN113444058 B CN 113444058B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The invention provides a continuous preparation method of alicyclic epoxy compounds. The preparation method comprises the following steps: s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a microemulsifier for emulsification to form an emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8wt%; s2, continuously introducing the emulsion into a micro-reactor for oxidation reaction to obtain crude mother liquor; s3, purifying the crude mother liquor to obtain the alicyclic epoxy compound. The preparation method adopts the dynamic microchannel reactor, ensures the uniformity of a reaction system through the combination of the micro-emulsifier and the micro-reactor, avoids the problem of poor mixing effect, and can realize higher reaction conversion rate and yield of the alicyclic epoxy compound preparation by adopting the low-concentration hydrogen peroxide aqueous solution as the oxidant. The invention adopts a continuous operation flow, and the process is low in danger and safe and controllable.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a continuous preparation method of an alicyclic epoxy compound.
Background
The alicyclic epoxy compound plays an important role in a cationic curing system, epoxy groups are not from epichlorohydrin, but are obtained through oxidation of olefin, so that the property of the alicyclic epoxy compound is different from that of bisphenol A epoxy resin or glycidyl ether, the epoxy groups of the alicyclic epoxy compound are directly connected to the alicyclic, a compact rigid molecular structure can be formed, the crosslinking density after curing is increased, the thermal deformation temperature is high, the curing shrinkage is small, the tensile strength is high, and the epoxy compound has good dielectric property and outstanding weather resistance because a chlorine-containing structure is not used in the synthesis process. There is therefore a great and stable need for cycloaliphatic epoxies, both in the coating, ink and adhesive fields.
Commercial industrialized alicyclic epoxy such as TTA21 is produced by oxidizing peroxy acid in the production process, the peroxy acid is dangerous to produce and store, explosion accidents are easy to occur, the safety is poor, the traditional process is carried out in a batch reaction kettle, the batch difference is difficult to control, and in addition, the reaction brings a large amount of solid waste, and the production cost is high.
Patent CN109912544 provides a method for preparing bis ((3, 4-epoxycyclohexyl) methyl) adipate by using a microchannel reactor, although the operation process is simple, the purity and yield of the product are high, and continuous production can be realized, the oxygen source used is high-concentration hydrogen peroxide aqueous solution (50 wt%) which has high production cost and great storage potential safety hazard and is not suitable for industrial production; however, if a low-concentration hydrogen peroxide aqueous solution (< 30wt%) is used as an oxygen source, the activity of the hydrogen peroxide aqueous solution is reduced, the water content is increased, the two-phase differentiation of the system is increased, the uniform mixing effect cannot be realized by the conventional static microtubule reactor, the reaction conversion rate is very low, the industrialization cannot be realized, and the oxidation effect is lower especially for the multifunctional alicyclic epoxy compound.
Disclosure of Invention
The invention mainly aims to provide a continuous preparation method of an alicyclic epoxy compound, which aims to solve the problems of low oxidizing activity of an oxidant, complex operation process and low conversion rate of a conventional static microtubule reactor in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a continuous production method of an alicyclic epoxy compound, comprising the steps of: s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a microemulsifier for emulsification to form an emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8wt%; s2, continuously introducing the emulsion into a micro-reactor for oxidation reaction to obtain crude mother liquor; s3, purifying the crude mother liquor to obtain the alicyclic epoxy compound.
Further, the concentration of the hydrogen peroxide aqueous solution is 18-35 wt%; preferably, in step S1, the double bond in the alicyclic olefin and H in the hydrogen peroxide aqueous solution 2 O 2 The molar ratio of (2) is 1 (0.7-1.5).
Further, in the step S1, before introducing the alicyclic olefin into the microemulsifier, a step of adding a catalyst into the alicyclic olefin is further included, and the catalyst is a heteropolyacid quaternary ammonium salt; preferably, the heteropolyacid quaternary ammonium salt is prepared from a heteropolyacid and a quaternary ammonium base, wherein the heteropolyacid is preferably a tungstic heteropolyacid, and the quaternary ammonium base is preferably one or more of cetyl pyridine chloride, cetyl trimethyl ammonium chloride and benzyl trimethyl ammonium hydroxide.
Further, the weight of the catalyst is 1 to 20% of the weight of the alicyclic olefin.
Further, in step S1, introducing the alicyclic olefin into the micro-emulsifier through a first pipeline, introducing the hydrogen peroxide water solution into the micro-emulsifier through a second pipeline, and arranging a first heating device outside the first pipeline, wherein the heating temperature is 60-80 ℃; the second heating device is arranged outside the second pipeline, and the heating temperature is 30-40 ℃.
Further, in step S1, before introducing the alicyclic olefin into the microemulsion, a buffer salt is added to the alicyclic olefin; preferably, the buffer salt is selected from one or more of dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid-triethylamine and formic acid amine; preferably, the buffer salt is added in an amount of 3 to 15% by weight of the alicyclic olefin.
Further, the micro-emulsifier is provided with a stirring device, and the rotating speed of the stirring device is controlled to be 2000-15000 rpm/min in the emulsification process; preferably, the alicyclic olefin and the hydrogen peroxide aqueous solution are introduced from the lower part of the micro-emulsifier, and the emulsion is discharged from the upper part of the micro-emulsifier; preferably, the volume of the microemulsions is 0.5-5L; preferably, the micro-emulsifier further comprises a third heating device, and the temperature inside the micro-emulsifier is controlled to be 40-80 ℃ by the third heating device in the emulsification process; the number of the microemulsions is one or more, and when a plurality of microemulsions are used, the plurality of microemulsions are disposed in parallel or in series with each other.
Further, the micro-reactor is a micro-tube reactor, wherein the aperture of a reaction channel in the micro-tube reactor is 1-6 mm, and the length is 50-200 m; preferably, the microreactors are single sets or multiple sets arranged in series.
Further, the residence time of the emulsion in the microreactor is 20 to 80min, more preferably 20 to 75min, and the pressure of the oxidation reaction is 1.05 to 1.80MPa; preferably, the microreactor further comprises a heat exchange device, and the temperature inside the microreactor is controlled to be 50-85 ℃ by the heat exchange device, more preferably 60-70 ℃ in the oxidation reaction process; preferably, the micro-reactor is also provided with a nitrogen inlet, and the oxidation reaction process is carried out under the nitrogen atmosphere; preferably, step S2 further comprises a step of preheating the emulsion, more preferably at a temperature of 50-75 ℃, before the emulsion enters the microreactor.
Further, step S3 includes: s31, separating and washing the crude mother liquor in a centrifugal extractor to obtain an organic phase and a water phase; s32, distilling the organic phase in a thin film evaporator to obtain an alicyclic epoxy compound; preferably, before the step of separating and washing the crude mother liquor in the centrifugal extractor, step S31 further comprises: cooling the crude mother liquor in a cooling zone tower to obtain a cooling material; filtering the cooling material in a filtering device to obtain filtrate; the filtrate was then separated in a centrifugal extractor and washed with water.
Further, the alicyclic olefin has the general formula shown below:
wherein R is a linear or branched aliphatic alkylene group of 0 to 8 carbon atoms, and any of R is-CH 2 -optionally substituted by carbonyl, -COO-, -O-, or-S-, R 1 、R 2 Respectively is hydrogen, C 1 ～C 3 Alkyl of (a); more preferably, the alicyclic olefin is 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene, 4-cyclohex-3-en-1-ylcyclohexene or cyclohex-3-en-1-ylmethyl cyclohex-3-en-1-carboxylate.
The invention provides a continuous preparation method of alicyclic epoxy compounds, which adopts a dynamic microtubule reactor, ensures the uniformity of a reaction system through the combination of a micro-emulsifier and the micro-reactor, avoids the problem of poor mixing effect, and enables the adoption of low-concentration hydrogen peroxide aqueous solution as an oxidant to realize higher reaction conversion rate and yield of alicyclic epoxy compound preparation. The invention adopts a continuous operation flow, and the process is low in danger and safe and controllable.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 shows a schematic diagram of an apparatus employed in a continuous production process of an alicyclic epoxy compound according to the present invention.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
As described in the background section, the problems of low oxidant oxidation activity, complex operation process and low conversion rate of conventional static microtube reactors in the prior art. In order to solve the problem, the invention provides a continuous preparation method of alicyclic epoxy compound, which comprises the following steps: s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a microemulsifier for emulsification to form an emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8wt%; s2, continuously introducing the emulsion into a micro-reactor for oxidation reaction to obtain crude mother liquor; s3, purifying the crude mother liquor to obtain the alicyclic epoxy compound.
The invention adopts a dynamic microtubule reactor, ensures the uniformity of a reaction system through the combination of a micro-emulsifier and a micro-reactor, avoids the problem of poor mixing effect, and can realize higher reaction conversion rate and yield of the preparation of the alicyclic epoxy compound by adopting a low-concentration hydrogen peroxide aqueous solution as an oxidant (the reaction time is overlong and the conversion rate is not high as long as the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8wt% and is lower than the lower limit in the invention). The invention adopts a continuous operation flow, and the process has small danger and is safe and controllable.
In particular, compared with the prior art, the invention has the following advantages:
(1) The low-concentration hydrogen peroxide aqueous solution is used as an oxidant, no solid waste is generated, the hydrogen peroxide aqueous solution is stable in source, controllable in cost and relatively safe to store;
(2) The dynamic microtubule reaction is utilized, the uniformity of a reaction system is ensured through the combination of a micro-emulsifier and a micro-reactor, so that the reaction forms uniform emulsion, the reaction rate and the yield are improved, and the potential safety hazard is reduced;
(3) Preferably, in a specific operation process, products with different specifications (viscosity and epoxy equivalent) can be obtained by adjusting different proportions of the alicyclic olefin and the hydrogen peroxide aqueous solution so as to meet application requirements of different fields.
The concentration of the aqueous hydrogen peroxide solution is more preferably 18 to 35wt% in view of safety, conversion and product yield. The concentration is too high, potential safety hazards exist in the storage and preparation of hydrogen peroxide, and industrialization is not facilitated.
In order to further increase the reaction conversion, in a preferred embodiment, in step S1, the double bond in the alicyclic olefin and H in the aqueous hydrogen peroxide solution 2 O 2 The molar ratio of (2) is 1 (0.7-1.5). More preferably, in step S1, before passing the alicyclic olefin into the microemulsifier, a step of adding a catalyst to the alicyclic olefin, wherein the catalyst is a heteropolyacid quaternary ammonium salt; preferably, the heteropolyacid quaternary ammonium salt is prepared from a heteropolyacid and a quaternary ammonium base, the heteropolyacid is preferably a tungstopolyacid, and the quaternary ammonium base is preferably one or more of cetyl pyridine chloride, cetyl trimethyl ammonium chloride and benzyl trimethyl ammonium hydroxide. The reaction efficiency can be further improved by adopting the catalyst. And in a preferred embodiment, the weight of the catalyst is 1 to 20% of the weight of the alicyclic olefin in view of improving the reaction efficiency while saving the catalyst amount as much as possible. In the actual operation process, the catalyst can be added into the alicyclic olefin feeding kettle, and the mixture is pumped into the microemulsifier after being uniformly stirred.
In a preferred embodiment, in the step S1, the alicyclic olefin is introduced into the micro-emulsifier through a first pipeline, the hydrogen peroxide aqueous solution is introduced into the micro-emulsifier through a second pipeline, and a first heating device is arranged outside the first pipeline, wherein the heating temperature is 60-80 ℃; the second heating device is arranged outside the second pipeline, and the heating temperature is 30-40 ℃. This is more advantageous for increasing the emulsification speed and for further increasing the emulsification effect.
In addition, in the step S1, a solvent can be added, the solvent is not particularly required, and the addition of the reaction solvent can further improve the stability of the reaction and reduce the safety risk. The reaction solvent used may be any solvent as long as it can dissolve or disperse the reaction raw materials, and is preferably methylene chloride, chloroform, dichloroethane, ethyl acetate, benzene, toluene, xylene, or the like.
The hydrogen peroxide aqueous solution can be purchased directly or prepared by adopting on-line preparation equipment, and the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8wt percent, preferably 18-35 wt percent. In a specific operation process, the alicyclic olefin feeding kettle can be set to be 2 sets or more than 2 sets, so that continuous and automatic feeding is convenient.
In a preferred embodiment, step S1 further comprises the step of adding a buffer salt to the alicyclic olefin prior to passing the alicyclic olefin into the microemulsifier; preferably, the buffer salt is selected from one or more of dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid-triethylamine and formic acid amine; preferably, the buffer salt is added in an amount of 3 to 15% by weight of the alicyclic olefin. The buffer salt can provide more stable pH conditions for the oxidation reaction, and can also adjust the oxidation rate and inhibit the generation of ring-opening byproducts, so that the conversion rate and the product yield of the reaction are further improved.
In a preferred embodiment, the microemulsifier is a microemulsifier with a stirring device, and the rotation speed of the stirring device is controlled between 2000 and 15000rpm/min during the emulsification process. Under this stirring condition, the emulsification effect is better. Preferably, the alicyclic olefin and the aqueous hydrogen peroxide solution are introduced from the lower part of the microemulsion, and the emulsion is discharged from the upper part of the microemulsion. Thus, after the alicyclic olefin and the aqueous hydrogen peroxide solution enter the microemulsifier, the mixture is emulsified while being mixed, and finally the mixture is discharged from the upper part, so that the emulsification efficiency is higher.
The volume of the specific microemulsion may be adjusted according to the amount of raw material processed, and preferably the volume of the microemulsion is 0.5 to 5L. The micro-emulsifying device with the volume, the stirring rotating speed and the subsequent oxidation reaction speed are more adaptive, so that a more stable continuous micro-emulsifying and oxidation reaction state can be formed, and the production is facilitated. In a preferred embodiment, the microemulsifier further comprises a third heating means, and the temperature inside the microemulsifier is controlled to be 40-80 ℃ during the emulsification process by using the third heating means. In this heated state, the emulsification process is more efficient and more conducive to the formation of a stable emulsion.
Preferably, the number of the microemulsions is one or more, and when a plurality of the microemulsions are employed, the plurality of the microemulsions are disposed in parallel or in series with each other. This is more advantageous for improving the continuity and stability of production.
The microreactor used in the invention can be the microreactor existing in the prior art, and in order to further improve the reaction stability and the reaction efficiency, in a preferred embodiment, in the step S2, the microreactor is a microtube reactor, and the aperture of a reaction channel in the microtube reactor is 1-6 mm, and the length is 50-200 m. Preferably, the microreactors are single sets or multiple sets arranged in series.
In a preferred embodiment, the residence time of the emulsion in the microreactor is from 20 to 80 minutes, more preferably from 20 to 75 minutes, and the pressure of the oxidation reaction is from 1.05 to 1.80MPa. Under the reaction conditions, the oxidation reaction has higher conversion rate. Preferably, the microreactor further comprises a heat exchange device, and the temperature inside the microreactor is controlled to be 50-85 ℃ and more preferably 60-70 ℃ by utilizing the heat exchange device during the oxidation reaction. The temperature condition can further promote the oxidation reaction, improve the reaction efficiency and the conversion rate, and further reduce the occurrence of side reactions. More preferably, the microreactor is also provided with a nitrogen inlet, and the oxidation reaction process is carried out under a nitrogen atmosphere, which is beneficial to improving the reaction safety and improving the color of the product. It should be noted that the emulsification process is also a pre-reaction stage, and the oxidation reaction may be started from the emulsification stage, so that the temperatures of the two stages may be crossed.
Preferably, step S2 further comprises a step of preheating the emulsion, more preferably at a temperature of 50-75 ℃, before the emulsion proceeds to the microreactor. Preheating the emulsion also helps to further increase the efficiency of the oxidation reaction.
In a preferred embodiment, step S3 comprises: s31, separating and washing the crude mother liquor in a centrifugal extractor to obtain an organic phase and a water phase; and S32, distilling the organic phase in a thin film evaporator to obtain the alicyclic epoxy compound. More preferably, a cold zone tower and a filtering device are connected between the outlet of the micro-reactor and the centrifugal extractor, and the reaction mother solution flows into the centrifugal extractor for two-phase separation after being cooled by the cold zone tower through the filtering device. The organic phase and the aqueous phase can be obtained by centrifugal extraction treatment, preferably the extractant used in the process is water, the treated product is in the organic phase, and the catalyst is in the aqueous phase. Through thin film evaporation treatment, products and solvents in an organic phase can be distilled out respectively through a temperature interval, so that a target product is obtained, and compared with other distillation modes, the thin film evaporation has the advantages of high efficiency and more thorough separation. The solvent distilled off in the process can be directly used for continuous reaction; the catalyst obtained by centrifugation after water removal of the aqueous phase can also be reused.
The continuous preparation method of the alicyclic epoxy compound provided by the invention can be widely applied to the synthesis process of various alicyclic epoxy compounds, in particular to the preparation process of the following alicyclic olefin as raw materials:
wherein R is a linear or branched aliphatic alkylene group of 0 to 8 carbon atoms, and any of R is-CH 2 -optionally substituted by carbonyl, -COO-, -O-, or-S-, R 1 、R 2 Respectively is hydrogen, C 1 ～C 3 Alkyl of (a); more preferably, the alicyclic olefin is 4- (2-cyclohex-3-en-1-yl-propyl-2-yl) cyclohexene, 4-cyclohex-3-en-1-yl cyclohexene or cyclohex-3-en-1-ylmethyl cyclohex-3-en-1-carboxylate.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
As shown in FIG. 1, 2040g of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene, 100g of catalyst cetylphospholate, 1200g of chloroform and 150g of sodium dihydrogen phosphate were metered into the alicyclic olefin feed tank 10, and introduced into the microemulsion 50 through the first metering pump 20 at a flow rate of 10L/h under stirring, and heated by a pipeline during this time so that the temperature reached 60 to 70℃when reaching the microemulsion 50. Meanwhile, a hydrogen peroxide solution feeding kettle 30 filled with 2510g of 27% hydrogen peroxide solution is introduced into the micro-emulsifier 50 through a second metering pump 40 at a flow rate of 5.8L/h, and the temperature reaches 30-40 ℃ when the micro-emulsifier 50 is reached by heating through a pipeline. In the continuous feeding process, double bonds in alicyclic olefin and H in hydrogen peroxide aqueous solution 2 O 2 The molar ratio of (2) is 1:1. The emulsification treatment is carried out in a 1L micro-emulsifier 50, the temperature of the emulsion is controlled to be 60-65 ℃ by a heating device, the upper outflow mother liquor enters the micro-reactor 60 at the flow rate of 15.8L/h, the inner diameter of a micro-channel of the micro-reactor 60 is 6mm, the length is 200m, the reaction temperature of the micro-reactor 60 is controlled to be 60-65 ℃, the crude mother liquor enters a collecting tank 70, then the crude mother liquor is cooled to 20-30 ℃ by a cooling tower and enters a centrifugal extractor for separation and water washing, the organic phase enters a film reactor, the film reactor is provided with two sections, the external temperature of the first section is controlled to be 40-60 ℃ for decompression recovery of chloroform, the external temperature of the second section is controlled to be 160-180 ℃ for vacuum 3-5 mmHg. The final distillation gave 210g of product having a viscosity of 230cps/25℃and an epoxy equivalent of 195g/mol, and measured an olefin conversion of 92%, 23% of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane, 65% of 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane and a total yield of 85%.
Example 2:
the difference from example 1 is that the flow rate of the hydrogen peroxide aqueous solution is controlled to be 4.3L/H, and the double bonds in the alicyclic olefin and H in the hydrogen peroxide aqueous solution are continuously introduced 2 O 2 The molar ratio of (2) was 1:0.7, and the upper effluent mother liquor was fed into the microreactor at a flow rate of 14.3L/h. The final product viscosity is 90cps/25 ℃, and the epoxy equivalent weight is 256g/mol; the conversion of olefin was 70%, the total yield was 87% of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane was 35%, and 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane was 33%.
Example 3:
the difference from example 1 is that the flow rate of the hydrogen peroxide aqueous solution is controlled to be 8.6L/H, and the double bonds in the alicyclic olefin and H in the hydrogen peroxide aqueous solution are continuously introduced 2 O 2 The molar ratio of (2) was 1:1.5, and the upper effluent mother liquor was fed into the microreactor at a flow rate of 18.6L/h. The viscosity of the product is 620cps/25 ℃, and the epoxy equivalent weight is 148g/mol; the conversion of olefin was 95%, the yield of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane was 15%, the yield of 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane was 80%, and the total was 86%.
Example 4:
the difference from example 1 is that the catalyst is used in an amount of 215g, the product viscosity is 720cps/25℃and the epoxy equivalent is 135g/mol; the conversion of olefin was 95%, the total yield was 86% of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane 6%, and 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 88%.
Example 5:
the difference from example 1 is that 2040g of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene is replaced by 1620g of 4-cyclohex-3-en-1-ylcyclohexene, and the double bond in the alicyclic olefin and H in the aqueous hydrogen peroxide solution are continuously introduced into the process 2 O 2 The molar ratio of (2) is 1:1. The final product viscosity was 68 cps/25deg.C, epoxy equivalent weight 110g/mol, olefin conversion 95%, 4-cyclohex-3-en-1-epoxycyclohexane 9%, 4-cyclohex-3-epoxy-1-epoxycyclohexane 85% and total yield 83%.
Example 6:
the difference from example 5 is that the catalyst is used in an amount of 215g. The final product viscosity was 75cps/25 ℃, the epoxy equivalent weight was 103g/mol, the olefin conversion was 98%, 4-cyclohex-3-en-1-epoxycyclohexane 3%, 4-cyclohex-3-epoxy-1-epoxycyclohexane 96% and the total yield was 80%.
Example 7:
the difference from example 5 is that the hydrogen peroxide is continuously produced by an on-line device, the concentration of the hydrogen peroxide is 8%, and in order to ensure the conversion rate and prolong the reaction time, two sets of microemulsions and microreactors are adopted for series operation, the reaction liquid is mixed in a first emulsifier and enters the first microreactor, and after flowing out, enters a second microemulsions to be emulsified again, and then enters the second microreactor (the single microemulsions and microreactors are consistent with those of example 5); the final product viscosity was 50cps/25 ℃, the epoxy equivalent weight was 112g/mol, the olefin conversion was 90%, 4-cyclohex-3-en-1-epoxycyclohexane 12%, 4-cyclohex-3-epoxy-1-epoxycyclohexane 78%, and the total yield was 83%.
Example 8:
the difference from example 1 is that the concentration of the hydrogen peroxide aqueous solution is 35%, and the double bond in the alicyclic olefin and H in the hydrogen peroxide aqueous solution are continuously introduced 2 O 2 The molar ratio of (2) is 1:1.3, the product viscosity is 540cps/25 ℃, and the epoxy equivalent weight is 163g/mol; the conversion of olefin was 93%,4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane 19%,4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 76% and the total yield was 85%.
Example 9:
the difference from example 1 is that the concentration of the hydrogen peroxide aqueous solution is 18%, and the double bond in the alicyclic olefin and H in the hydrogen peroxide aqueous solution are continuously introduced 2 O 2 The molar ratio of the emulsion in the micro-emulsifier is 1:1.3, the emulsion flows into the micro-reactor at the flow rate of 9.5L/h, the product viscosity is 180cps/25 ℃, and the epoxy equivalent weight is 233g/mol; olefin conversion was 76%,4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane 21%,4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 54% and total yield was 85%.
Example 10
The difference from example 1 is that: the reaction temperature of the micro-reactor is controlled to be maintained at 75-80 ℃, the viscosity of the final product is 95cps/25 ℃, and the epoxy equivalent is 248g/mol; the conversion of olefin was 75%, the yield of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane was 30%, the yield of 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane was 41%, and the total yield was 87%.
Comparative example 1
The difference from example 8 is that: the concentration of the aqueous hydrogen peroxide solution is 5%, the olefin conversion rate is 45%, the 4- (2-cyclohex-3-en-1-yl-propyl-2-yl) epoxycyclohexane is 41%, and the 4- (2-cyclohex-3-epoxy-1-yl-propyl-2-yl) epoxycyclohexane is 2%, so that the method is not feasible.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. A continuous preparation method of alicyclic epoxy compound, which is characterized by comprising the following steps:
s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a microemulsifier for emulsification to form an emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is 8-27wt%; in the step S1, the alicyclic olefin is introduced into the micro-emulsifier through a first pipeline, the hydrogen peroxide aqueous solution is introduced into the micro-emulsifier through a second pipeline, and a first heating device is arranged outside the first pipeline, wherein the heating temperature of the first heating device is 60-80 ℃; a second heating device is arranged outside the second pipeline, and the heating temperature of the second heating device is 30-40 ℃; the micro-emulsifier is provided with a stirring device, and the rotating speed of the stirring device is controlled to be 2000-15000 rpm/min in the emulsification process;
s2, continuously introducing the emulsion into a micro-reactor for oxidation reaction to obtain crude mother liquor; the micro-reactor is a micro-tube reactor, the aperture of a reaction channel in the micro-tube reactor is 1-6 mm, and the length is 50-200 m; the residence time of the emulsion in the micro-reactor is 20-80 min, and the pressure of the oxidation reaction is 1.05-1.80 mpa; the micro-reactor further comprises a heat exchange device, and the temperature inside the micro-reactor is controlled to be 50-85 ℃ by utilizing the heat exchange device in the oxidation reaction process;
s3, purifying the crude mother liquor to obtain the alicyclic epoxy compound;
wherein the alicyclic olefin has the following general formula:
2. The continuous preparation method according to claim 1, wherein the concentration of the aqueous hydrogen peroxide solution is 18-27 wt%.
3. The continuous production method according to claim 2, wherein in the step S1, the double bond in the alicyclic olefin and H in the aqueous hydrogen peroxide solution 2 O 2 The molar ratio of (2) is 1 (0.7-1.5).
4. The continuous production method according to claim 1, wherein in the step S1, before passing the alicyclic olefin into the microemulsion, a step of adding a catalyst to the alicyclic olefin is further included, and the catalyst is a heteropolyacid quaternary ammonium salt; the heteropolyacid quaternary ammonium salt is prepared from heteropolyacid and quaternary ammonium base, wherein the heteropolyacid is tungstic heteropolyacid, and the quaternary ammonium base is one or more of cetyl pyridine chloride, cetyl trimethyl ammonium chloride and benzyl trimethyl ammonium hydroxide.
5. The continuous production method according to claim 4, wherein the weight of the catalyst is 1 to 20% of the weight of the alicyclic olefin.
6. The method according to any one of claims 1 to 5, wherein in the step S1, a buffer salt is further added to the alicyclic olefin before passing the alicyclic olefin into the microemulsion.
7. The continuous production method according to claim 6, wherein the buffer salt is one or more selected from the group consisting of dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, phosphoric acid-triethylamine and formic acid amine.
8. The continuous production method according to claim 7, wherein the buffer salt is added in an amount of 3 to 15% by weight based on the alicyclic olefin.
9. The continuous production method according to any one of claims 1 to 4, wherein the alicyclic olefin and the aqueous hydrogen peroxide solution are introduced from the lower portion of the microemulsion and the emulsion is discharged from the upper portion of the microemulsion.
10. The continuous production method according to any one of claims 1 to 4, wherein the capacity of the microemulsion is 0.5 to 5l.
11. The continuous production method according to any one of claims 1 to 4, wherein the microemulsion further comprises a third heating device, and the temperature inside the microemulsion is controlled to 40 to 80 ℃ by the third heating device during the emulsification process; the number of the microemulsions is one or more, and when a plurality of the microemulsions are adopted, the microemulsions are mutually connected in parallel or in series.
12. The continuous production method according to any one of claims 1 to 4, wherein the microreactors are single sets or multiple sets arranged in series.
13. The continuous production method according to any one of claims 1 to 4, characterized in that the residence time of the emulsion in the microreactor is 20 to 75min.
14. The continuous production method according to any one of claims 1 to 4, wherein the temperature inside the microreactor is controlled to 60 to 70 ℃ by the heat exchange device during the oxidation reaction.
15. The continuous production method according to any one of claims 1 to 4, wherein the microreactor is further provided with a nitrogen inlet, and the oxidation reaction process is performed under a nitrogen atmosphere.
16. The continuous production method according to any one of claims 1 to 4, wherein the step S2 further comprises a step of preheating the emulsion before the emulsion enters the microreactor.
17. The continuous production method according to claim 16, wherein the preheating temperature is 50 to 75 ℃.
18. The continuous production method according to any one of claims 1 to 4, characterized in that the step S3 comprises:
s31, separating and washing the crude mother liquor in a centrifugal extractor to obtain an organic phase and a water phase;
and S32, distilling the organic phase in a thin film evaporator to obtain the alicyclic epoxy compound.
19. The continuous production method according to claim 18, wherein before the step of separating and washing the crude mother liquor in the centrifugal extractor, the step S31 further comprises: cooling the crude mother liquor in a cooling zone tower to obtain a cooling material; filtering the cooling material in a filtering device to obtain filtrate; and then separating and washing the filtrate in the centrifugal extractor.
20. The continuous production process according to any one of claims 1 to 4, characterized in that the alicyclic olefin is 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene, 4-cyclohex-3-en-1-ylcyclohexene or cyclohex-3-en-1-ylmethyl cyclohex-3-en-1-carboxylate.
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| CN101250169A (en) * | 2008-04-08 | 2008-08-27 | 大连天源基化学有限公司 | Method for synthesizing aliphatic diepoxides |
| CN103880781A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Continuous production method for preparing cyclohexene oxide through cyclohexene oxidation with hydrogen peroxide under normal pressure |
| CN109535103A (en) * | 2019-01-15 | 2019-03-29 | 河北科技大学 | A kind of method that cyclohexene oxide prepares 7-oxa-bicyclo[4.1.0 |
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| CN101250169A (en) * | 2008-04-08 | 2008-08-27 | 大连天源基化学有限公司 | Method for synthesizing aliphatic diepoxides |
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