CN105254476A - Method for preparing fluorine-containing halogenated ether - Google Patents
Method for preparing fluorine-containing halogenated ether Download PDFInfo
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- CN105254476A CN105254476A CN201510743219.5A CN201510743219A CN105254476A CN 105254476 A CN105254476 A CN 105254476A CN 201510743219 A CN201510743219 A CN 201510743219A CN 105254476 A CN105254476 A CN 105254476A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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Abstract
The invention relates to a method for preparing fluorine-containing halogenated ether, belonging to the technical field of organofluorine chemistry. The method comprises the following steps: using fluorooxytrifluoromethane and halogenated alkene as raw materials and continuously feeding gas phase halogenated alkene and gas phase fluorooxytrifluoromethane into a reactor to undergo thermal addition reaction to obtain fluorine-containing halogenated ether; controlling the spray pressure of fluorooxytrifluoromethane to be 0.1-1MPa, the reaction temperature to be 80-200 DEG C and the mole ratio of fluorooxytrifluoromethane to halogenated alkene to be (0.6-1.3) to 1. The method has the beneficial technical effects that the two raw materials are in gas phase; continuous obtainment of fluorine-containing halogenated ether with high yield and efficiency can be ensured by controlling the specific spray pressure of fluorooxytrifluoromethane, the specific reaction temperature and the specific reaction raw material ratio; the method only adopts two kinds of reaction raw materials, is simple in process, can be used for continuous production, has the advantages of low metering requirements, convenience in operation and high yield and efficiency and is very suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method preparing fluorine chemical intermediate, more particularly, the present invention relates to a kind of method prepared containing fluorohalogenethers, belong to organic fluorine chemistry technical field.
Background technology
Containing the fluorine chemical intermediate that fluorohalogenethers is important, perfluor ether wherein has a wide range of applications as inert fluid; Containing the important presoma that fluorohalogenethers is also the fluorine-containing halogenated vinyl ethers of preparation, obtain fluorine-containing halogenated vinyl ethers or perfluoroalkyl vinyl ether usually through dehalogenate or hydrogen halide.As everyone knows, perfluoroalkyl vinyl ether can be used as viton synthesis and fluororesin modified important monomer.
Preparation containing fluorohalogenethers can by fluorine oxycompound as fluorine oxygen base trifluoromethane and olefine reaction generate.Fluorine oxygen base trifluoromethane molecular formula is CF
3oF is a kind of comparatively special fluorochemicals.Because O-F key bond energy is lower, fluorine oxygen base trifluoromethane is made to have stronger oxidation capacity and higher reactive behavior.Can occur between fluorine oxygen base trifluoromethane and alkene fast, the chemical reaction of strong heat release, if control improper, usually have a large amount of by products and generate, cause target product yield lower.Therefore, prior art normally at low temperature or/and in solvent, with rare gas element as the fluorine oxygen base trifluoromethane of nitrogen dilution and the haloolefin of solvent cut carry out liquid phase addition reaction, although the severe degree of reaction can be alleviated to a certain extent, exist temperature low reaction time length, complicated operation, production efficiency low, can not the problem of continuous prodution.Also have the document of part research reaction mechanism to be realized by the gas phase thermal response of fluorine oxygen base trifluoromethane and alkene, these experimental installations are less, feeding quantity is less, although also can control the severe degree of reacting, but can not be applied to industrial production.
Patent US4077857 and US4149016 discloses a kind of method preparing perfluor ether.Described method be with fluorine oxygen base trifluoromethane and perfluoroolefine for raw material, under low temperature (-20 DEG C) and ultraviolet irradiation condition, carry out addition reaction.Perfluoroolefine described in it is five yuan or hexa-atomic perfluor cyclic olefins, and be not a kind of industrial chemicals be easy to get, light irradiation apparatus complexity is not easily amplified in addition, is not suitable for industrial production.
Patent US5648560 and US5877357 discloses a kind of method preparing perhalogeno ether.Described method is with the fluorine oxygen base trifluoromethane of nitrogen dilution, fluorine oxygen base pentafluoride ethane and fluorine gas for raw material, carries out liquid phase addition reaction respectively with fluorine-containing haloolefin or perfluoroalkyl vinyl ether at temperature, the inert organic solvents lower than 20 DEG C under existing.Described fluorine-containing haloolefin comprises R 1216, trifluorochloroethylene, 1,2-dichlorodifluoroethylene, and perfluoroalkyl vinyl ether comprises perfluoro methyl vinyl ether, perfluoroethylvinyl ether and perfluoro propyl vinyl ether.Production efficiency is reduced with nitrogen dilution reaction raw materials, lower temperature of reaction result also in the longer reaction times, reduce production efficiency equally, need to increase extra external source to control lower temperature of reaction (embodiment temperature of reaction-40 ~-100 DEG C) simultaneously, cause device complicated, this is disadvantageous in the industrial production.
Patent EP1801090 and EP1801091 discloses a kind of method preparing fluorohalogenethers, described method with haloolefin and with the fluorine oxycompound of inert gas dilution for raw material, implement under the organic solvent in inertia under liquid phase, temperature of reaction-130 ~ 0 DEG C, reaction conditions exists.Wherein said fluorine oxycompound comprises fluorine oxygen base trifluoromethane, fluorine oxygen base pentafluoride ethane and fluorine oxygen base heptafluoro-propane, and haloolefin is chloro-1, the 2-difluoroethylene of 1,2-dichlorodifluoroethylene and 1-.The shortcoming of this method is that production efficiency is low equally, and also need lower external source, embodiment is all reacted at-70 DEG C.
Chinese patent CN102001919A discloses a kind of Trifluoromethyl-1, the preparation method of fluoro-1, the 2-Dichloroethyl ether of 2,2-tri-.Specifically use the fluorine oxygen base trifluoromethane of nitrogen dilution and 1,2-dichlorodifluoroethylene of liquid phase-110 ~-5 DEG C of reactions, there is no content and yield data.The same production efficiency of this method is low, also needs lower external source, can only batch production, and this is disadvantageous in the industrial production.
Document J.Org.Chem.1983,48,242-250 and J.Org.Chem.1995,60,6441-6443 have studied fluorine oxygen base trifluoromethane and alkene liquid phase addition reaction at low temperatures in succession, and temperature of reaction is-160 ~ 22 DEG C, solvent is trichlorofluoromethane and methyl chlorofluoride etc.; Document Int.J.Chem.Kinet.1984,16,103-115 have studied the gas phase addition reaction of fluorine oxygen base trifluoromethane and R 1216, and temperature is respectively 25 DEG C, 50 DEG C and 75 DEG C; Document J.Fluorine.Chem.1994,66,1-4 and J.Fluorine.Chem.1995,74,199-201 have studied fluorine oxygen base trifluoromethane and trieline, the addition reaction of zellon gas phase respectively, and the former temperature of reaction is 50 DEG C, and the latter is 40-70 DEG C; Document J.Fluorine.Chem.2008,129,680-685 have studied low temperature (-80 DEG C ~-100 DEG C), (solvent is respectively CF to liquid phase
3oCFClCFCl
2with fluorine ether oil PFPEGalden1LS155) under condition, the fluorine oxygen base trifluoromethane of helium dilution under a small amount of fluorophosgene exists respectively with the reaction of perfluoro methyl vinyl ether, tetrafluoroethylene, 1,2-dichlorodifluoroethylene.Above-mentioned document is lab setup and periodical operation, even if in the gas phase addition reaction that temperature of reaction is higher, namely reaction neither add raw material and collect product continuously by continuous print continuously, can not be applied to industrial production.
To sum up, existingly react the method for preparation containing fluorohalogenethers by fluorine oxygen base trifluoromethane and haloolefin, normally at low temperature or/and in solvent, the fluorine oxygen base trifluoromethane of dilution and the haloolefin reaction preparation of liquid phase, there is complicated operation, production efficiency is low, can not quantity-produced problem.
Summary of the invention
The object of the invention is to for the above-mentioned deficiency in prior art, provide a kind of method prepared containing fluorohalogenethers, the method technique is simple, can continuous seepage, have that measuring requirement is low, convenient operation, yield and the high feature of efficiency, be suitable for industrialization continuous seepage.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
Prepare the method containing fluorohalogenethers, it is characterized in that: comprise following processing step:
A, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 0.6-1.3:1;
B, the haloolefin heat air of liquid phase is changed into gas phase, pass into reactor continuously with the fluorine oxygen base trifluoromethane of gas phase simultaneously, controlling fluorine oxygen base trifluoromethane, to spray into pressure be 0.1-1MPa;
C, control temperature of reaction are 80-200 DEG C, carry out thermal addition reaction, obtain containing fluorohalogenethers.
In step, described haloolefin is at least one in Ethylene Dichloride, trieline, zellon, difluoroethylene, dichlorodifluoroethylene, trifluorochloroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether in the present invention.
The present invention in step, at least one of described haloolefin preferably in trieline, zellon, dichlorodifluoroethylene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether.
In step, described fluorine oxygen base trifluoromethane and the mol ratio of haloolefin are 0.8-1.1:1 in the present invention.
The present invention is in step C, and described temperature of reaction is preferably 90-150 DEG C.
The present invention adopts gas phase thermal addition reaction, and two kinds of reaction raw materials fluorine oxygen base trifluoromethanes and haloolefin pass into reactor all in gaseous form, under normal temperature being liquid haloolefin, and need by passing into reactor reaction again after heating and gasifying.Two kinds of gaseous phase materials, all without the need to inert gas dilution, are certainly used inert gas dilution, also can be completed reaction process of the present invention, just can reduce production efficiency and production capacity, little on the impact of the control of reacting and yield.
The present invention can adopt the general tubular reactor with chuck to carry out, and is certainly also applicable to the reactor described by Chinese patent CN2757913.
The present invention sprays into pressure and feed rate by control valve opening control fluorine oxygen base trifluoromethane, and existing variable valve can solve the etching problem of fluorine oxygen base trifluoromethane.Haloolefin is corrosion-free to metering outfit, and its flow is regulated by delicate flow meter.Generally suitably excessive at operation time control haloolefin, poisonous and that corrodibility is extremely strong fluorine oxygen base trifluoromethane is exhausted in the reaction, is beneficial to environment protection.The boiling point containing fluorohalogenethers because of haloolefin and product differs greatly, and recycles haloolefin by simple tripping device, reduces the loss of material.When fluorine oxygen base trifluoromethane material inlet valve aperture is certain, by the content size of haloolefin residual in detection reaction product, then the size of feed rate according to its size adjustment haloolefin, to reach the object controlling reaction mass proportioning.
The control of temperature of reaction is by regulating the aperture of reactor cooling chuck circulating water intake valve.General chemical plant all has circulating water device, very cheap with water price lattice.
The Advantageous Effects that the present invention brings:
1, the invention solves preparation in prior art and contain the problem of fluorohalogenethers, two kinds of raw materials are all gas phase, spraying into pressure, specific temperature of reaction and specific reaction mass proportioning by controlling specific fluorine oxygen base trifluoromethane, can guarantee to obtain continuously containing fluorohalogenethers with high yield and efficiency.Reaction mass of the present invention only two kinds, technique is simple, can be continuously produced, has the advantage that measuring requirement is low, convenient operation, yield and efficiency are high, and be very suitable for industrial production.
2, the present invention controls fluorine oxygen base trifluoromethane to spray into pressure is 0.1-1MPa.If spray into hypotony, linear velocity can be caused low, mixing of materials weak effect, local excessive can be caused to react, and product purity and yield significantly reduce; If spray into hypertonia, the too high meeting of linear velocity causes material reaction incomplete, wastes raw material.Adopt and of the present inventionly spray into pressure range, can guarantee that fluorine oxygen base trifluoromethane has certain linear velocity, avoid local excessive to react, simultaneously also can hybrid reaction material better.
3, temperature of reaction of the present invention controls as 80-200 DEG C.If temperature of reaction is too low, the fluorohalogenethers that contains of generation is easy to along reactor wall cooling for reflux, causes hydrops and blocking material inlet; If temperature of reaction is too high, side reaction can increase, and causes target product yield to decline.Adopt temperature of reaction of the present invention, hydrops and blocking material inlet can be avoided, the increase of side reaction can be prevented again.Preferred temperature of reaction is 90-150 DEG C, can reach best yield and content.
4, the mol ratio of fluorine oxygen base trifluoromethane of the present invention and haloolefin controls as 0.6-1.3:1.If fluorine oxygen base trifluoromethane is too much excessive, can because the strong oxidizing property of fluorine oxygen base trifluoromethane cause runaway reaction, temperature sharply rises, and a large amount of side reactions occurs, target product seldom or does not almost have, the excessive waste that yet can cause material too much of fluorine oxygen base trifluoromethane simultaneously; If fluorine oxygen base trifluoromethane very little or haloolefin too much excessive, be also waste material, the reduction of yield and the increase of unit consumption can be caused.Adopt material rate scope of the present invention, a large amount of side reactions can be avoided to produce, cut the waste, improve yield.Preferred mol ratio is 0.8-1.1:1, can reach best yield.
Embodiment
embodiment 1
Prepare the method containing fluorohalogenethers, comprise following processing step:
A, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 0.6:1;
B, the haloolefin heat air of liquid phase is changed into gas phase, pass into reactor continuously with the fluorine oxygen base trifluoromethane of gas phase simultaneously, controlling fluorine oxygen base trifluoromethane, to spray into pressure be 0.1MPa;
C, control temperature of reaction are 80 DEG C, carry out thermal addition reaction, obtain containing fluorohalogenethers.
embodiment 2
Prepare the method containing fluorohalogenethers, comprise following processing step:
A, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 1.3:1;
B, the haloolefin heat air of liquid phase is changed into gas phase, pass into reactor continuously with the fluorine oxygen base trifluoromethane of gas phase simultaneously, controlling fluorine oxygen base trifluoromethane, to spray into pressure be 1MPa;
C, control temperature of reaction are 200 DEG C, carry out thermal addition reaction, obtain containing fluorohalogenethers.
embodiment 3
Prepare the method containing fluorohalogenethers, comprise following processing step:
A, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 0.95:1;
B, the haloolefin heat air of liquid phase is changed into gas phase, pass into reactor continuously with the fluorine oxygen base trifluoromethane of gas phase simultaneously, controlling fluorine oxygen base trifluoromethane, to spray into pressure be 0.55MPa;
C, control temperature of reaction are 140 DEG C, carry out thermal addition reaction, obtain containing fluorohalogenethers.
embodiment 4
Prepare the method containing fluorohalogenethers, comprise following processing step:
A, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 1.2:1;
B, the haloolefin heat air of liquid phase is changed into gas phase, pass into reactor continuously with the fluorine oxygen base trifluoromethane of gas phase simultaneously, controlling fluorine oxygen base trifluoromethane, to spray into pressure be 0.3MPa;
C, control temperature of reaction are 150 DEG C, carry out thermal addition reaction, obtain containing fluorohalogenethers.
embodiment 5
Prepare the method containing fluorohalogenethers, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the fluorine oxygen base trifluoromethane of the haloolefin of gas phase and gas phase is passed into continuously reactor and carry out thermal addition reaction and obtain containing fluorohalogenethers; Control fluorine oxygen base trifluoromethane and spray into pressure 1MPa, temperature of reaction is 200 DEG C, and the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 1.3:1.
embodiment 6
Prepare the method containing fluorohalogenethers, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the fluorine oxygen base trifluoromethane of the haloolefin of gas phase and gas phase is passed into continuously reactor and carry out thermal addition reaction and obtain containing fluorohalogenethers; Control fluorine oxygen base trifluoromethane and spray into pressure 0.6MPa, temperature of reaction is 115 DEG C, and the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 0.95:1.
embodiment 7
Prepare the method containing fluorohalogenethers, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the fluorine oxygen base trifluoromethane of the haloolefin of gas phase and gas phase is passed into continuously reactor and carry out thermal addition reaction and obtain containing fluorohalogenethers; Control fluorine oxygen base trifluoromethane and spray into pressure 0.1MPa, temperature of reaction is 80 DEG C, and the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 1.2:1.
embodiment 8
On the basis of embodiment 1-7:
Preferably, described haloolefin is at least one in Ethylene Dichloride, trieline, zellon, difluoroethylene, dichlorodifluoroethylene, trifluorochloroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether.
Preferably, at least one of described haloolefin preferably in trieline, zellon, dichlorodifluoroethylene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether.
Preferably, described fluorine oxygen base trifluoromethane and the mol ratio of haloolefin are 0.8:1.
Preferably, described temperature of reaction is 90 DEG C.
embodiment 9
On the basis of embodiment 1-7:
Preferably, described haloolefin is at least one in Ethylene Dichloride, trieline, zellon, difluoroethylene, dichlorodifluoroethylene, trifluorochloroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether.
Preferably or further, at least one of described haloolefin preferably in trieline, zellon, dichlorodifluoroethylene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether.
Preferably, described fluorine oxygen base trifluoromethane and the mol ratio of haloolefin are 1.1:1.
Preferably, described temperature of reaction is 150 DEG C.
embodiment 10
On the basis of embodiment 1-7:
Preferably, described haloolefin is at least one in Ethylene Dichloride, trieline, zellon, difluoroethylene, dichlorodifluoroethylene, trifluorochloroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether.
Preferably or further, at least one of described haloolefin preferably in trieline, zellon, dichlorodifluoroethylene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether.
Preferably, described fluorine oxygen base trifluoromethane and the mol ratio of haloolefin are 0.95:1.
Preferably, described temperature of reaction is 120 DEG C.
embodiment 11
On the basis of embodiment 1-7:
Preferably, described haloolefin is at least one in Ethylene Dichloride, trieline, zellon, difluoroethylene, dichlorodifluoroethylene, trifluorochloroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether.
Preferably or further, at least one of described haloolefin preferably in trieline, zellon, dichlorodifluoroethylene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether.
Preferably, described fluorine oxygen base trifluoromethane and the mol ratio of haloolefin are 0.9:1.
Preferably, described temperature of reaction is 110 DEG C.
embodiment 12
Fluorine oxygen base trifluoromethane (CF
3oF) referenced patent CN1051350 preparation, average content 82.4%.
In the stainless steel tubular reactor of band cooling jacket, by under meter with 1.3m
3the flow of/h passes into the perfluoro methyl vinyl ether (being called for short PMVE) of content 99.5% from the alkene import of reactor bottom.After PMVE stability of flow, start to have control with 0.8m
3the flow of/h is from the CF of reactor bottom
3oF import passes into the CF of average content 82%
3oF reacts, now CF
3it is 0.15MPa that OF sprays into pressure, and reaction starts rear temperature and sharply rises, and control valve opening recirculated water being entered reactor jacket is set as 100%.Maintain control valve opening 100% and PMVE flow constant, progressively increase CF after 10 minutes
3oF flow is to 1.5m
3/ h, CF
3it is 0.45MPa that OF sprays into pressure.The product collection generated is in-35 DEG C of freezing rewinding test tanks, and the gaseous product that can not cool passes through neutralizing treatment.The tail gas composition that sampling analysis test tank top is got rid of and content, controlling PMVE content in tail gas is 0 ~ 1%, if PMVE content is greater than 1%, needs suitably to reduce PMVE feed rate; Controlling temperature of reaction by controlled circulation water regulating valve aperture is 80-120 DEG C.Terminate reaction after 48 hours, adding up to pass into raw material PMVE is 439 kilograms, CF
3oF is 337 kilograms, CF
3oF and PMVE mol ratio is 1.01, collects liquid product totally 684 kilograms, two kinds of isomer C F in GC-MS combination analysis target product
3oCF
2cF
2oCF
3(CF
3o)
2cFCF
3content is respectively 76.31% and 7.45%.In PMVE, target compound yield is 80.7%.
embodiment 13
Perfluoro propyl vinyl ether (being called for short PPVE) with 98.7% replaces the PMVE in embodiment 12.PPVE passes into reactor after heating and gasifying, and flow is 1.7m
3/ h, the CF of 82%
3oF flow is 2.3m
3/ h, CF
3it is 1MPa that OF sprays into pressure, and control temperature of reaction is 80-100 DEG C, and by composition and the content of sampling analysis test tank rewinding product, controlling PPVE content in liquid phase is 0-1%.Terminate reaction after 15 hours, adding up to pass into raw material PPVE is 239 kilograms, CF
3oF is 162 kilograms, CF
3oF and PPVE mol ratio is 1.17 ,-20 DEG C of freezing collection liquid products totally 377 kilograms, target product CF
3cF
2cF
2oCF
2cF
2oCF
3content is 69.1%.In PPVE, target compound yield is 81.4%.
embodiment 14
1,2-dichlorodifluoroethylene (being called for short F1112a) with 99.2% replaces the PPVE in embodiment 13.F1112a flow is 1.7m
3/ h, the CF of 82%
3oF flow is 1.8m
3/ h, CF
3it is 0.7MPa that OF sprays into pressure, and control temperature of reaction is 140-170 DEG C, and controlling F1112a content in liquid phase is 0-1%.Terminate reaction after 190 hours, adding up to pass into raw material F1112a is 1935 kilograms, CF
3oF is 1623 kilograms, CF
3oF and F1112a mol ratio is 0.89 ,-20 DEG C of freezing collection liquid products totally 3147 kilograms, target product CF
3oCFClCF
2cl content is 87.23%.In F1112a, target compound yield is 80.3%.
embodiment 15
Trieline (being called for short TCE) with 99.5% replaces the PPVE in embodiment 13.TCE flow is 0.9m
3/ h, the CF of 86%
3oF flow is 0.9m
3/ h, CF
3it is 0.23MPa that OF sprays into pressure, and control temperature of reaction is 120-150 DEG C, and controlling TCE content in liquid product is 0-1%.Terminate reaction after 24 hours, adding up to pass into raw material TCE is 125 kilograms, CF
3oF is 94 kilograms, CF
3oF and TCE mol ratio is 0.82 ,-20 DEG C of freezing collection liquid products totally 213 kilograms, target product CF
3oCHClCFCl
2content is 88.54%.In TCE, target compound yield is 84.8%.
embodiment 16
Zellon (being called for short PCE) with 99.8% replaces the PPVE in embodiment 13.PCE flow is 0.5m
3/ h, the CF of 86%
3oF flow is 0.65m
3/ h, CF
3it is 0.1MPa that OF sprays into pressure, and control temperature of reaction is 160-195 DEG C, and controlling PCE content in liquid product is 0-1%.Terminate reaction after 31 hours, adding up to pass into raw material PCE is 121 kilograms, CF
3oF is 90 kilograms, CF
3oF and PCE mol ratio is 1.02 ,-20 DEG C of freezing collection liquid products totally 188 kilograms, target product CF
3oCCl
2cFCl
2content is 84.3%.In PCE, target compound yield is 80.7%.
Claims (5)
1. prepare the method containing fluorohalogenethers, it is characterized in that: comprise following processing step:
A, with fluorine oxygen base trifluoromethane and haloolefin for raw material, the mol ratio of fluorine oxygen base trifluoromethane and haloolefin is 0.6-1.3:1;
B, the haloolefin heat air of liquid phase is changed into gas phase, pass into reactor continuously with the fluorine oxygen base trifluoromethane of gas phase simultaneously, controlling fluorine oxygen base trifluoromethane, to spray into pressure be 0.1-1MPa;
C, control temperature of reaction are 80-200 DEG C, carry out thermal addition reaction, obtain containing fluorohalogenethers.
2. a kind of method prepared containing fluorohalogenethers according to claim 1, it is characterized in that: in step, described haloolefin is at least one in Ethylene Dichloride, trieline, zellon, difluoroethylene, dichlorodifluoroethylene, trifluorochloroethylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether.
3. a kind of method prepared containing fluorohalogenethers according to claim 1, it is characterized in that: in step, described haloolefin is at least one in trieline, zellon, dichlorodifluoroethylene, perfluoro methyl vinyl ether, perfluoro propyl vinyl ether.
4. according to a kind of method prepared containing fluorohalogenethers in claim 1-3 described in any one, it is characterized in that: in step, described fluorine oxygen base trifluoromethane and the mol ratio of haloolefin are 0.8-1.1:1.
5. a kind of method prepared containing fluorohalogenethers according to claim 1, is characterized in that: in step C, and described temperature of reaction is 90-150 DEG C.
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| CN109305893A (en) * | 2017-07-27 | 2019-02-05 | 中昊晨光化工研究院有限公司 | A kind of synthetic method and synthesizer of 1,2- difluoroethylene trifluoromethyl ethers |
| CN112079695A (en) * | 2020-08-19 | 2020-12-15 | 浙江巨化技术中心有限公司 | Preparation method for co-production of 1, 2-bis (trifluoromethoxy) difluoroethylene by 1, 1-bis (trifluoromethoxy) difluoroethylene |
| CN114174250A (en) * | 2020-11-06 | 2022-03-11 | 福建永晶科技股份有限公司 | Novel process for industrially synthesizing perfluoromethyl vinyl ether and 2-fluoro-1, 2-dichloro-trifluoromethoxyethylene |
| WO2022095625A1 (en) * | 2020-11-06 | 2022-05-12 | Fujian Yongjing Technology Co., Ltd | New industrial process for manufacturing of perfluoro (methyl vinyl ether) (pfmve) and of 2-fluoro-1, 2-dichloro-trifluoromethoxyethylene (fctfe) |
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| CN107867977A (en) * | 2016-09-27 | 2018-04-03 | 中昊晨光化工研究院有限公司 | A kind of preparation method of pentafluoroethyl group trifluoromethyl ethers |
| CN109305893A (en) * | 2017-07-27 | 2019-02-05 | 中昊晨光化工研究院有限公司 | A kind of synthetic method and synthesizer of 1,2- difluoroethylene trifluoromethyl ethers |
| CN109305893B (en) * | 2017-07-27 | 2020-10-30 | 中昊晨光化工研究院有限公司 | Synthesis method and synthesis device of 1, 2-difluoroethylene trifluoromethyl ether |
| CN112079695A (en) * | 2020-08-19 | 2020-12-15 | 浙江巨化技术中心有限公司 | Preparation method for co-production of 1, 2-bis (trifluoromethoxy) difluoroethylene by 1, 1-bis (trifluoromethoxy) difluoroethylene |
| CN112079695B (en) * | 2020-08-19 | 2022-07-29 | 浙江巨化技术中心有限公司 | Preparation method for co-production of 1, 2-bis (trifluoromethoxy) difluoroethylene by 1, 1-bis (trifluoromethoxy) difluoroethylene |
| CN114174250A (en) * | 2020-11-06 | 2022-03-11 | 福建永晶科技股份有限公司 | Novel process for industrially synthesizing perfluoromethyl vinyl ether and 2-fluoro-1, 2-dichloro-trifluoromethoxyethylene |
| WO2022095625A1 (en) * | 2020-11-06 | 2022-05-12 | Fujian Yongjing Technology Co., Ltd | New industrial process for manufacturing of perfluoro (methyl vinyl ether) (pfmve) and of 2-fluoro-1, 2-dichloro-trifluoromethoxyethylene (fctfe) |
| CN114174250B (en) * | 2020-11-06 | 2024-05-14 | 福建永晶科技股份有限公司 | New process for industrially synthesizing perfluoromethyl vinyl ether and 2-fluoro-1, 2-dichloro-trifluoromethoxy ethylene |
| CN114656338A (en) * | 2022-04-24 | 2022-06-24 | 四川道宏新材料有限公司 | Synthesis method of perfluoro-n-propyl vinyl ether |
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