CN111269079B - Preparation system and preparation method of perfluoro 1, 3-butadiene - Google Patents
Preparation system and preparation method of perfluoro 1, 3-butadiene Download PDFInfo
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- CN111269079B CN111269079B CN202010104503.9A CN202010104503A CN111269079B CN 111269079 B CN111269079 B CN 111269079B CN 202010104503 A CN202010104503 A CN 202010104503A CN 111269079 B CN111269079 B CN 111269079B
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- butadiene
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- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 40
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 claims abstract description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- PRJQLUNGZQZONS-UHFFFAOYSA-N chloro(diethyl)borane Chemical compound CCB(Cl)CC PRJQLUNGZQZONS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- HYDZYXLZFSZQLP-UHFFFAOYSA-N C(C)BCC.[Cl] Chemical compound C(C)BCC.[Cl] HYDZYXLZFSZQLP-UHFFFAOYSA-N 0.000 claims description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003750 ethyl chloride Drugs 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000000376 reactant Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 32
- 239000006227 byproduct Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- QVHWOZCZUNPZPW-UHFFFAOYSA-N 1,2,3,3,4,4-hexafluorocyclobutene Chemical compound FC1=C(F)C(F)(F)C1(F)F QVHWOZCZUNPZPW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001312 dry etching Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920006926 PFC Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KAVGMUDTWQVPDF-UHFFFAOYSA-N perflubutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 description 1
- 229950003332 perflubutane Drugs 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
Abstract
The invention discloses a preparation system and a preparation method of perfluoro-1, 3-butadiene, wherein a specific preparation system is adopted, 1, 4-diiodooctafluorobutane and chloro-diethyl-borane are reacted in a solvent tetrahydrofuran, and then the product is rectified for three times to improve the purity of the reactant.
Description
Technical Field
The invention belongs to the technical field of microfluidics and organic synthesis, and particularly relates to a preparation system and a preparation method of perfluoro-1, 3-butadiene.
Background
Perfluoro 1, 3-butadiene (CF) 2 ＝CF-CF＝CF 2 Abbreviated as C 4 F 6 ) Is a liquefied gas containing two double bonds. The molecular weight is 162, the melting point is-132 ℃, the boiling point is 6 ℃, the critical temperature is 140 ℃, the gas phase density relative to air is 6.79 (1.4 g/mL,15 ℃), and the combustion range is 7% -73%. GWP value of perfluorobutadieneOnly 290, the service life in the atmosphere is less than 2 days, and the environment is not affected basically.
The perfluoro-1, 3-butadiene has various industrial applications, not only can be used for preparing monomers of various fluorine-containing high-molecular elastic materials of poly-perfluorobutadiene, but also can be used as an environment-friendly high-efficiency dry etching gas with extremely low greenhouse effect. The perfluorobutadiene is used as a monomer with difunctional groups and is suitable for preparing and crosslinking a perfluorinated elastomer, and can be prepared into the perfluorobutadiene, and can also be used for synthesizing a fluorine-containing elastomer and a resin with excellent electrical properties with other monomers. Perfluoro-1, 3-butadiene is an excellent dry etching gas for integrated circuits, which not only can dry etch ultra-large integrated circuits with widths smaller than 90nm and even narrower, but also has high selectivity and high accuracy, and is more suitable for etching processes with high aspect ratios. Perfluorobutadiene has many advantages over C in terms of 0.13 μm technology in terms of etching 4 F 8 The photoresist and silicon nitride selectivity ratio is higher, the etching stability can be improved during use, and the etching rate and uniformity are improved, so that the product yield is improved. Perfluorobutadiene has anisotropy, can produce ideal high-width ratio in silicon and silicon oxide etching, and can protect side walls when etching to form a polymer film (photoresist). Perfluoro 1, 3-butadiene can be used not only in the etching of higher demanding electronics, but also to replace PFCs currently being used in dry etching of electronics. The perfluoro-1, 3-butadiene has small greenhouse effect and little harm to the ozone layer, is an environment-friendly dry etching gas, and has wide market prospect.
At present, the preparation method of perfluoro 1, 3-butadiene generally has the problems of more byproducts and low reaction yield, and mainly aims at generating perfluorocyclobutene as a byproduct in the process of generating perfluoro 1, 3-butadiene as a target product by dehalogenation of 1, 4-dihalide perfluorobutane, wherein the boiling points of the perfluorocyclobutene and the perfluorocyclobutene are only different by 0.8 ℃, so that great difficulty is brought to separation, and the perfluorocyclobutene dissolved in a solvent is difficult to extract, so that the yield of the product is reduced.
Disclosure of Invention
In order to overcome the technical defects, the invention adopts the following technical scheme:
the invention provides a perfluoro-1, 3-butadiene preparation system, which comprises a reaction mechanism, a purification mechanism and a collection mechanism which are sequentially connected through pipelines; wherein,
the reaction mechanism comprises a micro-reactor, a first rectifying tower and a first condenser which are arranged in a bottom-to-top communication manner, wherein two raw material inlets of the micro-reactor are respectively connected with a chlorine-diethyl-borane storage tank dissolved in tetrahydrofuran and a 1, 4-diiodooctafluorobutane storage tank dissolved in tetrahydrofuran, a tail gas outlet of the first condenser is connected to a tail gas tank, a product outlet is connected to the purification mechanism, and the purification mechanism is used for purifying the product and then conveying the purified product to the collection mechanism for collection;
the purification mechanism comprises a second rectifying tower and a second condenser, a product outlet of the first condenser is connected to the second rectifying tower, a steam outlet of the second rectifying tower is connected to a tail gas tank through the second condenser, and a product outlet of the second rectifying tower is connected to the collection mechanism; further preferably, the purification mechanism further comprises a third rectifying tower and a third condenser, wherein a product outlet of the second rectifying tower is connected to the third rectifying tower, a steam outlet of the third rectifying tower is connected to the third condenser, and an outlet of the third condenser is connected to the third rectifying tower and the collection mechanism;
further, the preparation system of the perfluoro 1, 3-butadiene further comprises a vacuum mechanism or an inert gas purging mechanism;
further preferably, the vacuum mechanism is connected to a pipeline to maintain an internal vacuum;
further preferably, the inert gas purging mechanism is connected to the pipeline to blow inert gas along the output direction of the product; by adopting the scheme, the separation speed of the perfluorobutadiene mixed system contained in the first rectifying tower and the solvent can be effectively improved under the condition of purging by inert gas, so that the chance of retention and self-polymerization in the solvent is reduced.
The second aspect of the invention also provides a method for continuously synthesizing perfluoro-1, 3-butadiene by adopting the perfluoro-1, 3-butadiene preparation system, which comprises the following steps of reacting 1, 4-diiodooctafluorobutane with chloro-diethyl-borane in tetrahydrofuran solvent in the preparation system;
further, the molar use ratio of the 1, 4-diiodooctafluorobutane to the chloro-diethyl-borane is 1:0.5-2; preferably, the molar ratio of the 1, 4-diiodooctafluorobutane to the chloro-diethyl-borane is 1:1;
further, the reaction temperature is 10-25 ℃; preferably, the reaction temperature is 20 ℃;
further, the reaction is carried out under vacuum conditions or normal pressure with inert gas purging; further preferably, the vacuum degree is 13.33 to 40kPa; or further preferably, the inert gas is N 2 The flow rate is 0.5-1.0L/h; more preferably, the N 2 The flow rate of (2) is 0.75L/h;
further, the specific steps of the method for continuously synthesizing perfluoro 1, 3-butadiene comprise:
s1: mixing and dripping a tetrahydrofuran solution of 1, 4-diiodooctafluorobutane and a tetrahydrofuran solution of chloro-diethyl-borane into a micro-reactor communicated with a first rectifying tower, and fully mixing and reacting in the micro-reactor to form a mixed system A comprising 1, 4-diiodooctafluorobutane, chloro-diethyl-borane, chloroethane, target products of perfluoro-1, 3-butadiene and tetrahydrofuran;
s2: introducing the mixed system A into a first condenser, and rectifying and condensing while continuing the reaction to remove tetrahydrofuran to form a mixed system B;
s3: introducing the mixed system B into a second rectifying tower and a second condenser for rectification, wherein the rectification temperature is lower than the boiling point of the target product of perfluoro 1, 3-butadiene so as to remove partial impurities with the boiling point lower than that of perfluoro 1, 3-butadiene and form a mixed system C;
s4: introducing the mixed system C into a third rectifying tower and a third condenser for rectification, wherein the rectification temperature is higher than the boiling point of the target product of perfluoro-1, 3-butadiene, and repeatedly rectifying to remove impurities with the boiling point higher than that of perfluoro-1, 3-butadiene.
Further, the micro-reactor in the step S1 is a micro-channel type, capillary type, falling film type, multi-strand parallel flow type, micro-pore array type or membrane dispersion type micro-reactor; preferably, the microreactor described in S1 is a microchannel microreactor.
The beneficial effects are that:
compared with the prior art, the invention has the following beneficial effects:
1. microreactors used in the present invention generally refer to microstructured chemical reactors whose internal fluid channels or dispersion space dimensions are on the order of micrometers. In the reactor, the mass transfer and the heat transfer process of a reaction system are greatly improved, so that the problems of heat transfer and mass transfer of the reaction are effectively solved, and the production of byproduct perfluorocyclobutene is effectively reduced.
2. The byproduct can be effectively removed by repeated fractional cyclic rectification, and the purity of the product is obviously improved.
3. The mixed system containing perfluorobutadiene in the first condenser can be effectively separated from the solvent by adopting inert gas to purge, so that the chance of retention and self-polymerization in the solvent is reduced, and the generation of byproducts is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. Like elements or portions are generally identified by like reference numerals throughout the several figures. In the drawings, elements or portions thereof are not necessarily drawn to scale.
Fig. 1 is a schematic structural view of embodiment 1 of the present invention.
Fig. 2 is a schematic structural view of embodiment 2 of the present invention.
The figure shows:
1. a microreactor;
2. a first rectifying column;
3. a first condenser;
4. a chloro-diethyl-borane storage tank;
5. a 1, 4-diiodooctafluorobutane storage tank;
6. a tail gas tank;
7. a second rectifying column;
8. a second condenser;
9. a third rectifying column;
10. a third condenser;
11. a filler;
12. pretreating a steel cylinder;
13. a vacuum pump;
14. an inert gas storage tank;
15. a blower.
Detailed Description
Embodiments of the technical scheme of the present invention will be described in detail below. The following examples are only for more clearly illustrating the technical aspects of the present invention, and thus are merely examples, which should not be construed as limiting the scope of the present invention. It is noted that unless otherwise indicated, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
Example 1:
as shown in FIG. 1, the system for preparing perfluorobutadiene provided in this embodiment comprises a reaction mechanism, a purification mechanism, a collection mechanism and a vacuum mechanism which are sequentially connected through a pipeline.
The reaction mechanism comprises a micro-reactor 1, a first rectifying tower 2 and a first condenser 3 which are arranged in a bottom-to-top communication way, wherein two raw material inlets of the micro-reactor 1 are respectively connected with a tetrahydrofuran-dissolved chlorine-diethyl-borane storage tank 4 and a tetrahydrofuran-dissolved 1, 4-diiodooctafluorobutane storage tank 5, a tail gas outlet of the first condenser 3 is connected to a tail gas tank 6, and a product outlet is connected to the purification mechanism.
The micro-reactor 1 and the first rectifying tower 2 are integrally arranged, the tetrahydrofuran-dissolved chlorine-diethyl-borane and the tetrahydrofuran-dissolved 1, 4-diiodooctafluorobutane are dropwise added into the micro-reactor 1, the two are fully mixed and reacted in a micro-channel in the micro-reactor 1, the problems of heat transfer and mass transfer of the reaction are effectively solved, the problem of side reaction is effectively solved, meanwhile, the two and a reaction product enter the first rectifying tower 2 and the first condenser 3, the rectification operation is carried out while the reaction, a mixed system (containing target product perfluorobutadiene) generated by the reaction is rapidly separated from a solvent, the generation of byproduct perfluorocyclobutene is effectively reduced, and then the product is further purified, so that the reaction yield and the selectivity of the product are effectively improved.
The purification mechanism comprises a second rectifying tower 7, a second condenser 8, a third rectifying tower 9 and a third condenser 10, wherein a product outlet of the first condenser 3 is connected to the second rectifying tower 7, a steam outlet of the second rectifying tower 7 is connected to the tail gas tank 6 through the second condenser 8, and a product outlet of the second rectifying tower 7 is connected to the third rectifying tower 9.
The second rectifying tower 7 is internally subjected to low-temperature rectification, and the rectification temperature is lower than the boiling point of target product perfluorobutadiene, so that tail gases such as chloroethane and the like generated by the reaction in the product are further removed, and the purity is improved.
The steam outlet of the third rectifying tower 9 is connected to a third condenser 10, and the outlet of the third condenser 10 is connected to the third rectifying tower 9 and the collecting mechanism.
The third rectifying tower 9 is internally subjected to low-temperature rectification, and the rectification temperature is slightly higher than the boiling point of the target product perfluorobutadiene, so that other reaction byproducts with higher boiling points are removed; the steam outlet of the third rectifying tower 9 is connected to a third condenser 10, the outlet part of the third condenser 10 is refluxed to the third rectifying tower 9 to form circulation, and part of the reflux is conveyed to a collecting mechanism to be collected, so that the purity of the product is improved.
The collection mechanism includes a filler 11 and a priming cylinder 12.
The vacuum mechanism comprises a vacuum pump 13, and the vacuum pump 13 is connected to a pipeline to maintain internal vacuum, so that the speed of separating the mixed system containing the perfluorobutadiene in the first condenser 3 from the solvent can be effectively improved, and the chance of the mixed system remaining in the solvent and self-polymerizing is reduced.
Example 2:
this embodiment is substantially the same as the first embodiment except that the vacuum mechanism is not used, but the separation speed of the perfluorobutadiene is clamped by an inert gas purging mechanism, which includes an inert gas storage tank 14 and a blower 15 connected to each other, and nitrogen is used as the inert gas in this embodiment, and the nitrogen is blown along the output direction of the product, so that the separation speed of the mixed system containing perfluorobutadiene in the first condenser 3 from the solvent can be effectively improved, and the chance of residence and self-polymerization in the solvent can be reduced.
Example 3:
a method for continuously synthesizing perfluoro 1, 3-butadiene by using the preparation system of example 1 comprises the following specific steps:
s1: at 20 ℃ and under the vacuum degree of 20kPa, the tetrahydrofuran solution of the 1, 4-diiodooctafluorobutane and the tetrahydrofuran solution of the chloro-diethyl-borane are mixed and dropwise added into a micro-reactor communicated with a first rectifying tower, and the micro-reactor is fully mixed and reacted to form a mixed system A comprising the 1, 4-diiodooctafluorobutane, the chloro-diethyl-borane, the chloroethane, the target product perfluoro 1, 3-butadiene and the tetrahydrofuran; wherein the molar dosage ratio of the 1, 4-diiodooctafluorobutane to the chloro-diethyl-borane is 1:1;
s2: introducing the mixed system A into a first condenser, and rectifying and condensing while continuing the reaction to remove tetrahydrofuran to form a mixed system B;
s3: introducing the mixed system B into a second rectifying tower and a second condenser for rectification, wherein the rectification temperature is lower than the boiling point of the target product of perfluoro 1, 3-butadiene so as to remove partial impurities with the boiling point lower than that of perfluoro 1, 3-butadiene and form a mixed system C;
s4: introducing the mixed system C into a third rectifying tower and a third condenser for rectification, wherein the rectification temperature is higher than the boiling point of the target product of perfluoro 1, 3-butadiene, and repeatedly rectifying to remove impurities with the boiling point higher than that of perfluoro 1, 3-butadiene, thereby obtaining the mixed system C; the purity of the obtained target product of perfluoro 1, 3-butadiene is 99.2% and the yield is 95.0% through detection.
Example 4
A method for continuously synthesizing perfluoro 1, 3-butadiene by using the preparation system of example 1 comprises the following specific steps:
s1: n with a flow rate of 0.75L/h at 20 DEG C 2 Under purging, mixing and dropwise adding a tetrahydrofuran solution of 1, 4-diiodooctafluorobutane and a tetrahydrofuran solution of chloro-diethyl-borane into a micro-reactor communicated with a first rectifying tower to form a mixed system A comprising the tetrahydrofuran solution of 1, 4-diiodooctafluorobutane, chloro-diethyl-borane and target product perfluoro-1, 3-butadiene; wherein, the molar dosage ratio of the 1, 4-diiodooctafluorobutane to the chloro-diethyl-borane is 1:1, a step of;
s2: introducing the mixed system A into a first condenser, and rectifying and condensing while continuing the reaction to remove tetrahydrofuran to form a mixed system B;
s3: introducing the mixed system B into a second rectifying tower and a second condenser for rectification, wherein the rectification temperature is lower than the boiling point of the target product of perfluoro 1, 3-butadiene so as to remove partial impurities with the boiling point lower than that of perfluoro 1, 3-butadiene and form a mixed system C;
s4: introducing the mixed system C into a third rectifying tower and a third condenser for rectification, wherein the rectification temperature is higher than the boiling point of the target product of perfluoro 1, 3-butadiene, and repeatedly rectifying to remove impurities with the boiling point higher than that of perfluoro 1, 3-butadiene, thereby obtaining the mixed system C; the purity of the obtained target product of perfluoro 1, 3-butadiene is 99.4% and the yield is 95.5% through detection.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (7)
1. A method for continuously synthesizing perfluoro-1, 3-butadiene by adopting a perfluoro-1, 3-butadiene preparation system is characterized by comprising the following steps of reacting 1, 4-diiodooctafluorobutane with chloro-diethyl-borane in tetrahydrofuran solvent in the preparation system to obtain the perfluoro-1, 3-butadiene;
wherein, the perfluoro 1, 3-butadiene preparation system comprises a reaction mechanism, a purification mechanism and a collection mechanism which are sequentially connected through a pipeline; the reaction mechanism comprises a micro-reactor, a first rectifying tower and a first condenser which are arranged in a bottom-to-top communication manner, wherein two raw material inlets of the micro-reactor are respectively connected with a tetrahydrofuran-dissolved chlorine-diethyl-borane storage tank and a tetrahydrofuran-dissolved 1, 4-diiodooctafluorobutane storage tank, a tail gas outlet of the first condenser is connected to a tail gas tank, a product outlet is connected to the purification mechanism, and the purification mechanism is used for purifying and then conveying the product to the collection mechanism for collection; the purification mechanism comprises a second rectifying tower and a second condenser, a product outlet of the first condenser is connected to the second rectifying tower, a steam outlet of the second rectifying tower is connected to a tail gas tank through the second condenser, and a product outlet of the second rectifying tower is connected to the collection mechanism; the purification mechanism further comprises a third rectifying tower and a third condenser, a product outlet of the second rectifying tower is connected to the third rectifying tower, a steam outlet of the third rectifying tower is connected to the third condenser, and an outlet of the third condenser is connected with the third rectifying tower and the collection mechanism;
the perfluoro 1, 3-butadiene production system further comprises a vacuum mechanism or an inert gas purge mechanism, wherein the vacuum mechanism is connected to a pipeline to maintain internal vacuum; the inert gas purging mechanism is connected to the pipeline to blow inert gas along the output direction of the product.
2. The process for the continuous synthesis of perfluoro 1, 3-butadiene according to claim 1, wherein the molar ratio of 1, 4-diiodooctafluorobutane to chloro-diethyl-borane is comprised between 1:0.5 and 2.
3. The method for continuously synthesizing perfluoro 1, 3-butadiene according to claim 1, wherein the reaction temperature is 10 to 25 ℃.
4. The process for the continuous synthesis of perfluoro 1, 3-butadiene according to claim 1, wherein the reaction is carried out under vacuum conditions or normal pressure with inert gas purging.
5. The method for continuously synthesizing perfluoro 1, 3-butadiene according to claim 4, wherein the vacuum degree of the vacuum condition is 13.33 to 40kPa.
6. The method for continuously synthesizing perfluoro 1, 3-butadiene according to claim 4, wherein the inert gas is N 2 The flow rate is 0.5-1.0L/h.
7. The method for continuously synthesizing perfluoro 1, 3-butadiene according to any one of claims 1 to 6, comprising the specific steps of:
s1: mixing and dripping a tetrahydrofuran solution of 1, 4-diiodooctafluorobutane and a tetrahydrofuran solution of chloro-diethyl-borane into a micro-reactor communicated with a first rectifying tower, and fully mixing and reacting in the micro-reactor to form a mixed system A comprising 1, 4-diiodooctafluorobutane, chloro-diethyl-borane, chloroethane, target products of perfluoro-1, 3-butadiene and tetrahydrofuran;
s2: introducing the mixed system A into a first condenser, and rectifying and condensing while continuing the reaction to remove tetrahydrofuran to form a mixed system B;
s3: introducing the mixed system B into a second rectifying tower and a second condenser for rectification, wherein the rectification temperature is lower than the boiling point of the target product of perfluoro 1, 3-butadiene so as to remove partial impurities with the boiling point lower than that of perfluoro 1, 3-butadiene and form a mixed system C;
s4: introducing the mixed system C into a third rectifying tower and a third condenser for rectification, wherein the rectification temperature is higher than the boiling point of the target product of perfluoro-1, 3-butadiene, and repeatedly rectifying to remove impurities with the boiling point higher than that of perfluoro-1, 3-butadiene.
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