CN104529695A - Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene - Google Patents

Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene Download PDF

Info

Publication number
CN104529695A
CN104529695A CN201510037748.3A CN201510037748A CN104529695A CN 104529695 A CN104529695 A CN 104529695A CN 201510037748 A CN201510037748 A CN 201510037748A CN 104529695 A CN104529695 A CN 104529695A
Authority
CN
China
Prior art keywords
hexafluoro
butylene
preparation
nitrae
isosorbide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510037748.3A
Other languages
Chinese (zh)
Other versions
CN104529695B (en
Inventor
周孝瑞
张元中
楼月瑛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Nuoya Fluorine Chemical Co., Ltd.
Original Assignee
HANGZHOU FANGHUAN TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by HANGZHOU FANGHUAN TECHNOLOGY Co Ltd filed Critical HANGZHOU FANGHUAN TECHNOLOGY Co Ltd
Priority to CN201510037748.3A priority Critical patent/CN104529695B/en
Publication of CN104529695A publication Critical patent/CN104529695A/en
Application granted granted Critical
Publication of CN104529695B publication Critical patent/CN104529695B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a method for preparing 1,1,1,4,4,4-hexafluoro-2-butene, which comprises the following steps: mixing CHmXnY[4-n-m] (m is 0 or 1, n is 1, 2 or 3, and X and Y are selected from F, Cl or Br.) and HCFO-1233zd (CHCl=CHCF3) to perform thermal addition reaction; carrying out gas-phase thermal cracking on the intermediate product hydrofluorochloro(bromo) butane to remove HCl, or carrying out HF fluoridation by using a fluoridation catalyst, or dechlorinating by using zinc powder; and filtering the reaction product, washing with alkali, washing with water, drying, compressing, and carrying out rectifying purification to obtain the high-purity 1,1,1,4,4,4-hexafluoro-2-butene product. The method has the advantages of simple technique and accessible raw materials, can easily implement industrialization, and is green and environment-friendly.

Description

One prepares 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene
Technical field
The invention belongs to perhaloalkenes preparing technical field, be specifically related to the preparation 1,1 that a kind of whipping agent, refrigeration agent and solvent industry use, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene.
Background technology
1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene (CF 3cH=CHCF 3) thermal conductivity close to HFC-365mfc and HFC-245fa, a little more than CFC-12, HCFC-141b, non-combustible, ODP(ozone-depleting is dived value) be that 0, GWP(Greenhouse effect are dived values) be only 5, therefore it is ideal common foaming, one of substitute of refrigeration agent and solvent.Therefore, as novel whipping agent, refrigeration agent and solvent, 1,1,1,4,4,4-hexafluoro-2-butylene has environmental protection, heat-insulation and heat-preservation, safety, do not consume ozone, nonflammable, the features such as Greenhouse effect are low, it, by becoming the application of future market and promoting object, has good market outlook and economic benefit.
At present, 1,1,1, the preparation method of 4,4,4-hexafluoro-2-butylene is more, mainly comprise hexafluoro-2-butyne hydrogenation, trichloromethane and R 1216 copolymerization, CFC-113 is coupled, fluoridize and dechlorination route, and tetracol phenixin and ethene telomerize synthesis and fluoridizes dechlorination route, HFC-347mef dehydrofluorination, HCFC-123 is coupled and tetracol phenixin and trifluoro propene telomerize the operational paths such as synthesis.
Be hydrogenated to raw material with hexafluoro-2-butyne, adopt Pd or Lindlar catalyst to catalyzing hydrogenating, selectivity can generate (Z)-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.Usually add arylamine in reaction system, the noxious solvent such as quinoline or pyridine carries out modification to catalyzer.CN102892738A finds to utilize has good shortening effect through the 3.5% saturnine 5%Pd catalyzer being carried on calcium carbonate.This route technique is simple, is applicable to industrial production, but its subject matter is reaction raw materials hexafluoro-2-butyne is difficult to preparation, and cost is higher.
CN102892738A reports by thermal addition reaction, CHCl 3c h bond insert R 1216, formed CCl 3cF 2cHFCF 3, then fluoridize through HF, hydrogenation takes off the steps such as HF and finally obtains hexafluoro-2-butyne, then forms 1,1 to hexafluoro-2-butyne selective hydrogenation, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.Can find, this route steps is numerous and diverse, and yield is low.
Utilize similar reactive mode, CCl 4with the reaction of 3,3,3-trifluoro propene, through three-step reaction, target product [CN102884030A] also can be produced.
Patent US 2011/01288350 finds CFC-113a(CCl 3cF 3) mix with 1,2 Ethylene Dichloride, under iron catalyst and the effect of 3-butyl phosphate, be placed in autoclave, reaction certain hour, can obtain CF 3cCl 2cHClCHCl 2intermediate product.CF is obtained again through chlorination 3cCl 2cCl 2cCl 3, fluoridize with HF and obtain CF 3cCl 2cCl 2cCF 3, form 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene through Cu/AC catalyzer 300-350 DEG C of hydrogenation reaction.
Utilize the most basic raw material CCl 4and CH 2=CH 2through telomerization, CN102892736A finds that product is CCl 3cH 2cH 2cl (HCC-250), de-HCl product C Cl 3cH=CH 2again with CCl 4telomerize, obtain CCl 3cHClCH 2cCl 3, it is 1,1 that HF fluoridizes after product, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.
With HCFC-123(CF 3cHCl 2) be raw material, mix with metallic copper and methylamine or ethamine etc. and load reactor, after 60 DEG C of about 10 h of reaction, target product 1,1 can be collected in the product, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene [CN 102015592A].Reaction is rhythmic 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, the object of the present invention is to provide that a kind of technique is simple, yield is high, step is few and be easy to industrialized preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene.
Described one prepares 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, it is characterized in that general formula being CH mx ny 4-n-mmethyl halide and HCFO-1233zd in tubular reactor, carry out continuous flow carry out mixture heat addition reaction, namely intermediate hydrogen fluorine chlorine (bromine) butane is obtained after alkali cleaning, washing, drying, 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 to fluoridize, or utilize zinc powder to carry out dechlorination, the product generated after filtration, alkali cleaning, washing, drying, compression, rectification and purification obtain highly purified 1,1,1,4,4,4-hexafluoro-2-butylene product, CH mx ny 4-n-mmiddle m be 0 or 1, n be 1,2 or 3, and X, Y are all selected from F, Cl or Br.Its molecular formula of HCFO-1233zd is CHCl=CHCF 3, it is the intermediate raw material of the conventional refrigeration agent such as HFO-1234ze, HFC-245fa, whipping agent, can fluoridize optionally obtain through HCO-240fa etc., and these raw material sources are extensive, are easy to get.Intermediate hydrogen fluorine chlorine (bromine) butane intermediate product comprises CF 3cH 2cHClCClF 2, CF 3cHClCH 2cF 3, CCl 2fCHClCH 2cF 3, CF 3cHClCHClCF 3, CClF 2cHClCHFCF 3, CCl 2fCHClCHFCF 3, CClF 2cHClCHClCF 3, CCl 3cHClCH 2cF 3, CHCl 2cHClCHClCF 3, CCl 2fCHClCHClCF 3, CCl 3cHClCHFCF 3deng.
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that described methyl halide is CHClF 2, CHF 3, CHCl 2f, CClF 3, CCl 2f 2, CHCl 3, CCl 3one or more mixtures in F.
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that the molar ratio of methyl halide and HCFO-1233zd is 1:1-4, is preferably 1:1.2 ~ 2; Mixture heat addition reaction temperature is 100-400 DEG C, and be preferably 250-350 DEG C, reaction pressure is 0.1-1MPa, and be preferably 0.3 ~ 0.6MPa, the residence time is 0.1-20s, is preferably 6 ~ 10s.
Described preparation 1,1,1, the method of 4,4,4-hexafluoro-2-butylene, it is characterized in that described hydrogen fluorine chlorine (bromine) butane gas phase thermo-cracking takes off HCl concrete steps and is: hydrogen fluorine chlorine (bromine) butane, after purification & isolation, passes into the gac, high-ratio surface graphite, graphite, the MgF that are equipped with through pickling 2, CsCl/MgF 2beds, under 200-400 DEG C of temperature of reaction, slough HCl, directly form 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene, intermediate hydrogen fluorine chlorine (bromine) butane of being freed HCl preparing product by vapor phase cracking is CF 3cHClCH 2cF 3.
Described preparation 1,1,1,4,4, the method of 4-hexafluoro-2-butylene, is characterized in that the concrete steps that described hydrogen fluorine chlorine (bromine) butane utilizes zinc powder to carry out dechlorination are: by being equipped with the reactor of excessive Zn powder and organic solvent, react 1-10h at 50-is 90 DEG C after, separating reaction mother liquor, namely highly purified 1 is obtained, 1,1 after alkali cleaning, washing, drying, compression, rectification and purification, 4,4,4-hexafluoro-2-butylene, intermediate hydrogen fluorine chlorine (bromine) butane utilizing zinc powder to carry out dechlorination preparing product is CF 3cHClCHClCF 3.
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, it is characterized in that described Zn powder is the fresh Zn powder after dilute hydrochloric acid activation, the mass ratio that feeds intake of described Zn powder add-on and hydrogen fluorine chlorine (bromine) butane is 2-3:1.
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that described organic solvent comprises DMF or tetramethylene sulfone.
Described preparation 1,1,1,4,4, the method of 4-hexafluoro-2-butylene, the concrete steps that it is characterized in that utilizing fluorination catalyst to carry out by described hydrogen fluorine chlorine (bromine) butane HF fluoridizes are: passed into by hydrogen fluorine chlorine (bromine) butane and be equipped with in the tubular reactor of fluorination catalyst, fluoridize at 200-400 DEG C, product utilization zinc powder carry out dechlorination or directly after filtration, alkali cleaning, washing, drying, compression, rectification and purification obtain highly purified 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene, hydrogen fluorine chlorine (bromine) butane that HF fluoridizes preparing product comprises CF to utilize fluorination catalyst to carry out 3cH 2cHClCClF 2, CCl 2fCHClCH 2cF 3, CCl 3cHClCH 2cF 3, CClF 2cHClCHFCF 3, CCl 2fCHClCHFCF 3, CClF 2cHClCHClCF 3, CHCl 2cHClCHClCF 3, CCl 2fCHClCHClCF 3and CCl 3cHClCHFCF 3, the product obtained is respectively 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene and CF 3cHClCHClCF 3, 1,1, Isosorbide-5-Nitrae, namely 4,4-hexafluoro-2-butylene directly obtains highly purified 1,1, Isosorbide-5-Nitrae after alkali cleaning, washing, drying, compression, rectification and purification, 4,4-hexafluoro-2-butylene; CF 3cHClCHClCF 3can pass through the dechlorination of Zn powder, namely separating reaction mother liquor obtains highly purified 1,1 after alkali cleaning, washing, drying, compression, rectification and purification, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.
Described preparation 1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that described fluorination catalyst is Cr 2o 3, Ni-Cr 2o 3, MgF 2-Cr 2o 3, Ni-Cr/MgF 2or gac, the high-ratio surface graphite after pickling.
Described preparation 1,1,1, the method of 4,4,4-hexafluoro-2-butylene, it is characterized in that described fluorination catalyst fluoridizes 2-5h in advance by anhydrous hydrogen fluoride 250 DEG C of original positions in tubular reactor before reactions, described tubular reactor is corrosion resistant nickel pipe, Inconel and Mo Naier compo pipe.
The principal reaction formula that the present invention relates to is as follows:
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows: 1) the present invention adopts with CHClF 2, CHF 3, CHCl 2f, CClF 3, CCl 2f 2, CHCl 3, CCl 3one or more mixtures of F etc. and HCFO-1233zd are raw material, and obtain intermediate hydrogen fluorine chlorine (bromine) butane through mixture heat addition reaction, this intermediate product frees HCl through vapor phase cracking, or utilize fluorination catalyst to carry out HF to fluoridize, or utilize zinc powder to carry out dechlorination, 1,1 of synthesis of high purity, 1,4,4,4-hexafluoro-2-butylene, its technique is simple, easy to operate, cheaper starting materials is easy to get, cost is low, is suitable for suitability for industrialized production;
2) preparation 1,1,1 provided by the invention, the method of 4,4,4-hexafluoro-2-butylene, overcome the shortcoming that the existing technological operation cycle is long, unit volume yields poorly, facility investment is large etc., its yield is high, step is few, be easy to industrialization, and the present invention is by the selection of reactant and the control of reaction conditions, highly purified 1 can be realized, 1, Isosorbide-5-Nitrae, the production of 4,4-hexafluoro-2-butylene.Method technique of the present invention is simple, and equipment used simplifies, and unit device production capacity can be made greatly to improve.
3) the present invention is owing to adopting Continuous Heat addition reaction route, can the continous-stable of realization response process, can keep long-time steady operation, more be conducive to 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 in this:
Embodiment 1 intermediate product CF 3cH 2cHClCClF 2preparation
With difluorochloromethane (R22) and HCFO-1233zd for raw material, prepare CF through thermal addition reaction 3cH 2cHClCClF 2this reaction is carried out in plug flow reactor, the reaction tubes of tubular reactor adopts internal diameter 18 mm, length is the Ni pipe of 50cm, and be placed in tube furnace heat temperature raising, the present invention is in order to prevent material condensation, all reaction forming pipelines adopt stainless steel tube, and with Heat preservation chuck constant temperature at about 70 DEG C, difluorochloromethane (R22) and HCFO-1233zd adopt mass flowmeter to control flow (100 mL/min) respectively, its flow ratio of modulation is 1, and temperature of reaction is stabilized in 300 DEG C, and reaction pressure is 0.5 MPa.Before reaction, be 200 m by surface-area 2powdered graphite 30 MPa compression moldings on tabletting machine of/g, broken, screening order number is that particle 15 mL of 14-20 order (1-1.4 mm) loads reactor, 250 DEG C of N 2dried in place 2 h, after using anhydrous HF in-situ activation 2.5 h at the same temperature, then switches to difluorochloromethane (R22) and HCFO-1233zd material, enters reactor and react.Namely the tail gas that reaction generates obtain CF after chilling, alkali cleaning, washing, drying, compression, rectification and purification 3cH 2cHClCClF 2, yield is more than 60%.
Embodiment 2 CF 3cH 2cHClCClF 2fluoridize preparation CF 3cH=CHCF 3
The high-purity C F that embodiment 1 is obtained 3cH 2cHClCClF 2reaction unit identical with embodiment 1 again carries out fluoridation, in reactor, loads Cr 2o 3catalyzer, wherein, Cr 2o 3catalyzer adopts precipitator method preparation, configures 0.5 mol/LCrCl 3solution 400 mL, drips the ammonia soln of 25% under the state of vigorous stirring, until stop when pH value of solution is 7.5, gained precipitates after filtration, after 110 DEG C of drying 11 h, and 500 DEG C of roasting 3h in retort furnace.15 mL catalyzer are warming up to 250 DEG C, pass into the N containing 25%HF after loading reaction tubes 2gas mixture 150 mL/min fluoridizes 3h, and then, reaction gas switches to CF 3cH 2cHClCClF 2with HF gas mixture.Mass flowmeter is adopted to control flow, modulation CF 3cH 2cHClCClF 2be respectively 50mL/min and 250mL/min (1:5) with HF flow, temperature of reaction constant temperature is at 280 DEG C, and namely the tail gas that reaction generates obtain CF after chilling, alkali cleaning, washing, drying, compression, rectification and purification 3cH=CHCF 3(1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene), along anti-1,1, Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoro-2-butylene is more than 85%.
Embodiment 3 intermediate CF 3cHClCHClCF 3preparation
Operating method is with embodiment 1, and difference changes difluorochloromethane (R22) into Freon 13 (R13), and namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, drying, compression, rectification and purification 3cHClCHClC F 3, yield is more than 50%.
Embodiment 4 CF 3cHClCHClCF 3zn powder dechlorination CF 3cH=CHCF 3
CF prepared by embodiment 3 is added in the glass flask of band condensation reflux unit 3cHClCHClCF 350g, then add fresh Zn powder 120g, DMF 1000 g through HCl process, with the air of Ar gas displacement flask, be warming up to 75 DEG C, react 8 h, filter, after rectifying, obtain CF 3cH=CHCF 3, along anti-1,1, Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoro-2-butylene is 71%.
Embodiment 5 intermediate product CF 3cH 2cHClCF 3preparation
Operating method is with embodiment 1, and difference changes difluorochloromethane (R22) into trifluoromethane (R23), and the charge ratio of R23 and HCFO-1233zd changes 3:1(into and is respectively 150 mL/min and 50 mL/min), temperature of reaction rises to 380 DEG C.Namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, drying, compression, rectification and purification 3cH 2cHClCF 3, yield is more than 46%.
Embodiment 6 CF 3cH 2cHClCF 3cracking CF 3cH=CHCF 3
Operating method is with embodiment 2.The cocoanut active charcoal (Hainan Ye Qiu gac company limited, 14-20 order) of 15mL through 20%HCl solution-treated is loaded in reaction tubes.Be warming up to 250 DEG C, pass into the N containing 25%HF 2gas mixture 150mL/min fluoridizes 3h.Use N 2the CF obtained by embodiment 5 of dilution 3cH 2cHClCF 3(N 2200mL/min, CF 3cH 2cHClCF 3100 mL/min) pass into reactor, temperature of reaction constant temperature to 290 DEG C reacts.Namely the tail gas that reaction generates obtain along anti-1,1 after alkali cleaning, washing, drying, compression, rectification and purification, and Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoro-2-butylene is more than 89%.
Embodiment 7 intermediate product CCl 2fCHClCH 2cF 3preparation
Operating method is with embodiment 1, and difference changes difluorochloromethane (R22) into dichloromonofluoromethane (R21), and the feed rate of R21 and HCFO-1233zd is respectively 100 mL/min, and temperature of reaction rises to 300 DEG C.Namely the tail gas that reaction generates obtain CCl after alkali cleaning, washing, drying, compression, rectification and purification 2fCHClCH 2cF 3, yield is more than 56%.
Embodiment 8 CCl 2fCHClCH 2cF 3fluoridize preparation CF 3cH=CHCF 3
Operating method is with embodiment 2, and difference is by the CF in fluoridation 3cH 2cHClCClF 2change the CCl obtained by embodiment 7 into 2fCHClCH 2cF 3.Namely the tail gas that reaction generates obtain along anti-1,1 after alkali cleaning, washing, drying, compression, rectification and purification, and Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoro-2-butylene is more than 88%.
Embodiment 9 intermediate product CCl 3cHClCH 2cF 3preparation
Operating method is with embodiment 1, and difference changes difluorochloromethane (R22) into chloroform (CHCl 3), the feed rate of chloroform and HCFO-1233zd is respectively 100 mL/min, and temperature of reaction rises to 300 DEG C.Namely the tail gas that reaction generates obtain CCl after alkali cleaning, washing, drying, compression, rectification and purification 3cHClCH 2cF 3, yield is more than 57%.
Embodiment 10 CCl 3cHClCH 2cF 3fluoridize preparation CF 3cH=CHCF 3
Operating method is with embodiment 2, and difference is by the CF in fluoridation 3cH 2cHClCClF 2change the CCl obtained by embodiment 9 into 3cHClCH 2cF 3.Namely the tail gas that reaction generates obtain along anti-1,1 after alkali cleaning, washing, drying, compression, rectification and purification, and Isosorbide-5-Nitrae, the total recovery of 4,4-hexafluoro-2-butylene is more than 83%.
Embodiment 11 intermediate product CClF 2cHClCHClCF 3preparation
Operating method is with embodiment 1, and difference changes difluorochloromethane (R22) into methyl chlorofluoride (R12), and the feed rate of R12 and HCFO-1233zd is respectively 100 mL/min, and temperature of reaction rises to 300 DEG C.Namely the tail gas that reaction generates obtain CClF after alkali cleaning, washing, drying, compression, rectification and purification 2cHClCHClCF 3, yield is more than 45%.
Embodiment 12 CClF 2cHClCHClCF 3fluoridize preparation CF 3cHClCHClCF 3
Operating method is with embodiment 2, and difference is by the CF in fluoridation 3cH 2cHClCClF 2change the CClF obtained by embodiment 11 into 2cHClCHClCF 3, temperature of reaction 250 oc.Namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, drying, compression, rectification and purification 3cHClCHClCF 3yield more than 93%.The CF obtained 3cHClCHClCF 3approach by embodiment 4 finally obtains CF 3cH=CHCF 3.
Embodiment 13 intermediate product CCl 2fCHClCHClCF 3preparation
Operating method is with embodiment 1, and difference changes difluorochloromethane (R22) into fluoro trichloromethane (R11), and the feed rate of R11 and HCFO-1233zd is respectively 100 mL/min, and temperature of reaction rises to 300 DEG C.Namely the tail gas that reaction generates obtain CCl after alkali cleaning, washing, drying, compression, rectification and purification 2fCHClCHClCF 3, yield is more than 51%.
Embodiment 14 CCl 2fCHClCHClCF 3fluoridize preparation CF 3cHClCHClCF 3
Operating method is with embodiment 2, and difference is by the CF in fluoridation 3cH 2cHClCClF 2change the CCl obtained by embodiment 13 into 2fCHClCHClCF 3, temperature of reaction 280 oc.Namely the tail gas that reaction generates obtain CF after alkali cleaning, washing, drying, compression, rectification and purification 3cHClCHClCF 3yield more than 92%.The CF obtained 3cHClCHClCF 3approach by embodiment 4 finally obtains CF 3cH=CHCF 3.

Claims (10)

1. prepare 1,1, Isosorbide-5-Nitrae for one kind, the method for 4,4-hexafluoro-2-butylene, it is characterized in that general formula being CH mx ny 4-n-mmethyl halide and HCFO-1233zd in tubular reactor, carry out continuous flow thermal addition reaction, namely intermediate hydrogen fluorine chlorine (bromine) butane is obtained after alkali cleaning, washing, drying, 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 to fluoridize, or utilize zinc powder to carry out dechlorination, the product generated after filtration, alkali cleaning, washing, drying, compression, rectification and purification obtain highly purified 1,1,1,4,4,4-hexafluoro-2-butylene product, CH mx ny 4-n-mmiddle m be 0 or 1, n be 1,2 or 3, and X, Y are all selected from F, Cl or Br.
2. preparation 1,1 according to claim 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that described methyl halide is CHClF 2, CHF 3, CHCl 2f, CClF 3, CCl 2f 2, CHCl 3, CCl 3one or more mixtures in F.
3. preparation 1,1 according to claim 1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that the molar ratio of methyl halide and HCFO-1233zd is 1:1-4, is preferably 1:1.5 ~ 2; Mixture heat addition reaction temperature is 100-400 DEG C, is preferably 250-350 DEG C; Reaction pressure is 0.1-1MPa, and be preferably 0.3-0.6MPa, the residence time is 0.1-20s, is preferably 6-10s.
4. preparation 1 according to claim 1,1,1,4,4, the method of 4-hexafluoro-2-butylene, is characterized in that described hydrogen fluorine chlorine (bromine) butane gas phase thermo-cracking takes off HCl concrete steps and is: hydrogen fluorine chlorine (bromine) butane, after purification & isolation, passes into the gac, high-ratio surface graphite, graphite, the MgF that are equipped with through pickling 2, CsCl/MgF 2beds, under 200-400 DEG C of temperature of reaction, slough HCl, directly form 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.
5. preparation 1,1,1 according to claim 1, the method of 4,4,4-hexafluoro-2-butylene, it is characterized in that the concrete steps that described hydrogen fluorine chlorine (bromine) butane utilizes zinc powder to carry out dechlorination are: by being equipped with the reactor of excessive Zn powder and organic solvent, react 1-10h at 50-is 90 DEG C after, separating reaction mother liquor, namely highly purified 1 is obtained after alkali cleaning, washing, drying, compression, rectification and purification, 1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.
6. preparation 1,1,1 according to claim 5, the method of 4,4,4-hexafluoro-2-butylene, it is characterized in that described Zn powder is the fresh Zn powder after dilute hydrochloric acid activation, the mass ratio that feeds intake of described Zn powder add-on 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-hexafluoro-2-butylene, is characterized in that described organic solvent comprises DMF or tetramethylene sulfone.
8. preparation 1,1,1 according to claim 1, the method of 4,4,4-hexafluoro-2-butylene, the concrete steps that it is characterized in that utilizing fluorination catalyst to carry out by described hydrogen fluorine chlorine (bromine) butane HF fluoridizes are: passed into by hydrogen fluorine chlorine (bromine) butane and be equipped with in the tubular reactor of fluorination catalyst, fluoridize at 200-400 DEG C, product utilization zinc powder carry out dechlorination or directly after filtration, alkali cleaning, washing, drying, compression, rectification and purification obtain highly purified 1,1,1,4,4,4-hexafluoro-2-butylene.
9. preparation 1,1 according to claim 8, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, is characterized in that described fluorination catalyst is Cr 2o 3, Ni-Cr 2o 3, MgF 2-Cr 2o 3, Ni-Cr/MgF 2or gac, the high-ratio surface graphite after pickling.
10. preparation 1 according to claim 8,1,1,4,4, the method of 4-hexafluoro-2-butylene, it is characterized in that described fluorination catalyst fluoridizes 2-5h in advance by anhydrous hydrogen fluoride 250 DEG C of original positions in tubular reactor before reactions, described tubular reactor is corrosion resistant nickel pipe, Inconel or Mo Naier compo pipe.
CN201510037748.3A 2015-01-26 2015-01-26 A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene Active CN104529695B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510037748.3A CN104529695B (en) 2015-01-26 2015-01-26 A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510037748.3A CN104529695B (en) 2015-01-26 2015-01-26 A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene

Publications (2)

Publication Number Publication Date
CN104529695A true CN104529695A (en) 2015-04-22
CN104529695B CN104529695B (en) 2016-06-22

Family

ID=52845382

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510037748.3A Active CN104529695B (en) 2015-01-26 2015-01-26 A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene

Country Status (1)

Country Link
CN (1) CN104529695B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109476567A (en) * 2016-07-27 2019-03-15 科慕埃弗西有限公司 Method for producing halogenated olefins
CN109553506A (en) * 2018-12-20 2019-04-02 西安近代化学研究所 A kind of method of synthesis of trans -1,1,1,4,4,4- hexafluoro -2- butylene
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-
CN110776393A (en) * 2019-09-26 2020-02-11 浙江大学 Method for producing R22 and R21 by liquid-phase method pipelining poly-generation
CN112645794A (en) * 2020-12-28 2021-04-13 山东东岳化工有限公司 Preparation method of hexafluoro-1, 3-butadiene
CN113661154A (en) * 2019-04-05 2021-11-16 科慕埃弗西有限公司 Process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene and intermediates useful for preparing same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110288350A1 (en) * 2010-05-21 2011-11-24 Honeywell International Inc. Process for the preparation of fluorinated cis-alkene
CN102884030A (en) * 2010-03-26 2013-01-16 霍尼韦尔国际公司 Method for making hexafluoro-2-butene
CN102892739A (en) * 2010-05-21 2013-01-23 霍尼韦尔国际公司 Process for cis-1,1,1,4,4,4,-hexafluoro-2-butene
CN102892738A (en) * 2010-05-21 2013-01-23 霍尼韦尔国际公司 Process for the production of fluorinated alkenes
CN103373896A (en) * 2012-04-13 2013-10-30 中化蓝天集团有限公司 Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene
CN104370690A (en) * 2014-11-20 2015-02-25 西安近代化学研究所 Synthetic method of trans-1, 1, 1, 4, 4, 4-hexafluoro-2-butene

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102884030A (en) * 2010-03-26 2013-01-16 霍尼韦尔国际公司 Method for making hexafluoro-2-butene
US20110288350A1 (en) * 2010-05-21 2011-11-24 Honeywell International Inc. Process for the preparation of fluorinated cis-alkene
CN102892739A (en) * 2010-05-21 2013-01-23 霍尼韦尔国际公司 Process for cis-1,1,1,4,4,4,-hexafluoro-2-butene
CN102892738A (en) * 2010-05-21 2013-01-23 霍尼韦尔国际公司 Process for the production of fluorinated alkenes
CN103373896A (en) * 2012-04-13 2013-10-30 中化蓝天集团有限公司 Method for preparing 1,1,1,4,4,4-hexafluoro-2-butene
CN104370690A (en) * 2014-11-20 2015-02-25 西安近代化学研究所 Synthetic method of trans-1, 1, 1, 4, 4, 4-hexafluoro-2-butene

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
XIAOQING JIA，ET AL.: "Preparation of cis-1,1,1,4,4,4-hexafluorobut-2-ene by cis-selective semi-hydrogenation of perfluoro-2-butyne", 《JOURNAL OF FLUORINE CHEMISTRY》 *
XIAOQING JIA，ET AL.: "Preparation of cis-1,1,1,4,4,4-hexafluorobut-2-ene by cis-selective semi-hydrogenation of perfluoro-2-butyne", 《JOURNAL OF FLUORINE CHEMISTRY》, vol. 132, 13 June 2011 (2011-06-13), pages 1188 - 1193 *
付庆等: "六氟-2-丁烯的合成研究进展", 《有机氟工业》 *
赵波等: "(顺)-1,1,1,4,4,4-六氟-2-丁烯的合成研究进展", 《化工进展》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109476567A (en) * 2016-07-27 2019-03-15 科慕埃弗西有限公司 Method for producing halogenated olefins
CN109476567B (en) * 2016-07-27 2022-08-09 科慕埃弗西有限公司 Process for producing halogenated olefins
CN109553506A (en) * 2018-12-20 2019-04-02 西安近代化学研究所 A kind of method of synthesis of trans -1,1,1,4,4,4- hexafluoro -2- butylene
CN113661154A (en) * 2019-04-05 2021-11-16 科慕埃弗西有限公司 Process for preparing Z-1,1,1,4,4, 4-hexafluorobut-2-ene and intermediates useful for preparing same
CN113661154B (en) * 2019-04-05 2024-04-09 科慕埃弗西有限公司 Process for preparing Z-1, 4-hexafluorobut-2-ene and intermediates for preparing the 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-
CN110776393A (en) * 2019-09-26 2020-02-11 浙江大学 Method for producing R22 and R21 by liquid-phase method pipelining poly-generation
CN112645794A (en) * 2020-12-28 2021-04-13 山东东岳化工有限公司 Preparation method of hexafluoro-1, 3-butadiene
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

Also Published As

Publication number Publication date
CN104529695B (en) 2016-06-22

Similar Documents

Publication Publication Date Title
CN104529695B (en) A kind of method preparing 1,1,1,4,4,4-hexafluoro-2-butylene
JP6650523B2 (en) Method for simultaneous production of 1-chloro-3,3,3-trifluoropropylene, 2,3,3,3-tetrafluoropropylene and 1,3,3,3-tetrafluoropropylene
CN102405203B (en) Process for preparation of 2,3,3,3-tetrafluoropropene
CN101351427B (en) Method for producing fluorinated organic compounds
US8530711B2 (en) Process for producing 2,3,3,3-tetrafluoropropene
CN102884031B (en) For the formation of the dehydrofluorination of five fluothane of tetrafluoroolefin
CN106866354B (en) A kind of preparation method of 1,1- difluoroethylene
CN110833837B (en) Catalyst for resource utilization of trifluoromethane
JP2016513138A (en) Chlorinated propane production process
WO2014094587A1 (en) 1, 3, 3, 3-tetrafluoropropene preparation process
CN102199071B (en) Method for synthesizing 2,3,3,3-tetrafluoropropene
CN104159878A (en) Process for 1,3,3,3-tetrafluoropropene
WO2019047447A1 (en) Method for co-producing various halogenated olefins and fluoroalkanes
CN111875473B (en) Preparation method of HFC-365mfc and HFC-245fa
CN108383679A (en) A kind of co-production of anti-form-1-chloro- 3,3,3- trifluoro propenes and 2,3,3,3- tetrafluoropropenes
CN105399599A (en) Method for preparing hexafluorobutadiene
WO2014094590A1 (en) Hfo-1234ze and hfc-245fa co-production preparation process
CN104496746A (en) Method for simultaneously preparing 1,1,1,2,2-pentachloropropane and 2,3,3,3-tetrachloropropene
CN102459137B (en) Process for preparing fluoroolefin compounds
CN102211974B (en) Preparation method of 1,3,3,3-tetrafluoropropylene
CN116060010B (en) Initiator, fluorination catalyst and process for the preparation of E-1, 4-hexafluoro-2-butene
CN105753640A (en) Preparation method of 1,3,3,3-tetrafluoropropene
CN102120714B (en) Method for preparing pentafluoroethane
CN109331864B (en) Hydrogenation coupling catalyst, preparation method thereof and method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene
CN107739293B (en) Method for preparing fluoroalkane from alkyl ether gas phase

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20180427

Address after: 312300 Zhejiang Shaoxing Shangyu Hangzhou Bay Shangyu economic and Technological Development Zone

Patentee after: Zhejiang Nuoya Fluorine Chemical Co., Ltd.

Address before: 310023 room 1007, 2 UN commune, 135 Yu He road, Xihu District, Hangzhou, Zhejiang.

Patentee before: HANGZHOU FANGHUAN TECHNOLOGY CO., LTD.