CN113444058A - Continuous preparation method of alicyclic epoxy compound - Google Patents
Continuous preparation method of alicyclic epoxy compound Download PDFInfo
- Publication number
- CN113444058A CN113444058A CN202010225333.XA CN202010225333A CN113444058A CN 113444058 A CN113444058 A CN 113444058A CN 202010225333 A CN202010225333 A CN 202010225333A CN 113444058 A CN113444058 A CN 113444058A
- Authority
- CN
- China
- Prior art keywords
- micro
- hydrogen peroxide
- alicyclic olefin
- emulsifier
- aqueous solution
- 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
Images
Classifications
-
- 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
-
- 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
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a continuous preparation method of an alicyclic epoxy compound. The preparation method comprises the following steps: s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a micro emulsifier for emulsification to form emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8 wt%; s2, continuously introducing the emulsion into a microreactor for oxidation reaction to obtain a crude mother solution; 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 by combining 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 preparation of the alicyclic epoxy compound by adopting the low-concentration hydrogen peroxide aqueous solution as the oxidant. And the invention adopts continuous operation flow, and the process has small danger and is 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, the epoxy group of the alicyclic epoxy compound is not derived from epichlorohydrin, but is obtained by oxidizing olefin, so that the property of the alicyclic epoxy compound is different from that of bisphenol A type epoxy resin or glycidyl ether, the epoxy group of the alicyclic epoxy compound is directly connected to an alicyclic ring, a compact rigid molecular structure can be formed, the crosslinking density is increased after curing, the thermal deformation temperature is higher, the curing shrinkage is small, the tensile strength is high, and the 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 constant demand for cycloaliphatic epoxies, whether in the coating, ink or adhesive fields.
Commercial alicyclic epoxy such as TTA21 is produced by oxidizing peroxy acid, so that the production and storage of peroxy acid are dangerous, explosion accidents easily occur, the safety is poor, and the traditional process is carried out in a batch reaction kettle, the batch-to-batch difference is difficult to control, and in addition, the reaction brings a large amount of solid wastes, 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 product purity and yield are high, and continuous production can be realized, the oxygen source used by the method is high-concentration hydrogen peroxide aqueous solution (50 wt%), the production cost of the hydrogen peroxide aqueous solution is very high, the storage safety hidden danger is very large, and the method is not suitable for industrial production; however, if a low-concentration aqueous hydrogen peroxide solution (less than 30 wt%) is used as an oxygen source, the activity is reduced, the water content is increased, the two-phase differentiation of the system is aggravated, a uniform mixing effect cannot be realized in a conventional static microtube type reactor, the conversion rate of the reaction is low, industrialization cannot be realized, and particularly, the oxidation effect of the multifunctional alicyclic epoxy compound is lower.
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 oxidizing agent, complex operation process and low conversion rate of a conventional static microtubular 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 a cycloaliphatic epoxy compound, comprising the steps of: s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a micro emulsifier for emulsification to form emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8 wt%; s2, continuously introducing the emulsion into a microreactor for oxidation reaction to obtain a crude mother solution; 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 aqueous solution of hydrogen peroxide2O2The molar ratio of (1) is (0.7-1.5).
Further, in step S1, before the alicyclic olefin is introduced into the microemulsion, a step of adding a catalyst to the alicyclic olefin is further included, and the catalyst is a heteropoly acid quaternary ammonium salt; preferably, the heteropoly acid quaternary ammonium salt is prepared from heteropoly acid and quaternary ammonium base, the heteropoly acid is preferably tungstic heteropoly acid, and the quaternary ammonium base is preferably one or more of cetyl pyridinium chloride, cetyl trimethyl ammonium chloride and benzyl trimethyl ammonium hydroxide.
Further, the weight of the catalyst is 1-20% of the weight of the alicyclic olefin.
Further, in step S1, introducing alicyclic olefin into the microemulsion device through a first pipeline, and introducing hydrogen peroxide aqueous solution into the microemulsion device through a second pipeline, wherein a first heating device is arranged outside the first pipeline, and the heating temperature of the first heating device is 60-80 ℃; the outside of second pipeline is provided with second heating device, and its heating temperature is 30 ~ 40 ℃.
Further, step S1 includes the step of adding a buffer salt to the alicyclic olefin before the alicyclic olefin is introduced into the microemulsion device; 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 ammonium formate; the amount of the buffer salt added is preferably 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 at 2000-15000 rpm/min in the emulsification process; preferably, alicyclic olefin and hydrogen peroxide aqueous solution are introduced from the lower part of the micro emulsifier, and emulsion is discharged from the upper part of the micro emulsifier; preferably, the volume of the micro emulsifier is 0.5-5L; preferably, the micro emulsifier also comprises a third heating device, and the temperature in the micro emulsifier is controlled to be 40-80 ℃ by the third heating device in the emulsification process; the number of the micro-emulsifying devices is one or more, and when a plurality of micro-emulsifying devices are adopted, the plurality of micro-emulsifying devices are mutually connected in parallel or in series.
Further, the microreactor is a micro-tube type reactor, the aperture of a reaction channel in the micro-tube type reactor is 1-6 mm, and the length of the reaction channel is 50-200 m; preferably, the microreactors are a single set or multiple sets arranged in series.
Further, the residence time of the emulsion in the microreactor is 20-80 min, more preferably 20-75 min, and the pressure of the oxidation reaction is 1.05-1.80 MPa; preferably, the microreactor further comprises a heat exchange device, and in the oxidation reaction process, the temperature in the microreactor is controlled to be 50-85 ℃ by using the heat exchange device, and more preferably controlled to be 60-70 ℃; preferably, the microreactor is also provided with a nitrogen inlet, and the oxidation reaction process is carried out in a nitrogen atmosphere; preferably, step S2 further includes a step of preheating the emulsion before the emulsion enters the microreactor, and more preferably, the preheating temperature is 50 to 75 ℃.
Further, step S3 includes: s31, separating and washing the crude product 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, step S31 further comprises, before the step of separating and washing the crude mother liquor in the centrifugal extractor: 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; then the filtrate is separated and washed by water in a centrifugal extractor.
Further, the alicyclic olefin has the general formula shown below:
wherein R is a linear or branched aliphatic alkylene group having 0 to 8 carbon atoms, and any of R is-CH2-optionally substituted by carbonyl, -COO-, -O-or-S-, R1、R2Are respectively hydrogen and C1～C3Alkyl groups of (a); more preferably the alicyclic olefin is 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene, 4-cyclohex-3-en-1-cyclohexene or cyclohex-3-en-1-ylmethyl-cyclohex-3-ene-1-carboxylate.
The invention provides a continuous preparation method of alicyclic epoxy compounds, which adopts a dynamic micro-tube 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 compounds by adopting a low-concentration hydrogen peroxide aqueous solution as an oxidant. And the invention adopts continuous operation flow, and the process has small danger and is safe and controllable.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view showing an apparatus used in the continuous production method of the alicyclic epoxy compound according to the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background section, the prior art has problems of low oxidizing activity of the oxidizing agent, complicated operation process, and low conversion rate of the conventional static microtubular reactor. In order to solve the problem, the invention provides a continuous preparation method of an alicyclic epoxy compound, which comprises the following steps: s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a micro emulsifier for emulsification to form emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8 wt%; s2, continuously introducing the emulsion into a microreactor for oxidation reaction to obtain a crude mother solution; s3, purifying the crude mother liquor to obtain the alicyclic epoxy compound.
The invention adopts a dynamic microtubular 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 (in the invention, the reaction time is too long and the conversion rate is not high as long as the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8 wt%, and is lower than the lower limit). And the invention adopts a continuous operation process, and the process has small danger and is safe and controllable.
Specifically, compared with the prior art, the invention has the following advantages:
(1) the low-concentration hydrogen peroxide solution is used as an oxidant, so that no solid waste is generated, the hydrogen peroxide solution has stable source, controllable cost and relatively safe storage;
(2) by utilizing the dynamic microtube type reaction, the uniformity of a reaction system is ensured by combining a micro-emulsifier and a micro-reactor, so that uniform emulsion is formed in the reaction, the reaction rate and the yield are improved, and the potential safety hazard is reduced;
(3) preferably, in the 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.
For further consideration of safety, conversion rate and product yield, the concentration of the hydrogen peroxide solution is more preferably 18-35 wt%. The concentration is too high, potential safety hazards exist in the storage and preparation of the hydrogen peroxide, and the industrialization is not facilitated to realize.
In order to further increase the reaction conversion rate, in a preferred embodiment, in step S1, the double bond in the alicyclic olefin and H in the aqueous hydrogen peroxide solution2O2The molar ratio of (1) is (0.7-1.5). More preferably, step S1, before alicyclic olefin is introduced into the micro emulsifier, the method also comprises the step of adding a catalyst into the alicyclic olefin, wherein the catalyst is heteropoly acid quaternary ammonium salt; preferably, the heteropoly acid quaternary ammonium salt is prepared from heteropoly acid, preferably heteropoly tungstic acid, and quaternary ammonium base, preferably one or more of cetyl pyridinium chloride, cetyl trimethyl ammonium chloride and benzyl trimethyl ammonium hydroxide. The reaction efficiency can be further improved by adopting the catalyst. In order to improve the reaction efficiency and save the amount of the catalyst as much as possible, in a preferred embodiment, the weight of the catalyst is 1 to 20% of the weight of the alicyclic olefin. In the actual operation process, the catalyst can be added into the alicyclic olefin feeding kettle, and the mixture is pumped into the microemulsion device after being uniformly stirred.
In a preferred embodiment, in step S1, alicyclic olefin is introduced into the microemulsion device through the first pipeline, and the hydrogen peroxide aqueous solution is introduced into the microemulsion device through the second pipeline, wherein a first heating device is disposed outside the first pipeline, and the heating temperature of the first heating device is 60 to 80 ℃; the outside of second pipeline is provided with second heating device, and its heating temperature is 30 ~ 40 ℃. This is more advantageous in increasing the emulsification speed and further in improving the emulsification effect.
In addition, a solvent can be added in the step S1, the solvent does not make special requirements, and the addition of the reaction solvent can further improve the stability of the reaction and reduce the safety risk. Specifically, the reaction solvent used may be any solvent capable of dissolving or dispersing the reaction raw material, and preferably, the reaction solvent is dichloromethane, chloroform, dichloroethane, ethyl acetate, benzene, toluene, xylene, or the like.
The hydrogen peroxide solution can be purchased directly or prepared by adopting online preparation equipment, and the concentration of the hydrogen peroxide solution is more than or equal to 8 wt%, preferably 18-35 wt%. In the specific operation process, the alicyclic olefin feeding kettles can be set to 2 or more than 2, so that continuous and automatic feeding is facilitated.
In a preferred embodiment, step S1 further comprises the step of adding a buffer salt to the cycloaliphatic olefin before passing the cycloaliphatic olefin into the microemulsion; 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 ammonium formate; the amount of the buffer salt added is preferably 3 to 15% by weight of the alicyclic olefin. The buffer salt can provide a more stable pH condition for the oxidation reaction, and can also adjust the oxidation rate and inhibit the generation of ring-opening byproducts, thereby being beneficial to further improving the conversion rate of the reaction and the product yield.
In a preferred embodiment, the micro emulsifier is a micro emulsifier with a stirring device, and the rotating speed of the stirring device is controlled to be 2000-15000 rpm/min during the emulsification process. Under the stirring condition, the emulsifying effect is better. 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. Thus, after the alicyclic olefin and the hydrogen peroxide aqueous solution enter the micro emulsifier, the alicyclic olefin and the hydrogen peroxide aqueous solution are mixed and emulsified at the same time, and finally discharged from the upper part, so that the emulsification efficiency is higher.
The volume of the microemulsion device can be adjusted according to the treatment amount of raw materials, and preferably, the volume of the microemulsion device is 0.5-5L. The microemulsion emulsifier with the volume is selected to be more adaptive to the stirring rotating speed and the subsequent oxidation reaction speed, so that a more stable continuous microemulsion and oxidation reaction state can be formed, and the production is facilitated. In a preferred embodiment, the micro-emulsifier further comprises a third heating device, and the temperature in the micro-emulsifier is controlled to be 40-80 ℃ by the third heating device in the emulsification process. Under this heating state, the emulsification process is more efficient, more favorable to forming stable emulsion.
Preferably, the number of the microemulsifiers is one or more, and when a plurality of the microemulsifiers are adopted, the plurality of the microemulsifiers are mutually connected in parallel or in series. This is more advantageous in improving the continuity and stability of production.
In order to further improve the reaction stability and the reaction efficiency, in a preferred embodiment, in step S2, the microreactor is a micro-tube reactor, and the diameter of the reaction channel in the micro-tube reactor is 1-6 mm and the length is 50-200 m. Preferably, the microreactors are a single set or multiple sets arranged in series.
In a preferred embodiment, the residence time of the emulsion in the microreactor is 20-80 min, more preferably 20-75 min, and the pressure of the oxidation reaction is 1.05-1.80 MPa. Under the reaction condition, the oxidation reaction has higher conversion rate. Preferably, the microreactor further comprises a heat exchange device, and in the oxidation reaction process, the temperature in the microreactor is controlled to be 50-85 ℃ by using the heat exchange device, and more preferably controlled to be 60-70 ℃. 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 further provided with a nitrogen inlet, and the oxidation reaction process is carried out under a nitrogen atmosphere, so that the reaction safety is improved, and the product color is improved. It should be noted that the emulsification process is also a pre-reaction stage, and the oxidation reaction starts from the emulsification stage, so that the temperatures of the two stages can be crossed.
Preferably, before the emulsion is further processed into the microreactor, the step S2 further comprises a step of preheating the emulsion, and more preferably, the preheating temperature is 50-75 ℃. The emulsion is heated in advance, which also contributes to further improvement of the oxidation reaction efficiency.
In a preferred embodiment, step S3 includes: s31, separating and washing the crude product 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 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 reaction mother liquor flows into the centrifugal extractor through the filtering device after being cooled by the cold zone tower to carry out two-phase separation. 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 film evaporation treatment, the product and the solvent in the organic phase can be respectively evaporated out through a temperature interval to obtain a target product, and compared with other distillation modes, the film evaporation has the advantages of high efficiency and more thorough separation. The solvent distilled off in the period can be directly used for continuous reaction; the catalyst obtained by centrifugation after water removal from 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 taking the alicyclic olefin as a raw material:
wherein R is a linear or branched aliphatic alkylene group having 0 to 8 carbon atoms, and any of R is-CH2-optionally substituted by carbonyl, -COO-, -O-or-S-, R1、R2Are respectively hydrogen and C1～C3Alkyl groups of (a); more preferably, the alicyclic olefin is 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene, 4-cyclohex-3-en-1-cyclohexene or cyclohex-3-en-1-ylmethyl-cyclohex-3-ene-1-carboxylate.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
As shown in figure 1, 2040g of 4- (2-cyclohexyl-3-en-1-ylpropyl-2-yl) cyclohexene, 100g of cetylpyridinium phosphotungstate quaternary ammonium salt serving as a catalyst, 1200g of chloroform and 150g of sodium dihydrogen phosphate are metered into an alicyclic olefin feeding kettle 10, and are introduced into a micro-emulsifier 50 through a first metering pump 20 at a flow rate of 10L/h under the stirring condition, and the temperature reaches 60-70 ℃ when the alicyclic olefin feeding kettle reaches the micro-emulsifier 50 through pipeline heating. Meanwhile, a hydrogen peroxide aqueous solution feeding kettle 30 filled with 2510g of 27% hydrogen peroxide aqueous solution is introduced into the micro-emulsifier 50 through a second metering pump 40 at the flow rate of 5.8L/h, and the temperature reaches 30-40 ℃ when the hydrogen peroxide aqueous solution reaches the micro-emulsifier 50 through pipeline heating. In the continuous feeding process, double bonds in alicyclic olefin and H in hydrogen peroxide aqueous solution2O2Is 1:1. Emulsifying in 1L microemulsion 50, and controlling the temperature of the emulsion by heating device60-65 ℃, feeding the mother liquor flowing out of the upper part into a micro-reactor 60 at a flow rate of 15.8L/h, controlling the inner diameter of a micro-channel of the micro-reactor 60 to be 6mm and the length to be 200m, controlling the reaction temperature of the micro-reactor 60 to be maintained at 60-65 ℃, feeding the crude mother liquor into a collection tank 70, cooling the crude mother liquor to 20-30 ℃ by a cooling tower, feeding the crude mother liquor into a centrifugal extractor for separation and washing, feeding an organic phase into a thin film reactor, arranging two sections of the thin film reactor, controlling the external temperature of the first section to be 40-60 ℃ and decompressing and recovering trichloromethane, controlling the external temperature of the second section to be 160-180 ℃ and vacuumizing to be 3-5 mmHg. 210g of product are finally distilled off, the product viscosity is 230cps/25 ℃, the epoxide equivalent weight is 195g/mol, the olefin conversion rate is measured to be 92%, the 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane is measured to be 23%, the 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane is measured to be 65%, and the total yield is 85%.
Example 2:
the difference from the example 1 is that the flow rate of the aqueous solution of hydrogen peroxide is controlled to be 4.3L/H, and during the continuous feeding process, the double bonds in the alicyclic olefin and the H in the aqueous solution of hydrogen peroxide2O2The molar ratio of (1: 0.7), and the upper outflow mother liquor enters the microreactor at the flow rate of 14.3L/h. The viscosity of the final product is 90cps/25 ℃, and the epoxy equivalent is 256 g/mol; the olefin conversion rate was 70%, the 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane was 35%, the 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane was 33%, and the overall yield was 87%.
Example 3:
the difference from the example 1 is that the flow rate of the aqueous solution of hydrogen peroxide is controlled to be 8.6L/H, and during the continuous feeding process, the double bonds in the alicyclic olefin and the H in the aqueous solution of hydrogen peroxide2O2The molar ratio of (1: 1.5), and the upper outflow mother liquor enters the microreactor at the flow rate of 18.6L/h. The product viscosity is 620cps/25 ℃, and the epoxy equivalent is 148 g/mol; olefin conversion 95%, 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane 15%, 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 80%, total yield 86%.
Example 4:
the difference from example 1 is that the amount of the catalyst used is 215g, the product viscosity is 720cps/25 ℃, and the epoxy equivalent is 135 g/mol; olefin conversion 95%, 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane 6%, 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 88%, total yield 86%.
Example 5:
the difference from example 1 is that 2040g of 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene was replaced by 1620g of 4-cyclohex-3-en-1-cyclohexene, and the double bond in the alicyclic olefin and H in the aqueous hydrogen peroxide solution were continuously fed into the reactor during the continuous feeding2O2Is 1:1. The viscosity of the final product is 68cps/25 ℃, the epoxy equivalent is 110g/mol, the olefin conversion rate is 95%, the 4-cyclohexyl-3-alkene-1-epoxycyclohexane is 9%, the 4-cyclohexyl-3-epoxy-1-epoxycyclohexane is 85%, and the total yield is 83%.
Example 6:
the difference from example 5 is that the amount of catalyst used is 215 g. The viscosity of the final product is 75cps/25 ℃, the epoxy equivalent is 103g/mol, the olefin conversion rate is 98%, the 4-cyclohexyl-3-alkene-1-epoxy cyclohexane is 3%, the 4-cyclohexyl-3-epoxy-1-epoxy cyclohexane is 96%, and the total yield is 80%.
Example 7:
the difference from the embodiment 5 is that the hydrogen peroxide is continuously produced by online equipment, the concentration of the hydrogen peroxide is 8%, in order to ensure the conversion rate and prolong the reaction time, the series operation of two sets of microemulsions and microreactors is adopted, the reaction liquid is mixed in the first emulsifier and enters the first microreactor, and after flowing out, the reaction liquid enters the second microemulsions and re-emulsifies, and then enters the second microreactor (the single microemulsions and microreactors are consistent with the embodiment 5); the viscosity of the final product is 50cps/25 ℃, the epoxy equivalent is 112g/mol, the olefin conversion rate is 90%, the 4-cyclohexyl-3-alkene-1-epoxy cyclohexane is 12%, the 4-cyclohexyl-3-epoxy-1-epoxy cyclohexane is 78%, and the total yield is 83%.
Example 8:
the difference from the example 1 is that the concentration of the aqueous solution of hydrogen peroxide is 35%, and during the continuous feeding, the double bonds in the alicyclic olefin and the H in the aqueous solution of hydrogen peroxide2O2The molar ratio of (1: 1.3), the product viscosity of 540cps/25 ℃, and the epoxy equivalent of 163 g/mol; olefin conversion 93%, 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxyCyclohexane 19%, 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 76%, total yield 85%.
Example 9:
the difference from the example 1 is that the concentration of the aqueous solution of hydrogen peroxide is 18 percent, and during the continuous feeding process, the double bonds in the alicyclic olefin and the H in the aqueous solution of hydrogen peroxide2O2The molar ratio of (1: 1.3), the emulsion in the micro-emulsifier flows into the micro-reactor at the flow rate of 9.5L/h, the viscosity of the product is 180cps/25 ℃, and the epoxy equivalent is 233 g/mol; the olefin conversion rate was 76%, 21% for 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane, 54% for 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane, and the total yield was 85%.
Example 10
The difference from example 1 is that: controlling the reaction temperature of the micro-reactor to be 75-80 ℃, keeping the viscosity of a final product at 95cps/25 ℃, and keeping the epoxy equivalent at 248 g/mol; olefin conversion rate 75%, 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) epoxycyclohexane 30%, 4- (2-cyclohex-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane 41%, total yield 87%.
Comparative example 1
The difference from example 8 is that: the concentration of the hydrogen peroxide solution is 5%, the olefin conversion rate is 45%, the 4- (2-cyclohexyl-3-en-1-ylpropyl-2-yl) epoxycyclohexane is 41%, and the 4- (2-cyclohexyl-3-epoxy-1-ylpropyl-2-yl) epoxycyclohexane is 2%, so that the feasibility is not available.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A method for continuously preparing alicyclic epoxy compounds, which is characterized by comprising the following steps:
s1, continuously introducing alicyclic olefin and hydrogen peroxide aqueous solution into a micro emulsifier for emulsification to form emulsion, wherein the concentration of the hydrogen peroxide aqueous solution is more than or equal to 8 wt%;
s2, continuously introducing the emulsion into a microreactor for oxidation reaction to obtain a crude mother solution;
s3, purifying the crude mother liquor to obtain the alicyclic epoxy compound.
2. The continuous preparation method of claim 1, wherein the concentration of the hydrogen peroxide solution is 18-35 wt%; preferably, in step S1, the double bond in the alicyclic olefin and H in the hydrogen peroxide aqueous solution2O2The molar ratio of (1) is (0.7-1.5).
3. The continuous production method according to claim 1, wherein in the step S1, before the alicyclic olefin is passed into the microemulsion, the method further comprises a step of adding a catalyst to the alicyclic olefin, and the catalyst is a heteropoly acid quaternary ammonium salt; preferably, the heteropoly acid quaternary ammonium salt is prepared from heteropoly acid, preferably tungstophosphoric acid, and quaternary ammonium base, preferably one or more of cetyl pyridinium chloride, cetyl trimethyl ammonium chloride and benzyl trimethyl ammonium hydroxide.
4. The continuous production method according to claim 3, wherein the weight of the catalyst is 1 to 20% of the weight of the alicyclic olefin.
5. The continuous preparation method according to any one of claims 1 to 4, wherein in step S1, the alicyclic olefin is introduced into the microemulsion through a first pipeline, and the hydrogen peroxide aqueous solution is introduced into the microemulsion through a second pipeline, wherein a first heating device is arranged outside the first pipeline, and the heating temperature of the first heating device is 60-80 ℃; and a second heating device is arranged outside the second pipeline, and the heating temperature of the second heating device is 30-40 ℃.
6. The method according to claim 5, wherein said step S1 further comprises a step of adding a buffer salt to said alicyclic olefin before passing said alicyclic olefin into said microemulsion; 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 ammonium formate; preferably, the amount of the buffer salt added is 3 to 15% by weight of the alicyclic olefin.
7. The continuous production method according to any one of claims 1 to 6, wherein the micro-emulsifier is a micro-emulsifier with a stirring device, and the rotation speed of the stirring device is controlled to 2000-15000 rpm/min during 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 micro emulsifier is 0.5-5L;
preferably, the micro emulsifier further comprises a third heating device, and in the emulsification process, the third heating device is used for controlling the temperature inside the micro emulsifier to be 40-80 ℃;
the number of the micro-emulsifying devices is one or more, and when a plurality of the micro-emulsifying devices are adopted, the plurality of the micro-emulsifying devices are mutually connected in parallel or in series.
8. The preparation method according to claim 7, wherein the microreactor is a microtubular reactor, and the diameter of a reaction channel in the microtubular reactor is 1-6 mm, and the length of the reaction channel is 50-200 m;
preferably, the microreactors are single set or multiple sets arranged in series.
9. The continuous preparation method according to claim 8, wherein the residence time of the emulsion in the microreactor is 20-80 min, more preferably 20-75 min, and the pressure of the oxidation reaction is 1.05-1.80 MPa;
preferably, the microreactor further comprises a heat exchange device, and in the oxidation reaction process, the temperature in the microreactor is controlled to be 50-85 ℃ by using the heat exchange device, and more preferably controlled to be 60-70 ℃;
preferably, the microreactor is further provided with a nitrogen inlet, and the oxidation reaction process is carried out in a nitrogen atmosphere;
preferably, before the emulsion enters the microreactor, the step S2 further includes a step of preheating the emulsion, and more preferably, the preheating temperature is 50 to 75 ℃.
10. The continuous production method according to any one of claims 1 to 6, wherein the step S3 includes:
s31, separating and washing the crude product 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 the alicyclic epoxy compound;
preferably, 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.
11. The continuous production method according to any one of claims 1 to 6, wherein the alicyclic olefin has a general formula shown below:
wherein R is a linear or branched aliphatic alkylene group having 0 to 8 carbon atoms, and any of R is-CH2-optionally substituted by carbonyl, -COO-, -O-or-S-, R1、R2Are respectively asHydrogen, C1～C3Alkyl groups of (a); more preferably, the alicyclic olefin is 4- (2-cyclohex-3-en-1-ylpropyl-2-yl) cyclohexene, 4-cyclohex-3-en-1-cyclohexene or cyclohex-3-en-1-ylmethyl-cyclohex-3-ene-1-carboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010225333.XA CN113444058B (en) | 2020-03-26 | 2020-03-26 | Continuous preparation method of alicyclic epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010225333.XA CN113444058B (en) | 2020-03-26 | 2020-03-26 | Continuous preparation method of alicyclic epoxy compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113444058A true CN113444058A (en) | 2021-09-28 |
| CN113444058B CN113444058B (en) | 2023-04-21 |
Family
ID=77807324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010225333.XA Active CN113444058B (en) | 2020-03-26 | 2020-03-26 | Continuous preparation method of alicyclic epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113444058B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073396A (en) * | 2022-06-29 | 2022-09-20 | 江苏泰特尔新材料科技股份有限公司 | Synthesis method of alicyclic epoxy resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109721609A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A method of synthesis bicyclopentadiene dioxide |
| CN109721568A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method of solid acid catalysis oxyalkylene |
-
2020
- 2020-03-26 CN CN202010225333.XA patent/CN113444058B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109721609A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A method of synthesis bicyclopentadiene dioxide |
| CN109721568A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of method of solid acid catalysis oxyalkylene |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073396A (en) * | 2022-06-29 | 2022-09-20 | 江苏泰特尔新材料科技股份有限公司 | Synthesis method of alicyclic epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113444058B (en) | 2023-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2848435A (en) | Process for the manufacture of epoxy resins | |
| CN113444058B (en) | Continuous preparation method of alicyclic epoxy compound | |
| CN110143847A (en) | A kind of 1S, 4R-1- methyl -4-(1- methyl ethylene) -2- cyclohexene -1- alcohol preparation method | |
| JP2004099467A (en) | Method for producing alicyclic epoxy compound | |
| CN111995524A (en) | Continuous synthesis method of 5-nitroisophthalic acid | |
| CN108276409B (en) | Method for preparing medicine and medicine intermediate by continuous solid-liquid-gas three-phase reaction | |
| Tibbetts et al. | Sustainable catalytic epoxidation of biorenewable terpene feedstocks using H 2 O 2 as an oxidant in flow microreactors | |
| CN110878077A (en) | Method for continuously preparing ethylene carbonate | |
| CN113429376B (en) | Continuous synthesis method of epsilon-caprolactone | |
| CN103880782B (en) | A kind of method preparing expoxy propane | |
| CN109796411B (en) | Method for preparing 4, 5-dinitroimidazole by using microchannel reactor | |
| CN104672431B (en) | A kind of tetra functional epoxy resin and preparation method and application | |
| CN113372300A (en) | Continuous flow synthesis process of cyclohexene-based epoxide and cyclohexene-based epoxide | |
| CN108610314A (en) | The method that biphenyl dianhydride is synthesized in continuous flow micro passage reaction | |
| CN111072598B (en) | Process for producing epichlorohydrin by direct oxidation of titanium-silicon molecular sieve catalyst | |
| US8759553B2 (en) | Method for producing epoxy compound | |
| CN113845495B (en) | Continuous synthesis method of two-stage glycidyl neodecanoate | |
| CN115650825A (en) | Method for synthesizing dihydric alcohol monovinyl ether | |
| CN113893875A (en) | Preparation method of double-bond epoxidation phase transfer catalyst with high recovery rate | |
| CN113493372B (en) | Preparation method of photoinitiator | |
| CN114671808A (en) | Preparation method of caprolactam | |
| CN211771013U (en) | Device for continuously producing epoxy chloropropane by oxidizing chloropropene with titanium-silicon molecular sieve | |
| CN113105332A (en) | Method for preparing eltrombopag nitration intermediate in micro-channel continuous flow reactor | |
| US4954583A (en) | Arylcyclobutene carboxylate esters | |
| CN112239450A (en) | Method for synthesizing epsilon-caprolactone |
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 |