CN104529695B - A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene - Google Patents
A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene Download PDFInfo
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Abstract
The invention discloses one and prepare 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, is CH by formulamXnY4-n-m(m is 0 or 1, n is 1,2 or 3, and X, Y are selected from F, Cl or Br。) and HCFO-1233zd(CHCl=CHCF3) heat of mixing additive reaction。Obtained intermediate hydrogen fluorine chlorine (bromine) butane or free HCl through vapor phase cracking, or utilize fluorination catalyst carry out HF fluoride or utilize zinc powder to carry out dechlorination。The product that reaction generates through filtrations, alkali cleaning, washing, dry, compress, after rectification and purification namely respectively highly purified 1,1,1,4,4,4-hexafluoro-2-butylene product。It is simple that the present invention has technique, and raw material is easy to get, it is easy to industrialization, environmental protection advantage。
Description
Technical field
The invention belongs to perhaloalkenes preparing technical field, be specifically related to the preparation 1,1 that a kind of foaming agent, cold-producing medium and solvent industry use, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene。
Background technology
1,1,1,4,4,4-hexafluoro-2-butylene (CF3CH=CHCF3) heat conductivity close to HFC-365mfc and HFC-245fa, slightly above CFC-12, HCFC-141b, non-combustible, ODP(ozone-depleting is dived value) be that 0, GWP(greenhouse effect is dived value) it is only 5, therefore it is one of succedaneum of ideal common foaming, cold-producing medium and solvent。Accordingly, as novel foaming agent, cold-producing medium and solvent, 1,1,1,4,4,4-hexafluoros-2-butylene has environmental protection, heat-insulation and heat-preservation, safety, not consuming ozone, nonflammable, the features such as greenhouse effect is low, it, by becoming the application of future market and promoting object, has good market prospect and economic benefit。
At present, 1,1,1, the preparation method of 4,4,4-hexafluoros-2-butylene is more, mainly include hexafluoro-2-butyne hydrogenation, chloroform and hexafluoropropene copolymerization, CFC-113 couples, fluoride and dechlorination route, carbon tetrachloride and ethylene telomerize synthesis and fluoride dechlorination route, HFC-347mef dehydrofluorination, HCFC-123 couples and carbon tetrachloride and trifluoro propene telomerize the process routes such as synthesis。
It is hydrogenated to raw material with hexafluoro-2-butyne, adopts Pd or Lindlar catalyst to catalyzing hydrogenating, it is possible to selectively produce (Z)-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。Being usually added into arylamine in reaction system, catalyst is modified by the toxic solvent such as quinoline or pyridine。CN102892738A finds to utilize has good catalytic hydrogenation effect through the 3.5% saturnine 5%Pd catalyst being carried on calcium carbonate。This route technique is simple, is suitable for commercial production, but its subject matter is reaction raw materials hexafluoro-2-butyne is difficult to prepare, relatively costly。
CN102892738A reports by thermal addition reaction, CHCl3C h bond insert hexafluoropropene, formed CCl3CF2CHFCF3, it being then passed through HF fluoride, hydrogenation takes off the steps such as HF and finally gives hexafluoro-2-butyne, then hexafluoro-2-butyne selective hydrogenation is formed 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。It is found that this route steps is numerous and diverse, yield is low。
Utilize similar reactive mode, CCl4React with 3,3,3-trifluoro propenes, through three-step reaction, it is possible to produce target product [CN102884030A]。
Patent US2011/01288350 finds CFC-113a(CCl3CF3) mix with 1,2 dichloroethylene, under iron catalyst and 3-butylphosphoric acid ester effect, it is placed in autoclave, reacts certain time, CF can be obtained3CCl2CHClCHCl2Intermediate product。CF is obtained then through chlorination3CCl2CCl2CCl3, obtain CF with HF fluoride3CCl2CCl2CCF3, form 1,1 through 300-350 DEG C of hydrogenation reaction of Cu/AC catalyst, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。
Utilize most basic raw material CCl4And CH2=CH2Through telomerisation, CN102892736A finds that product is CCl3CH2CH2Cl (HCC-250), de-HCl product CCl3CH=CH2Again with CCl4Telomerize, obtain CCl3CHClCH2CCl3, HF fluoride afterproduct is 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。
With HCFC-123(CF3CHCl2) for raw material, mix loading reactor with metallic copper and methylamine or ethamine etc., after reacting about 10h at 60 DEG C, it is possible to collect target product 1 in the product, 1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene [CN102015592A]。Reaction is intermittent reaction, and the time is long, and industrial production campaign is long, and the metallic copper cost that equivalent consumes is also higher。
Summary of the invention
For the weak point of prior art problem, technique is simple, yield is high, step is few and is prone to industrialized preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene to it is an object of the invention to provide one。
Described one prepares 1, and 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that be CH by formulamXnY4-n-mHalide and HCFO-1233zd in tubular reactor, carry out continuously flowing carry out heat of mixing additive reaction, namely intermediate hydrogen fluorine chlorine (bromine) butane is obtained after alkali cleaning, washing, dry, compression, rectification and purification, hydrogen fluorine chlorine (bromine) butane of gained or free HCl through vapor phase cracking, or utilize fluorination catalyst to carry out HF fluoride, or utilize zinc powder to carry out dechlorination, the product generated through filtrations, alkali cleaning, washing, dry, compress, rectification and purification obtains highly purified 1,1,1,4,4,4-hexafluoros-2-butylene product, CHmXnY4-n-mMiddle m is 0 or 1, n is 1,2 or 3, and X, Y are selected from F, Cl or Br。Its molecular formula of HCFO-1233zd is CHCl=CHCF3, it is the intermediate raw material of the conventional cold-producing medium such as HFO-1234ze, HFC-245fa, foaming agent, it is possible to optionally prepare through fluorides such as HCO-240fa, and these raw material sources are extensive, are easy to get。Intermediate hydrogen fluorine chlorine (bromine) butane intermediate product includes CF3CH2CHClCClF2、CF3CHClCH2CF3、CCl2FCHClCH2CF3、CF3CHClCHClCF3、CClF2CHClCHFCF3、CCl2FCHClCHFCF3、CClF2CHClCHClCF3、CCl3CHClCH2CF3、CHCl2CHClCHClCF3、CCl2FCHClCHClCF3、CCl3CHClCHFCF3Deng。
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that described halide is CHClF2、CHF3、CHCl2F、CClF3、CCl2F2、CHCl3、CCl3One or more mixture in F。
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that the molar ratio of halide and HCFO-1233zd is 1:1-4, it is preferred to 1:1.2 ~ 2；Heat of mixing additive reaction temperature is 100-400 DEG C, it is preferred to 250-350 DEG C, and reaction pressure is 0.1-1MPa, it is preferred to 0.3 ~ 0.6MPa, and the time of staying is 0.1-20s, it is preferred to 6 ~ 10s。
Described preparation 1,1,1, the method of 4,4,4-hexafluoros-2-butylene, it is characterized in that the de-HCl of described hydrogen fluorine chlorine (bromine) butane gas phase thermal cracking concretely comprises the following steps: after the hydrogen purified separation of fluorine chlorine (bromine) butane, pass into equipped with through the activated carbon of pickling, high-ratio surface graphite, graphite, MgF2、CsCl/MgF2Beds, under 200-400 DEG C of reaction temperature, slough HCl, directly form 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene, freeing HCl by vapor phase cracking, to prepare intermediate hydrogen fluorine chlorine (bromine) butane of product be CF3CHClCH2CF3。
Described preparation 1,1,1, the method of 4,4,4-hexafluoros-2-butylene, it is characterized in that described hydrogen fluorine chlorine (bromine) butane utilizes zinc powder to carry out concretely comprising the following steps of dechlorination: by the reactor equipped with excessive Zn powder and organic solvent, after reacting 1-10h at 50-90 DEG C, separating reaction mother solution, namely highly purified 1,1,1 is obtained after alkali cleaning, washing, dry, compression, rectification and purification, 4,4,4-hexafluoros-2-butylene, utilizing zinc powder to carry out dechlorination, to prepare intermediate hydrogen fluorine chlorine (bromine) butane of product be CF3CHClCHClCF3。
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that the mass ratio that feeds intake that described Zn powder is the fresh Zn powder after dilute hydrochloric acid activates, described Zn powder addition and hydrogen fluorine chlorine (bromine) butane is 2-3:1。
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that described organic solvent includes DMF or sulfolane。
Described preparation 1,1,1,4,4, the method of 4-hexafluoro-2-butylene, it is characterized in that described hydrogen fluorine chlorine (bromine) butane utilizes fluorination catalyst to carry out concretely comprising the following steps of HF fluoride: passed into by hydrogen fluorine chlorine (bromine) butane equipped with in the tubular reactor of fluorination catalyst, 200-400 DEG C of fluoride, product utilization zinc powder carry out dechlorination or be directly over filter, alkali cleaning, washing, dry, compression, rectification and purification obtain highly purified 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene, utilizes fluorination catalyst to carry out HF fluoride and prepares hydrogen fluorine chlorine (bromine) butane of product and include CF3CH2CHClCClF2, CCl2FCHClCH2CF3, CCl3CHClCH2CF3, CClF2CHClCHFCF3, CCl2FCHClCHFCF3, CClF2CHClCHClCF3, CHCl2CHClCHClCF3, CCl2FCHClCHClCF3And CCl3CHClCHFCF3, the product that obtains respectively 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene and CF3CHClCHClCF3, 1,1, Isosorbide-5-Nitrae, namely 4,4-hexafluoros-2-butylene obtains highly purified 1,1 after being directly over alkali cleaning, washing, dry, compression, rectification and purification, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene；CF3CHClCHClCF3Can passing through Zn powder dechlorination, namely separating reaction mother solution obtains highly purified 1,1 after alkali cleaning, washing, dry, compression, rectification and purification, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that described fluorination catalyst is Cr2O3、Ni-Cr2O3、MgF2-Cr2O3、Ni-Cr/MgF2Or activated carbon after pickling, high-ratio surface graphite。
Described preparation 1,1,1, the method of 4,4,4-hexafluoros-2-butylene, it is characterized in that described fluorination catalyst uses anhydrous hydrogen fluoride 250 DEG C of pre-fluoride 2-5h of original position in tubular reactor before reactions, described tubular reactor is corrosion resistant nickel pipe, Inconel and Mo Naier compo pipe。
The dominant response formula that the present invention relates to is as follows:
By adopting above-mentioned technology, compared with prior art, beneficial effects of the present invention is as follows: 1) present invention adopts with CHClF2、CHF3、CHCl2F、CClF3、CCl2F2、CHCl3、CCl3One or more mixture of F etc. and HCFO-1233zd are raw material, and blended thermal addition reaction obtains intermediate hydrogen fluorine chlorine (bromine) butane, and this intermediate product frees HCl through vapor phase cracking, or utilize fluorination catalyst to carry out HF fluoride, or utilize zinc powder to carry out dechlorination, the 1,1 of synthesis of high purity, 1,4,4,4-hexafluoros-2-butylene, its technique is simple, easy to operate, cheaper starting materials is easy to get, cost is low, is suitable to industrialized production；
2) preparation 1,1,1 provided by the invention, the method of 4,4,4-hexafluoros-2-butylene, overcome existing technological operation cycle length, unit volume yields poorly, equipment investment is big etc. shortcoming, its yield is high, step is few, be prone to industrialization, the control of the present invention selection by reactant and reaction condition, highly purified 1 can be realized, 1, Isosorbide-5-Nitrae, the production of 4,4-hexafluoros-2-butylene。The method technique of the present invention is simple, and equipment used simplifies, and unit device production capacity can be made to be greatly improved。
3) due to the fact that employing Continuous Heat additive reaction route, it may be achieved the continuous-stable of course of reaction, operation can be remained stable over, be more beneficial for industrially scalable continuous prodution；
Specific implementation method
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to that:
Embodiment 1 intermediate product CF3CH2CHClCClF2Preparation
With monochlorodifluoromethane (R22) and HCFO-1233zd for raw material, prepare CF through thermal addition reaction3CH2CHClCClF2This reaction carries out in plug flow reactor, the reaction tube of tubular reactor adopts internal diameter 18mm, length is the Ni pipe of 50cm, it is placed in tube furnace heat temperature raising, the present invention condenses to prevent material, all reaction forming pipelines adopt stainless steel tube, and with Heat preservation chuck constant temperature at about 70 DEG C, monochlorodifluoromethane (R22) and HCFO-1233zd are respectively adopted mass flowmenter and control flow (100mL/min), its flow ratio of modulation is 1, and reaction temperature is stable at 300 DEG C, and reaction pressure is 0.5MPa。Before reaction, it is 200m by surface area2The powdered graphite of/g 30MPa compression molding on tablet machine, broken, the granule 15mL that screening order number is 14-20 order (1-1.4mm) loads reactor, 250 DEG C of N2Dried in place 2h, after using anhydrous HF in-situ activation 2.5h at the same temperature, then switches to monochlorodifluoromethane (R22) and HCFO-1233zd material, enters reactor and reacts。Namely the tail gas that reaction generates obtain CF after chilling, alkali cleaning, washing, dry, compression, rectification and purification3CH2CHClCClF2, yield is more than 60%。
Embodiment 2CF3CH2CHClCClF2CF is prepared in fluoride3CH=CHCF3
By high-purity C F obtained for embodiment 13CH2CHClCClF2Reaction unit identical with embodiment 1 again carries out fluorination reaction, reactor loads Cr2O3Catalyst, wherein, Cr2O3Catalyst adopts the sedimentation method to prepare, and configures 0.5mol/LCrCl3Solution 400mL, drips the ammonia spirit of 25% when being stirred vigorously, until stopping when pH value of solution is 7.5, gained precipitation is through filtering, after 110 DEG C of dry 11h, and 500 DEG C of roasting 3h in Muffle furnace。15mL catalyst is warming up to 250 DEG C, passes into the N containing 25%HF after loading reaction tube2Gaseous mixture 150mL/min fluoride 3h, then, reaction gas switches to CF3CH2CHClCClF2With HF gaseous mixture。Mass flowmenter is adopted to control flow, modulation CF3CH2CHClCClF2With HF flow respectively 50mL/min and 250mL/min (1:5), reaction temperature constant temperature is at 280 DEG C, and namely the tail gas that reaction generates obtain CF after chilling, alkali cleaning, washing, dry, compression, rectification and purification3CH=CHCF3(1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene), along anti-1,1, Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoros-2-butylene is more than 85%。
Embodiment 3 intermediate CF3CHClCHClCF3Preparation
Mode of operation is with embodiment 1, and institute is the difference is that monochlorodifluoromethane (R22) changes into Freon 13 (R13), and namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, dry, compression, rectification and purification3CHClCHClCF3, yield is more than 50%。
Embodiment 4CF3CHClCHClCF3Zn powder dechlorination CF3CH=CHCF3
CF prepared by embodiment 3 is added in the glass flask of condensation reflux unit3CHClCHClCF350g, adds through HCl fresh Zn powder 120g, the DMF1000g processed, replaces the air of flask with Ar gas, be warming up to 75 DEG C, react 8h, filter, obtain CF after rectification3CH=CHCF3, along anti-1,1, Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoros-2-butylene is 71%。
Embodiment 5 intermediate product CF3CH2CHClCF3Preparation
Mode of operation is with embodiment 1, and institute is the difference is that monochlorodifluoromethane (R22) changes into fluoroform (R23), and the charge ratio of R23 and HCFO-1233zd changes 3:1(respectively 150mL/min and 50mL/min into), reaction temperature rises to 380 DEG C。Namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, dry, compression, rectification and purification3CH2CHClCF3, yield is more than 46%。
Embodiment 6CF3CH2CHClCF3Cracking CF3CH=CHCF3
Mode of operation is with embodiment 2。Reaction tube loads the 15mL cocoanut active charcoal (Hainan Ye Qiu activated carbon company limited, 14-20 order) through 20%HCl solution-treated。It is warming up to 250 DEG C, passes into the N containing 25%HF2Gaseous mixture 150mL/min fluoride 3h。Use N2The CF obtained by embodiment 5 of dilution3CH2CHClCF3(N2200mL/min,CF3CH2CHClCF3100mL/min) passing into reactor, reaction temperature constant temperature reacts to 290 DEG C。Namely the tail gas that reaction generates obtain the total recovery along anti-1,1,1,4,4,4-hexafluoro-2-butylene more than 89% after alkali cleaning, washing, dry, compression, rectification and purification。
Embodiment 7 intermediate product CCl2FCHClCH2CF3Preparation
Mode of operation is with embodiment 1, and institute is the difference is that monochlorodifluoromethane (R22) changes into monofluorodichloromethane (R21), and the feed rate of R21 and HCFO-1233zd respectively 100mL/min, reaction temperature rises to 300 DEG C。Namely the tail gas that reaction generates obtain CCl after alkali cleaning, washing, dry, compression, rectification and purification2FCHClCH2CF3, yield is more than 56%。
Embodiment 8CCl2FCHClCH2CF3CF is prepared in fluoride3CH=CHCF3
Mode of operation with embodiment 2, the difference is that by the CF in fluorination reaction3CH2CHClCClF2Change the CCl obtained by embodiment 7 into2FCHClCH2CF3。Namely the tail gas that reaction generates obtain the total recovery along anti-1,1,1,4,4,4-hexafluoro-2-butylene more than 88% after alkali cleaning, washing, dry, compression, rectification and purification。
Embodiment 9 intermediate product CCl3CHClCH2CF3Preparation
Mode of operation is with embodiment 1, and institute is the difference is that changing monochlorodifluoromethane (R22) into chloroform (CHCl3), the feed rate of chloroform and HCFO-1233zd respectively 100mL/min, reaction temperature rises to 300 DEG C。Namely the tail gas that reaction generates obtain CCl after alkali cleaning, washing, dry, compression, rectification and purification3CHClCH2CF3, yield is more than 57%。
Embodiment 10CCl3CHClCH2CF3CF is prepared in fluoride3CH=CHCF3
Mode of operation with embodiment 2, the difference is that by the CF in fluorination reaction3CH2CHClCClF2Change the CCl obtained by embodiment 9 into3CHClCH2CF3。Namely the tail gas that reaction generates obtain the total recovery along anti-1,1,1,4,4,4-hexafluoro-2-butylene more than 83% after alkali cleaning, washing, dry, compression, rectification and purification。
Embodiment 11 intermediate product CClF2CHClCHClCF3Preparation
Mode of operation is with embodiment 1, and institute is the difference is that monochlorodifluoromethane (R22) changes into dichlorodifluoromethane (R12), and the feed rate of R12 and HCFO-1233zd respectively 100mL/min, reaction temperature rises to 300 DEG C。Namely the tail gas that reaction generates obtain CClF after alkali cleaning, washing, dry, compression, rectification and purification2CHClCHClCF3, yield is more than 45%。
Embodiment 12CClF2CHClCHClCF3CF is prepared in fluoride3CHClCHClCF3
Mode of operation with embodiment 2, the difference is that by the CF in fluorination reaction3CH2CHClCClF2Change the CClF obtained by embodiment 11 into2CHClCHClCF3, reaction temperature 250oC。Namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, dry, compression, rectification and purification3CHClCHClCF3Yield more than 93%。The CF obtained3CHClCHClCF3CF can be finally given by the approach of embodiment 43CH=CHCF3。
Embodiment 13 intermediate product CCl2FCHClCHClCF3Preparation
Mode of operation is with embodiment 1, and institute is the difference is that monochlorodifluoromethane (R22) changes into fluoro trichloromethane (R11), and the feed rate of R11 and HCFO-1233zd respectively 100mL/min, reaction temperature rises to 300 DEG C。Namely the tail gas that reaction generates obtain CCl after alkali cleaning, washing, dry, compression, rectification and purification2FCHClCHClCF3, yield is more than 51%。
Embodiment 14CCl2FCHClCHClCF3CF is prepared in fluoride3CHClCHClCF3
Mode of operation with embodiment 2, the difference is that by the CF in fluorination reaction3CH2CHClCClF2Change the CCl obtained by embodiment 13 into2FCHClCHClCF3, reaction temperature 280oC。Namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, dry, compression, rectification and purification3CHClCHClCF3Yield more than 92%。The CF obtained3CHClCHClCF3CF can be finally given by the approach of embodiment 43CH=CHCF3。
Claims (10)
1. prepare 1 for one kind, 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that be CH by formulamXnY4-n-mHalide and HCFO-1233zd flow continuously in tubular reactor thermal addition reaction, namely intermediate hydrogen fluorine chlorine (bromine) butane is obtained after alkali cleaning, washing, dry, compression, rectification and purification, hydrogen fluorine chlorine (bromine) butane of gained or free HCl through vapor phase cracking, or utilize fluorination catalyst to carry out HF fluoride, or utilize zinc powder to carry out dechlorination, the product generated through filtrations, alkali cleaning, washing, dry, compress, rectification and purification obtains highly purified 1,1,1,4,4,4-hexafluoros-2-butylene product, CHmXnY4-n-mMiddle m is 0 or 1, n is 1,2 or 3, and X, Y are selected from F, Cl or Br, and the de-HCl of described hydrogen fluorine chlorine (bromine) butane gas phase thermal cracking concretely comprises the following steps: after the hydrogen purified separation of fluorine chlorine (bromine) butane, pass into equipped with through the activated carbon of pickling, graphite, MgF2Or CsCl/MgF2Beds, under 200-400 DEG C of reaction temperature, slough HCl, directly form 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。
2. preparation 1,1 according to claim 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that described halide is CHClF2、CHF3、CHCl2F、CClF3、CCl2F2、CHCl3、CCl3One or more mixture in F。
3. preparation 1,1 according to claim 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that the molar ratio of halide and HCFO-1233zd is 1:1-4；Heat of mixing additive reaction temperature is 100-400 DEG C；Reaction pressure is 0.1-1MPa, and the time of staying is 0.1-20s。
4. preparation 1,1 according to claim 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that the molar ratio of halide and HCFO-1233zd is 1:1.5 ~ 2；Heat of mixing additive reaction temperature is 250-350 DEG C；Reaction pressure is 0.3-0.6MPa, and the time of staying is 6-10s。
5. preparation 1,1,1 according to claim 1, the method of 4,4,4-hexafluoros-2-butylene, it is characterized in that described hydrogen fluorine chlorine (bromine) butane utilizes zinc powder to carry out concretely comprising the following steps of dechlorination: by the reactor equipped with excessive Zn powder and organic solvent, after reacting 1-10h at 50-90 DEG C, separating reaction mother solution, namely highly purified 1 is obtained after alkali cleaning, washing, dry, compression, rectification and purification, 1, Isosorbide-5-Nitrae, 4,4-hexafluoros-2-butylene。
6. preparation 1,1,1 according to claim 5, the method of 4,4,4-hexafluoros-2-butylene, it is characterized in that the mass ratio that feeds intake that described Zn powder is the fresh Zn powder after dilute hydrochloric acid activates, described Zn powder addition and hydrogen fluorine chlorine (bromine) butane is 2-3:1。
7. preparation 1,1 according to claim 5, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that described organic solvent includes DMF or sulfolane。
8. preparation 1,1,1 according to claim 1, the method of 4,4,4-hexafluoros-2-butylene, it is characterized in that described hydrogen fluorine chlorine (bromine) butane utilizes fluorination catalyst to carry out concretely comprising the following steps of HF fluoride: pass into equipped with in the tubular reactor of fluorination catalyst by hydrogen fluorine chlorine (bromine) butane, 200-400 DEG C of fluoride, product utilization zinc powder carry out dechlorination or be directly over filter, alkali cleaning, washing, dry, compression, rectification and purification obtain highly purified 1,1,1,4,4,4-hexafluoros-2-butylene。
9. preparation 1,1 according to claim 8, Isosorbide-5-Nitrae, the method for 4,4-hexafluoros-2-butylene, it is characterised in that described fluorination catalyst is Cr2O3、Ni-Cr2O3、MgF2-Cr2O3、Ni-Cr/MgF2Or activated carbon after pickling, high-ratio surface graphite。
10. preparation 1 according to claim 8,1,1,4,4, the method of 4-hexafluoro-2-butylene, it is characterised in that described fluorination catalyst uses anhydrous hydrogen fluoride 250 DEG C of pre-fluoride 2-5h of original position in tubular reactor before reactions, and described tubular reactor is corrosion resistant nickel pipe, Inconel or Mo Naier compo pipe。
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| CN109553506B (en) * | 2018-12-20 | 2021-10-01 | 西安近代化学研究所 | Method for synthesizing trans-1, 1,1,4,4, 4-hexafluoro-2-butene |
| MX2021011163A (en) * | 2019-04-05 | 2021-10-22 | Chemours Co Fc Llc | Processes for producing z-1,1,1,4,4,4-hexafluorobut-2-ene and intermediates for producing same. |
| CN110372472A (en) * | 2019-07-26 | 2019-10-25 | 西安近代化学研究所 | A kind of synthetic method of the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- |
| CN110776393B (en) * | 2019-09-26 | 2021-01-26 | 浙江大学 | Method for producing R22 and R21 by liquid-phase method pipelining poly-generation |
| CN112645794B (en) * | 2020-12-28 | 2022-12-27 | 山东东岳化工有限公司 | Preparation method of hexafluoro-1,3-butadiene |
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| US8461401B2 (en) * | 2010-03-26 | 2013-06-11 | Honeywell International Inc. | Method for making hexafluoro-2-butene |
| US8530709B2 (en) * | 2010-05-21 | 2013-09-10 | Honeywell International Inc. | Process for the production of fluorinated alkenes |
| US8901360B2 (en) * | 2010-05-21 | 2014-12-02 | Honeywell International Inc. | Process for cis 1,1,1,4,4,4-hexafluoro-2-butene |
| US8604257B2 (en) * | 2010-05-21 | 2013-12-10 | Honeywell International Inc. | Process for the preparation of fluorinated cis-alkene |
| CN103373896B (en) * | 2012-04-13 | 2015-03-18 | 中化蓝天集团有限公司 | Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene |
| CN104370690B (en) * | 2014-11-20 | 2016-08-17 | 西安近代化学研究所 | A kind of anti-form-1, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene |
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