CN101774884A - Preparation method of hexachlorobutadiene - Google Patents
Preparation method of hexachlorobutadiene Download PDFInfo
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- CN101774884A CN101774884A CN201010031356A CN201010031356A CN101774884A CN 101774884 A CN101774884 A CN 101774884A CN 201010031356 A CN201010031356 A CN 201010031356A CN 201010031356 A CN201010031356 A CN 201010031356A CN 101774884 A CN101774884 A CN 101774884A
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 title description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 31
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 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 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 238000010926 purge Methods 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 238000000066 reactive distillation Methods 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 239000002798 polar solvent Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 80
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- BUYZGJWCDWUMQK-UHFFFAOYSA-N 1,1,1,2,2,3,3,4-octafluoro-4,4-diiodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(I)I BUYZGJWCDWUMQK-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- -1 aromatic organic compounds Chemical class 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 39
- 239000000047 product Substances 0.000 description 25
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 20
- 238000010992 reflux Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 238000002309 gasification Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- 230000009466 transformation Effects 0.000 description 9
- 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 8
- 239000012043 crude product Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 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 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000000608 laser ablation Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SMDYQFCZGKZHDG-UHFFFAOYSA-N 1-fluoro-1-iodoethane Chemical compound CC(F)I SMDYQFCZGKZHDG-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KVBKAPANDHPRDG-UHFFFAOYSA-N dibromotetrafluoroethane Chemical compound FC(F)(Br)C(F)(F)Br KVBKAPANDHPRDG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 2
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWWUGYJWSVESJC-UHFFFAOYSA-N 1,4-dibromo-1,1,2,2,3,3,4,4-octafluorobutane Chemical compound FC(F)(Br)C(F)(F)C(F)(F)C(F)(F)Br RWWUGYJWSVESJC-UHFFFAOYSA-N 0.000 description 1
- JJFOBACUIRKUPN-UHFFFAOYSA-N 2-bromoethoxybenzene Chemical compound BrCCOC1=CC=CC=C1 JJFOBACUIRKUPN-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 102100030678 HEPACAM family member 2 Human genes 0.000 description 1
- 101150115066 Hepacam2 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WCLHNDXRIBKVEI-UHFFFAOYSA-N bromobenzene;oxolane Chemical compound C1CCOC1.BrC1=CC=CC=C1 WCLHNDXRIBKVEI-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical compound FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及一种六氟丁二烯的制备方法。用I-CF2-CF2-CF2-CF2-I在极性溶剂存在下，与Mg、Zn或Li等金属与芳香族有机化合物合成的格氏试剂在精馏塔中通过反应精馏的方式进行，反应温度为相应溶剂在反应条件下的沸点温度，反应在真空条件下进行；或者反应在常压下进行同时反应过程中使用氮气吹扫。本发明通过反应精馏方式进行，在反应过程中，可以保证反应区域最大的蒸汽量，同时在真空或者氮气吹扫的帮助下，使反应产物迅速从溶剂中脱离，减少副反应的发生，有效的提高反应的收率和选择性，反应收率最高可达97.6％，选择性达到97.78％。同时，反应完成后，溶剂的回收可在同一装置中进行，降低了设备投资，减少了操作步骤。
The invention relates to a preparation method of hexafluorobutadiene. Using I-CF 2 -CF 2 -CF 2 -CF 2 -I in the presence of polar solvents, the Grignard reagent synthesized with Mg, Zn or Li and other metals and aromatic organic compounds is rectified by reaction in the rectification tower The reaction temperature is the boiling point temperature of the corresponding solvent under the reaction conditions, and the reaction is carried out under vacuum conditions; or the reaction is carried out under normal pressure and nitrogen purging is used during the reaction. The present invention is carried out through reactive distillation. During the reaction process, the maximum amount of steam in the reaction area can be guaranteed, and at the same time, with the help of vacuum or nitrogen purge, the reaction product can be quickly separated from the solvent, reducing the occurrence of side reactions, effectively Improve the yield and selectivity of the reaction, the highest reaction yield can reach 97.6%, and the selectivity can reach 97.78%. At the same time, after the reaction is completed, the recovery of the solvent can be carried out in the same device, which reduces equipment investment and operation steps.
Description
Technical field
The present invention relates to field of chemical technology, particularly relate to a kind of preparation method of hexachlorobutadiene.
Background technology
Electronic gas hexachlorobutadiene (C
4F
6) be state-of-the art laser ablation agent, it can replace the laser ablation agent tetrafluoro-methane (CF of present employing
4), hexafluoroethane (C
2F
6), octafluoropropane (C
3F
8), Perfluorocyclobutane (C
4F
8) being used for the dry etch process of the sharp keen etching semiconductor electrical condenser of KrF laser figure (patterns), the etching live width can reach below the 90nm.Only reach the etching gas Perfluorocyclobutane (C of 130nm with the present best live width of result of use
4F
8) compare hexachlorobutadiene (C
4F
6) have that degradation speed is fast in atmosphere, Greenhouse effect are little, aspect ratio is high and the selectivity advantages of higher.Hexachlorobutadiene is not only state-of-the art laser ablation agent simultaneously, and still the synthon of the novel fluoro-resin of much researching and developing, fluoroplastics, viton has boundless market application foreground.Raw material-perfluor the diiodide of preparation hexachlorobutadiene is again the synthetic precursor of a lot of straight chain perfluoro-compounds and fluorine-containing medicines, fluoro-containing pesticide, also has a wide range of applications.
Haszeldine (US 3046304) utilizes trifluorochloroethylene to prepare hexachlorobutadiene for raw material through three-step reaction.At first trifluorochloroethylene and equimolar iodine chloride reaction 2 hours under the pressure that 35～40 ℃ and self produce obtains 1 after removing free-iodine, 2-two chloro-1,2, and 2-three fluoro-1-iodoethane, yield is 97%.Then with 1,2-two chloro-1,2, the mercury of 2-three fluoro-1-iodoethane and equivalent mixes, and reaction 48h obtains 1,2,3 under UV-light, and 4-tetrachloro-hexafluoro butane, yield are 86%.Carry out dechlorination reaction with zinc powder in ethanolic soln more at last, obtain the product hexachlorobutadiene, yield is 98%.The aforesaid method reaction conditions is relatively harsher, and reaction needed is used hazardous and noxious substances such as mercury, aceticanhydride or iodine chloride simultaneously, and waste liquid is difficult for handling, and exists than the serious environmental pollution problem.Contain the incomplete chlorine-containing compound of a lot of reactions in the product of final step dechlorination reaction, bring bigger difficulty for follow-up purification.
Miler etc. (us2668182) generate 3 with trifluorochloroethylene 550 ℃ of pyrolytic reactions, 4-two chloro-1,1,2,3,4,4-hexafluoro-1-butylene and 1,2-dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane.Transformation efficiency is that the yield of 34%, two kind of mixture is 21%.Because these two kinds of compound boiling points are approaching, are not easy fractionation, directly will obtain 1,2,3 behind mixture and the chlorine reaction, 4-tetrachloro-1,1,2,3,4,4-hexafluoro butane and 1,2 ,-dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane.The former obtains hexachlorobutadiene with the zinc powder dechlorination again.1,2-dichloro trans-1,1,2,2,3,4-Hexafluorocyclobutane can obtain the hexafluoro cyclobutene with zinc powder and alcohol solvent reaction.The hexafluoro cyclobutene can be reset under 650 ℃ temperature and transform into hexachlorobutadiene, and transformation efficiency is 12%.In the presence of catalyzer CsF/KF, temperature of reaction 510-590 ℃, yield is 60%-80%.These two kinds of methods are all with 1,2,3, and 4-tetrachloro-perfluorinated butane is a reaction intermediate, the reaction process complexity, and the condition harshness, the transformation efficiency of reaction and yield are all lower, realize industrialization difficulty height, and the chlorine that uses in the reaction process, and mercury etc. have very high toxicity.
In addition, a kind of method is with tetrafluoroethylene (CF
2=CF
2) be that raw material synthesizes target product (GB1315785).At first need tetrafluoroethylene and bromine reaction to generate 1,2-dibromotetrafluoroethane, total yield are 98%.Then 1,2-dibromotetrafluoroethane and tetrafluoroethylene react under UV-light, and conversion of raw material is 65.1%.Selectivity is 38.2%.Isolated 1,4-dibromo Octafluorobutane in tetrahydrofuran (THF) under situation about refluxing with Grignard reagent (C
2H
5MgBr) reaction (US5082981).The yield of product hexachlorobutadiene is 96%.
MIKI, reports such as Jun and YOSHIMI (EP1247791) use I-CF
2-CF
2-CF
2-CF
2-I be warming up to 120 ℃ after Zn mixes, keep and add a certain amount of DMF initiation reaction after 30 minutes, react and obtain mixed gas after 30 minutes, its perfluorobutadiene content is 65%.Yield is 54.4%.Though this method operation is simple, reaction is once a large amount of heat is emitted in initiation, and reaction is violent, is difficult to control, is difficult to the realization suitability for industrialized production.
Reports such as Gianangelo (US4654448) are with 11.4gI-CF
2-CF
2-CF
2-CF
2-I is heated to boiling with after 50ml tetrahydrofuran (THF) (THF) mixes, and slowly drips the Grignard reagent 50ml of 1M concentration, has to a kind of gas 2.9g after the reaction, is perfluorobutadiene, and yield 71.6% also has the 1g perfluorobutadiene in the analytical solution, and total recovery is 96%.Confirm that by experiment the gas that generates in this process is the mixture of perfluorobutadiene and perfluor cyclobutene, and the boiling point of isomer perfluor cyclobutene and perfluorobutadiene differs and have only 0.8 ℃, bring very big difficulty to separation.Be dissolved in difficult extraction of perfluor cyclobutene in the solvent simultaneously, cause the decline of product yield.
Summary of the invention
The present invention relates to a kind of synthetic method of new perfluorobutadiene, this method can effectively reduce synthetic in the growing amount of by product perfluor cyclobutene, improve the yield and the selectivity of reaction.
The synthetic method of a kind of hexachlorobutadiene of the present invention is used I-CF
2-CF
2-CF
2-CF
2-I is in the presence of polar solvent, carry out with metals such as Mg, Zn or Li and aromatic organic compounds synthetic Grignard reagent mode by reactive distillation in rectifying tower, temperature of reaction is the boiling temperature of coordinative solvent under reaction conditions, is reflected under the vacuum condition and carries out; Perhaps be reflected at and carry out under the normal pressure using nitrogen purging in the while reaction process.
The reinforced proportioning of grignard reagent and diiodo perfluo alkane is 2: 1 in the reaction process.But for making 1,4-diiodo-Octafluorobutane can react completely, and the add-on of grignard reagent can be excessive a little.
This method comprises uses I-CF
2-CF
2-CF
2The aromatic organic compounds of-CF-I and Mg, Zn or Li etc. reacts.Raw material 1,4-diiodo-Octafluorobutane is to pass through I-CF
2-CF
2It is resultant that-I and tetrafluoroethylene carry out telomerization, and synthetic method can adopt described in our the patent CN1686985, resulting telomerize mixing solutions through rectification under vacuum separate back acquisition purity be 99% 1,4-diiodo-Octafluorobutane.
Owing to be reflected in the rectifying tower and carry out, the quantity of solvent of actual participation reaction is less, and is too fierce for avoiding reaction, raw material 1, and 4-diiodo-Octafluorobutane will dilute before adding.Use a certain amount of and reaction selected identical solvent and 1,4-diiodo-Octafluorobutane mixes mutually, and the solution of making concentration and be 2mol/l-3mol/l drips.
The aromatic organic compounds of Mg, Zn or Li etc. is mainly metal and Organohalogen compounds at ether solvents synthetic Grignard reagent.Concentration can be generally 0.1M-5M.Wherein concentration is that 1M-3M is optimum.
The solvent that uses in present method can be tetrahydrofuran (THF) (THF), dme, ether or 1,4-dioxane etc.Wherein be optimum with the tetrahydrofuran (THF).
Temperature of reaction is generally the boiling temperature of selected solvent in present method.When temperature of reaction was lower, speed of response descended very fast; When temperature was too high, content of by-products can increase in the reaction, and for obtaining preferable reaction yield and reaction efficiency, the boiling temperature of reacting selected solvent is an optimum with 30 ℃-100 ℃ generally.
Reaction is carried out under vacuum condition in present method.Reaction process is taked certain vacuum, can rapidly product be separated from solvent, and the minimizing product retains the chance with autohemagglutination in solvent.Though the higher reaction product that can make of vacuum tightness is detached from solvent rapidly, too high vacuum tightness can cause the temperature in the reaction tower low excessively, and the yield of reaction is reduced; Because vacuum tightness is too high, also can cause the liquid flooding of tower simultaneously, reduce separation efficiency.Vacuum tightness is crossed to hang down and is not then had the effect that detaches, so the appropriate vacuum degree scope is 100mmHg-300mmHg.In addition, also can use the mode of nitrogen bubble that product is taken out of from solvent in present method, but because the increase of gas generating capacity, condenser duty is also bigger, so suitable nitrogen flow rate is 0.1l/h-5l/h.
The rate of addition of two kinds of materials and mode also have very big influence to the yield of reaction in present method.Different dropping modes, the content of the productive rate of hexachlorobutadiene crude product, content and by product perfluor cyclobutene all has very big difference.Simultaneously rate of addition is also bigger to the influence of reaction, and dropping slow excessively can make the load of reactor excessive, thereby cause the productive rate reduction; On the contrary, rate of addition is too fast, perfluorobutadiene future of generation and overflow fully and and Grignard reagent continue to react, perhaps change reaction mechanism, generate other material, and the yield that causes reacting descends.Suitable dropping mode is that two kinds of materials drip respectively, and controlling drop rate simultaneously is 5-10ml/min.
Among the present invention, reaction is that the mode with reactive distillation is carried out in rectifying tower.Because the product perfluorobutadiene has certain solubleness in solvent, so product has the long residence time in reactor, carry out enrichment easily, and then the autohemagglutination of generation itself, perhaps react, cause yield and optionally reduction with initiate grignard reagent.And undertaken by the reactive distillation mode, in reaction process, can guarantee that the conversion zone solvent constantly vaporizes, simultaneously under the help of vacuum or nitrogen purging, reaction product is broken away from from solvent rapidly, reduce the generation of side reaction, effectively improve the yield and the selectivity of reaction, reaction yield reaches as high as 97.6%, and selectivity reaches 97.78%.Simultaneously, after reaction was finished, the recovery of solvent can be carried out in same device, has reduced facility investment, has reduced operation steps.
Description of drawings
Fig. 1: preparation method's synoptic diagram of hexachlorobutadiene.
Wherein 1 and 2 is airtight constant pressure funnels, drips 1 respectively, the tetrahydrofuran solution and the Grignard reagent of 4-diiodo-Octafluorobutane.3 is the tower still, and 4 is thermopair, and 5 is the product receiving trap, and heat-eliminating medium is-90 ℃.The high diameter of filling 3m is the triangle packing tower of 38mm in the tower.
Embodiment
The preparation of Grignard reagent:
A) in the round bottom there-necked flask of 3L band condenser, add 108g magnesium rod (4.5mol), several iodine, add about 500ml anhydrous diethyl ether simultaneously, be heated to boiling, the 4.5mol bromobenzene is melted in the 200ml diethyl ether solution, drip several earlier, after causing grignard reaction, remaining Bromoethyl phenyl ether solution is slowly dropwised, generate the Grignard reagent that about concentration is 3mol/l.Bromobenzene and magnesium that the consumption of increase ether can obtain different concns such as 1mol/l, 2mol/ prepare grignard reagent.
B) in the round bottom there-necked flask of 3L band condenser, add 27.8g metallic lithium (4.0mol), several iodine, add about 1000ml tetrahydrofuran (THF) simultaneously, under the normal temperature, the 4.0mol bromobenzene is melted in the 800ml tetrahydrofuran solution, drip several earlier, after causing grignard reaction, remaining bromobenzene tetrahydrofuran solution is slowly dropwised, generate the Grignard reagent that about concentration is 2mol/l.Change the consumption of tetrahydrofuran (THF), can obtain concentration and be respectively the bromobenzene of 1mol/l and 3mol/l and the grignard reagent of lithium preparation.
C) adopt identical method can prepare concentration and be respectively the bromobenzene of 1mol/l, 2mol/l and 3mol/l and the grignard reagent of zinc preparation.
Embodiment 1:
In the Sealing Arrangement, in the tower still 3 that has thermopair 4 of 2000ml, add solvent 400ml tetrahydrofuran (THF) in advance as shown in Figure 1.Shown in the figure 1, add concentration in 2 liang of dropping funnels respectively and be 2mol/l by the Grignard reagent 1000ml (2.0mol) of above-mentioned A method preparation and the 500ml tetrahydrofuran solution of 454g (1.0mol) diiodo-Octafluorobutane, logical nitrogen all vacuumizes the gas in the equipment after the displacement, vacuum tightness maintains 300mmHg, heating tower's still, keep tetrahydrofuran (THF) to boil to total reflux, the cat head cooling temperature is controlled in 6-7 ℃, after treating total reflux, slowly drip Grignard reagent and diiodo-Octafluorobutane solution simultaneously from the body of the tower middle part, the control rate of addition, complete soln is dropwised at about 3-4h, collect thick product in product collection device 5, heat-eliminating medium is-90 ℃ in the product collection device, after reaction finishes, thick product is placed fully gasification under the normal temperature, and gasification back gas freezes weighs in the steel cylinder, gets hexachlorobutadiene crude product 163g.After GC detected, wherein the content of perfluorobutadiene was 96%, and all the other major impurities are respectively: air and light constituent impurity 0.5%; Hexafluoro cyclobutene 2.8%; Ether 0.7%, transformation efficiency: 99.4%, yield is: 96.01%, selectivity is: 96.59%.
Embodiment 2:
As the equipment described in the embodiment 1, have at 2000ml and to add solvent 400ml tetrahydrofuran (THF) in the tower still of thermopair, 1, add bromobenzene that concentration is 3mol/l and Mg in 2 two dropping funnels respectively by the Grignard reagent 1000ml (3.0mol) of above-mentioned A method preparation and the 500ml tetrahydrofuran solution of 682g (1.5mol) diiodo-Octafluorobutane, with the device in air all with behind the nitrogen replacement, vacuumize, keeping vacuum tightness is 100mmHg, heating tower's still, keep tetrahydrofuran (THF) to boil to total reflux, the cat head cooling temperature is controlled in 6-7 ℃, keep the certain quantity of reflux of tower still, after treating total reflux, slowly drip Grignard reagent and diiodo-Octafluorobutane solution, control rate of addition simultaneously from the body of the tower middle part, complete soln is dropwised at about 3-4h, collect thick product in-90 ℃ cryotrap, after reaction finished, thick product was placed normal temperature fully gasification down, gasification back gas freezes weighing in the high-pressure cylinder, gets hexachlorobutadiene crude product 245g.After GC detected, wherein the content of perfluorobutadiene was 96.32%, and all the other major impurities are respectively: air, 0.6%; The hexafluoro cyclobutene, 2.4%; Ether 0.67%, transformation efficiency: 99.53%, yield is: 96.66%, selectivity is: 97.11%.
Embodiment 3:
In the tower still that has thermopair of 2000ml, add the 400ml tetrahydrofuran (THF) in advance, 1, add concentration in 2 liang of dropping funnels respectively and be 3mol/l with bromobenzene and Li the Grignard reagent 670ml (2.01mol) for preparing of B and the 500ml tetrahydrofuran solution of 454g (1.0mol) diiodo-Octafluorobutane as stated above, nitrogen tube is inserted in the still below the liquid level, feed nitrogen, the maintenance nitrogen flow is 0.5l/h, heating tower's still to tetrahydrofuran (THF) seethes with excitement, the cat head cooling temperature is controlled in 6-7 ℃, keep the certain quantity of reflux of tower still, after treating total reflux, slowly drip Grignard reagent and diiodo-Octafluorobutane solution simultaneously from the body of the tower middle part, the control rate of addition, complete soln is dropwised at about 3-4h, collect thick product in-90 ℃ cryotrap, after reaction finished, thick product was placed normal temperature fully gasification down, gasification back gas freezes weighing in the high-pressure cylinder, gets hexachlorobutadiene crude product 164g.After GC detected, wherein the content of perfluorobutadiene was about 96.02%, and all the other major impurities are respectively: air and light constituent impurity, 0.8%; The hexafluoro cyclobutene, 2.3%; Ether 0.88%, transformation efficiency: 99.53%, yield is: 96.75%, selectivity is: 97.2%.
Embodiment 4:
As shown in Figure 1 in the Sealing Arrangement, in the tower still that has thermopair of 2000ml, add 500ml 1 in advance, the 4-dioxane, 1, add concentration in 2 liang of dropping funnels respectively and be 3mol/l with bromobenzene and Zn the Grignard reagent 670ml (2.01mol) for preparing of C and the 500ml 1 of 454g (1.0mol) diiodo-Octafluorobutane as stated above, the 4-dioxane solution, nitrogen tube is inserted in the still below the liquid level, feed nitrogen, the maintenance nitrogen flow is 5l/h, heating tower's still to tetrahydrofuran (THF) seethes with excitement, the cat head cooling temperature is controlled in 6-7 ℃, keeps the certain quantity of reflux of tower still, treat total reflux after, slowly drip Grignard reagent and diiodo-Octafluorobutane solution simultaneously from the body of the tower middle part, the control rate of addition makes complete soln dropwise at about 3-4h, collects thick product in-90 ℃ cryotrap, after reaction finishes, thick product is placed fully gasification under the normal temperature, and gasification back gas freezes weighing in the high-pressure cylinder, gets hexachlorobutadiene crude product 162g.After GC detected, wherein the content of perfluorobutadiene was about 95.1%, and all the other major impurities are respectively: air and light constituent impurity, 1.0%; The hexafluoro cyclobutene, 3.9%; Transformation efficiency: 99%, yield is: 94.14%, selectivity is: 95.1%.
Embodiment 5:
As shown in Figure 1 in the Sealing Arrangement, in the tower still that has thermopair of 2000ml, add the 400ml ether in advance, 1, add 1000ml concentration in 2 liang of dropping funnels respectively and be 1mol/l with bromobenzene and the Zn Grignard reagent for preparing of C and the 500ml tetrahydrofuran solution of 227g (0.5mol) diiodo-Octafluorobutane as stated above, nitrogen tube is inserted in the still below the liquid level, feed nitrogen, the maintenance nitrogen flow is 0.1l/h, heating tower's still to ether seethes with excitement, the cat head cooling temperature is controlled in 6-7 ℃, keep the certain quantity of reflux of tower still, after treating total reflux, slowly drip Grignard reagent and diiodo-Octafluorobutane solution simultaneously from the body of the tower middle part, the control rate of addition makes complete soln dropwise at about 3-4h, collects thick product in-90 ℃ cryotrap, after reaction finishes, thick product is placed fully gasification under the normal temperature, and gasification back gas freezes weighing in the high-pressure cylinder, gets hexachlorobutadiene crude product 86g.After GC detected, wherein the content of perfluorobutadiene was about 89.33%, and all the other major impurities are respectively: air and light constituent impurity, 0.7%; The hexafluoro cyclobutene, 3.8%; Ether, 6.17%; Transformation efficiency: 99%, yield is: 94.84%, selectivity is: 95.8%.
Embodiment 6
In Sealing Arrangement, in the tower still that has thermopair of 2000ml, add the 500ml tetrahydrofuran (THF) in advance, 1, add concentration in 2 liang of dropping funnels respectively and be 2mol/l with bromobenzene and Li the Grignard reagent 1000ml (2.01mol) for preparing of B and the 500ml tetrahydrofuran solution of 454g (1.0mol) diiodo-Octafluorobutane as stated above, after replacing air in the tower entirely with nitrogen, vacuumize, vacuum tightness is 200mmHg, heating tower's still to tetrahydrofuran (THF) seethes with excitement, the cat head cooling temperature is controlled in 6-7 ℃, keep the certain quantity of reflux of tower still, after treating total reflux, slowly drip Grignard reagent and diiodo-Octafluorobutane solution simultaneously from the body of the tower middle part, the control rate of addition makes complete soln dropwise at about 3-4h, collects thick product in-90 ℃ cryotrap, after reaction finishes, thick product is placed fully gasification under the normal temperature, and gasification back gas freezes weighing in the high-pressure cylinder, gets hexachlorobutadiene crude product 163g.After GC detected, wherein the content of perfluorobutadiene was about 97%, and all the other major impurities are respectively: air and light constituent impurity, 0.8%; The hexafluoro cyclobutene, 2.2%; Transformation efficiency: 99.81%, yield is: 97.6%, selectivity is: 97.78%.
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| CN109232167A (en) * | 2018-11-06 | 2019-01-18 | 南通宝凯化工有限公司 | A kind of preparation process of perfluorobutadiene |
| JP6465224B1 (en) * | 2017-02-03 | 2019-02-06 | ダイキン工業株式会社 | Method for producing perfluoroalkadiene compound |
| CN111269080A (en) * | 2020-02-20 | 2020-06-12 | 扬州虹扬科技发展有限公司 | A kind of microreactor preparation system of perfluoro 1,3-butadiene and preparation method thereof |
| CN111269079A (en) * | 2020-02-20 | 2020-06-12 | 扬州虹扬科技发展有限公司 | Preparation system and preparation method of perfluoro 1, 3-butadiene |
| CN114014743A (en) * | 2021-12-02 | 2022-02-08 | 苏州金宏气体股份有限公司 | Method for continuously producing hexafluorobutadiene |
| CN115160103A (en) * | 2022-06-27 | 2022-10-11 | 苏州金宏气体股份有限公司 | A kind of industrial synthesis method and device of hexafluorobutadiene |
| CN115254163A (en) * | 2022-07-04 | 2022-11-01 | 大连科利德光电子材料有限公司 | Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene |
| CN115903705A (en) * | 2022-11-30 | 2023-04-04 | 福建省杭氟电子材料有限公司 | Production management control system for preparing electronic grade hexafluobutadiene |
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| JP6465224B1 (en) * | 2017-02-03 | 2019-02-06 | ダイキン工業株式会社 | Method for producing perfluoroalkadiene compound |
| JP2019069931A (en) * | 2017-02-03 | 2019-05-09 | ダイキン工業株式会社 | Method for producing perfluoroalkadiene compounds |
| CN109232167A (en) * | 2018-11-06 | 2019-01-18 | 南通宝凯化工有限公司 | A kind of preparation process of perfluorobutadiene |
| CN111269080A (en) * | 2020-02-20 | 2020-06-12 | 扬州虹扬科技发展有限公司 | A kind of microreactor preparation system of perfluoro 1,3-butadiene and preparation method thereof |
| CN111269079A (en) * | 2020-02-20 | 2020-06-12 | 扬州虹扬科技发展有限公司 | Preparation system and preparation method of perfluoro 1, 3-butadiene |
| CN111269080B (en) * | 2020-02-20 | 2022-07-01 | 扬州虹扬科技发展有限公司 | A kind of microreactor preparation system of perfluoro 1,3-butadiene and preparation method thereof |
| CN111269079B (en) * | 2020-02-20 | 2024-04-05 | 扬州虹扬科技发展有限公司 | A preparation system and preparation method of perfluoro-1,3-butadiene |
| CN114014743A (en) * | 2021-12-02 | 2022-02-08 | 苏州金宏气体股份有限公司 | Method for continuously producing hexafluorobutadiene |
| CN115160103A (en) * | 2022-06-27 | 2022-10-11 | 苏州金宏气体股份有限公司 | A kind of industrial synthesis method and device of hexafluorobutadiene |
| CN115254163A (en) * | 2022-07-04 | 2022-11-01 | 大连科利德光电子材料有限公司 | Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene |
| CN115903705A (en) * | 2022-11-30 | 2023-04-04 | 福建省杭氟电子材料有限公司 | Production management control system for preparing electronic grade hexafluobutadiene |
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