CN102992945B - 1-chloro-2,2-difluoroethylene preparation method - Google Patents
1-chloro-2,2-difluoroethylene preparation method Download PDFInfo
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- CN102992945B CN102992945B CN201110270198.1A CN201110270198A CN102992945B CN 102992945 B CN102992945 B CN 102992945B CN 201110270198 A CN201110270198 A CN 201110270198A CN 102992945 B CN102992945 B CN 102992945B
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Abstract
The invention discloses a method for preparing 1-chloro-2,2-difluoroethylene through treating difluorotrichloroethane which is a byproduct in the production of trifluorodichloroethane as a raw material. The addition of a reaction assistant in a reaction process can substantially improve the raw material conversion rate and the product yield. The prepared 1-chloro-2,2-difluoroethylene is an important fluorine fine chemical engineering raw material, and can be used in the production of fluorine-containing finishing agents, fluorine-containing surfactants and other fluorine-containing fine chemicals as a key intermediate.
Description
Technical field
The present invention relates to the preparation method of chloro-2, the 2-difluoroethylenes of a kind of 1-, especially relate to two trifluorotrichloroethanes for the method for chloro-2, the 2-difluoroethylenes of 1-prepared by raw material.
Background technology
Trifluorobichloroethane (HCFC-123) is a kind of novel refrigerant, in its production process, have a certain amount of two trifluorotrichloroethanes (HCFC-122) by product generate, through product rectification and purification, the HCFC-122 by product that purity is greater than 95% can be obtained.At present HCFC-122 by product mainly being adopted to the method process of burning, is a kind of waste from utilization of resources angle.
Chloro-2, the 2-difluoroethylenes of 1-are a kind of important fluorine fine chemical materials, are the key intermediates producing fluorine-contained finishing agent, fluorochemical surfactant and other fluoride-containing PMMA.Can be used for heat exchange material, space flight push agent, whipping agent, solvent, clean-out system, alternative dry drying prescription, rumbling compound, polymerization medium, polyolefine spreading agent, urethane spreading agent, gaseous dielectric, fire-fighting medium etc.
The method of chloro-2, the 2-difluoroethylenes of prior art report preparation 1-mainly contains following two kinds:
(1) two trifluorotrichloroethanes (HCFC-122) are adopted to prepare chloro-2, the 2-difluoroethylenes of 1-for raw material
A kind of preparation method of catalyzer is reported in European patent EP 556893, adopt gac as carrier, loaded metal copper and group VIIIB precious metal element, such as Cu-Pt binary metal obtains a kind of Hydrodechlorinating catalyst, be 1.0MPa at hydrogen pressure, temperature of reaction is adopt this catalyzer under the condition of 240 DEG C, carries out the obtained 1-chloro-2 of hydrodechlorination reaction to two trifluorotrichloroethanes, 2-difluoroethylene, as shown in reaction formula Scheme_1.This technology adopts catalytic hydrogenation and dechlorination catalyzer will adopt group VIIIB precious metal element, and therefore catalyzer cost is higher, in addition under the reaction conditions, chlorine atom in part material is had to be reduced into as hydrogen atom, thus chloro-2, the 2-C2H4F2 C2H4F2s of 1,1-bis-may be produced, 1-chloro-2,2-C2H4F2 C2H4F2, the impurity such as 2,2-C2H4F2 C2H4F2, so not only affect the yield of reaction, bring difficulty also to the purification of product.
(2) bromo-2,2, the 2-Halothane of the chloro-1-of 1-are adopted to be that chloro-2, the 2-difluoroethylenes of 1-prepared by raw material:
Hudlicky, and Lejhancova M., I. report and adopt the chloro-1-of 1-bromo-2,2,2-Halothane is the method that raw material obtains chloro-2, the 2-difluoroethylenes of 1-, and author adopts zinc powder to be raw material, with 1,4-dioxane is solvent, is to react two hours under the condition of 100 DEG C in temperature, obtains 1-chloro-2, the productive rate of 2-difluoroethylene is 71%, as shown in Scheme_2, (reference: Collection of Czechoslovak Chemical Communications, 1965,30 (7), 2491-3.).This technology subject matter is the adopted chloro-1-of raw material 1-bromo-2,2,2-Halothane not easily obtains, and the yield of this reaction is not high, solvent Isosorbide-5-Nitrae-dioxane the consumption used in reaction process is also very large, and these unfavorable factors all affect 1-chloro-2,2-difluoroethylene production cost, this synthetic route is not suitable for suitability for industrialized production.
Zinc powder is adopted to be that reductive agent carries out the method that dechlorination reaction prepares similar Fluorine containing olefine and has following several in prior art:
(1) people such as Edward G.Locke (reference: Edward G.Locke, Wallace R B, Albert L H. is once at J.Am.Chem.Soc., 1934,56 (8), 1726 – 1728.) employing zinc powder is reductive agent, methyl alcohol is solvent, with 1,1,1-tri-chloro-2,2-C2H4F2 C2H4F2 is raw material, under temperature is 60 ~ 63 DEG C of reaction conditionss, carries out reduction dechlorination prepares chloro-2, the 2-difluoroethylenes of 1,1-bis-; J.C.Sauer is optimized and improves (reference: J.C.Sauer.Org.Synth., 1963, Coll.Vol.4 to above-mentioned reaction, 268), add a small amount of zinc chloride in the starting stage of reaction, make the yield of this reaction bring up to 89% ~ 95%, as shown in Scheme_3.
(2) people such as M.S.Raasch and Maynard S.Raasch adopts zinc powder to be reductive agent, ethanol is solvent, with 1, and 1,2-tri-chloro-2,3,3-trifluoro tetramethylene is raw material, and under heated reflux condition, reaction is carried out reduction dechlorination for 1 hour and prepared 1-chloro-2,3,3-trifluoro cyclobutene, yield about 70%, as shown in Scheme_4.(reference: M.S.Raasch and J.E.Castle.Org.Synth.1973, Coll.Vol.5,393.Maynard S.Raasch, Ralph E.Miegel, John E.Castle, J.Am.Chem.Soc., 1959,81 (11), 2678 – 2680).
In sum, existing preparation 1-chloro-2, there is expensive catalyst in the method for 2-difluoroethylene, reaction preference is poor, or expensive raw material price, cost are high, reaction solvent consumption is large, produce the series of problems such as a large amount of three wastes in the low or reaction process of product yield, cause the suitability for industrialized production being difficult to realize chloro-2, the 2-difluoroethylenes of 1-.Therefore, find one simple to operate, the synthetic route that environment amenable Suitable commercial amplifies chloro-2, the 2-difluoroethylenes of 1-produced is engaged in task and the challenge of organic fluorine chemistry technician.
Summary of the invention
A kind of employing HCFC-122 is the object of the present invention is to provide to be that 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, have that raw materials cost is low, simple to operate, reaction temperature and, speed of response is fast, productive rate is high, cost is low, selectivity is high and advantages of environment protection, can be used for suitability for industrialized production.
For achieving the above object, the present inventor is reductive agent to adopting zinc powder in prior art, carries out the method that reduction dechlorination reaction prepares alkene and conducts in-depth research:
The technology of alkene is prepared with reference to existing zinc powder reduction dechlorination reaction, the discarded HCFC-122 in HCFC-123 production process is adopted to be raw material, reductive agent is made with zinc powder, carry out reduction dechlorination reaction preparation 1-chloro-2, 2-difluoroethylene, the solvent adopted has alcohols, ethers, amides, anhydrides, containing oxygen-nitrogen compound and sulfocompound, these solvents specifically comprise: methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, glycerine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF), 1, 4-dioxane, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, diacetyl oxide, acetone, acetonitrile, morpholine, N-methylmorpholine, dimethyl sulfoxide (DMSO), tetramethylene sulfone etc., temperature of reaction is 50 ~ 200 DEG C, reaction times reaches 20 ~ 120 hours.Found through experiments and adopt zinc powder to be reductive agent, carry out reduction dechlorination reaction and can prepare 1-chloro-2,2-difluoroethylene, but the productive rate of reaction is very low only has 20 ~ 50%, contriver has carried out a large amount of experiments and improvement to this preparation method, particularly carried out screening widely to solvent, temperature of reaction and reaction times, find that the productive rate of this reaction is not significantly improved, this technology does not have industrialized value.
Contriver finds that there is most HCFC-122 raw material in experimentation and zinc powder does not react, and this is the major cause causing productive rate low, and in reaction system, remaining zinc powder affects recovery and the purification of zinc chloride in post-reaction treatment process.Contriver adds a small amount of zinc chloride with reference to prior art in the reaction starting stage, finds that the productive rate of this reaction is not also significantly improved.But the present inventor adds a kind of reaction promoter through test repeatedly and exploration discovery in reaction system, such as: V-Brite B, iodine, 1,2-ethylene dibromide, Diisopropyl azodicarboxylate (AIBN), dibenzoyl peroxide (BPO) etc., these materials significantly can reduce the content of HCFC-122 raw material and zinc powder in reaction system, and the reaction times is also shortened greatly, the 1-chloro-2 of gained, 2-difluoroethylene yield significantly improves, and the efficiency of reaction also improves.And find that reaction promoter only needs to add on a small quantity through exploratory experiment, therefore the increase of cost is not almost affected.
The technical scheme adopted for reaching the object of the invention is:
A kind of with two trifluorotrichloroethanes for 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, in the presence of solvent, under the effect of reaction promoter, two trifluorotrichloroethanes (HCFC-122) and the reaction of zinc powder generation reduction dechlorination generate 1-chloro-2,2-difluoroethylene, described reaction promoter is selected from one or more combinations in V-Brite B, iodine, glycol dibromide, Diisopropyl azodicarboxylate or dibenzoyl peroxide.
In technical scheme of the present invention, reaction promoter V-Brite B, iodine, 1, the add-on of 2-ethylene dibromide, Diisopropyl azodicarboxylate or dibenzoyl peroxide only needs on a small quantity, as preferred embodiment, the mol ratio of described reaction promoter and two trifluorotrichloroethanes is 0.01 ~ 0.2:1; As further preferred embodiment, the mol ratio of described reaction promoter and two trifluorotrichloroethanes is 0.01 ~ 0.06:1.
In the present invention, the mol ratio of described zinc powder and two trifluorotrichloroethanes is preferably 0.8 ~ 3.0:1, more preferably 0.8 ~ 1.5:1.
The present invention use solvent is preferably alcohols, amides, ethers, anhydrides, containing oxygen-nitrogen compound or sulfocompound, described alcohols is preferably methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol or glycerine; Described amides is preferably DMF or N,N-dimethylacetamide; Described ethers is preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF) or Isosorbide-5-Nitrae-dioxane; Described anhydrides is preferably diacetyl oxide; Described oxygen-the nitrogen compound that contains is preferably acetone, acetonitrile, morpholine or N-methylmorpholine; Described sulfocompound is preferably dimethyl sulfoxide (DMSO) or tetramethylene sulfone.
The volume ratio of solvent of the present invention and two trifluorotrichloroethanes is preferably 10 ~ 1:1, more preferably 2 ~ 5:1.
The purity requirement of the present invention to raw material two trifluorotrichloroethane is not too high, and directly can use the by product HCFC-122 produced in HCFC-123 production process, the content of general HCFC-122 is more than 60%.
In the present invention, temperature of reaction is preferably 50 ~ 200 DEG C, more preferably 80 ~ 160 DEG C.Reaction times is preferably 5 ~ 10 hours.
The zinc powder that the present invention uses, before the reaction preferably in advance through activation treatment, comprises the steps:
(1) a certain amount of zinc powder is stirred together with dilute hydrochloric acid, filter to remove disacidify, zinc powder is placed in beaker, first wash once with dilute hydrochloric acid, then use distilled water wash three times, then use 95% washing with alcohol twice, finally wash once with anhydrous diethyl ether, all filter after each washing to remove washings, such zinc powder, just by finish-drying, has block then to grind in mortar;
(2) zinc powder after step (1) being processed stirs in 10% hydrochloric acid, and filter, first wash zinc powder with water, then use washing with acetone, the zinc powder after process is for subsequent use.
The building method of reaction unit of the present invention and product collection device is as follows:
The reaction flask that mechanical stirrer, constant pressure funnel are housed accesses two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Wherein adopt outside the condensation of refrigerator circulation alcohol at second stage reflux condensing tube, also can adopt current laboratory and industrial other conventional refrigerant, such as: chilled brine.And outside-50 ~-60 DEG C of raw spirit freeze cycle adopted when collecting product, also can adopt at present known by the technical staff other refrigerant or collection and confinement of gases technology, such as: adopt dry ice-propanone, the freezing collection product of dry ice-ethanol, or employing airbag, product collected by gas holder, or adopts compressor to collect in the gas press-in steel cylinder generated.
Present invention also offers the rectification and purification method of chloro-2, the 2-difluoroethylenes of a kind of product 1-:
Adopt autoclave rectifying, wherein the condition of compression rectification is: the distillation temperature of autoclave is preferably 0 DEG C ~ 80 DEG C, more preferably 10 ~ 65 DEG C, pressure is preferably 0.2-1.8MPa, more preferably 0.2 ~ 1.3MPa, sterling is obtained after rectifying, GC purity is greater than 98%, productive rate 60% ~ 90%, and the product obtained is through GC-MS, NMR Structural Identification is chloro-2, the 2-difluoroethylenes of 1-.
The present invention still further provides the recycling of reaction solvent and the recovery method of purification of zinc chloride:
For liquid when waste liquid is released from reactor, be mashed prod after cooling, main component is zinc chloride, and the solvent containing about 31%, a small amount of zinc powder and other metallic impurity ion, be made into neutral solution by this mashed prod dilute hydrochloric acid.Elimination insolubles, the solution EDTA obtained measures zinc ion concentration, surveys the concentration of other metal ion with atomic absorption spectrum.For composition and the environmental requirement of waste liquid, first desolventizing will be removed.Again by ordinary method removing iron ion and heavy metal ion, the solder(ing)acid after being purified.Zinc chloride scavenging solution evaporate to dryness can be obtained Zinc chloride solid.Also zinc chloride can be further converted to other zinc salt, react, can obtain zinc hydroxide with ammoniacal liquor and liquor zinci chloridi, react can obtain zinc subcarbonate with sodium bicarbonate and liquor zinci chloridi, pyrolytic decomposition zinc hydroxide or zinc subcarbonate can obtain zinc oxide.
The present invention compared to existing technology tool has the following advantages:
(1) low, simple to operate, the reaction temperature of raw materials cost and, speed of response is fast, productive rate is high, cost is low, selectivity is high and environmental friendliness, can be used for suitability for industrialized production;
(2) recycle and reuse of solvent, reduces costs;
(3) obtain qualified Zinc Chloride Anhydrous, can use as product;
(4) the by product HCFC-122 utilizing HCFC-123 to produce rationally transforms into chloro-2, the 2-difluoroethylenes of value product 1-, and the HCFC-122 by product originally burnt is converted into value product.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that all alternativess, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
Below in an example, the structural formula of compound is determined by nucleus magnetic resonance (NMR) or mass spectrum (MS).NMR displacement (δ) provides with the unit of 1,000,000/(ppm).The mensuration of NMR adopts Varian 400MHz nuclear magnetic resonance spectrometer.The mensuration solvent of NMR is deuterochloroform (CDCl
3), TMS as interior mark,
19f NMR calibrates as fluoroform (CFCl
3),
13c NMR calibrates as deuterochloroform (CDCl
3, 77.00ppm), chemical shift is with 10
-6(ppm) provide as unit.
Reacting all liquid starting materials and product adopts gas-chromatography to carry out quantitative analysis, adopts GC-MS to carry out qualitative analysis.Gas chromatographicanalyzer device is: gas chromatograph GC-2010, SHIMADZU.
GC-MS qualitative analysis adopts Voyager mass spectrograph _ Trace 2000 gas chromatograph for determination.
The pre-treatment of embodiment 1 zinc powder
1 hour is stirred together with 3L 2% hydrochloric acid with 1.2kg zinc powder, filter to remove disacidify, zinc powder is placed in 5L beaker, first use 3L 2% salt acid elution once, then distilled water wash three times (at every turn using 3L) is used, use 95% washing with alcohol twice (at every turn using 2L) again, finally wash once with 2L anhydrous diethyl ether.All washings is filtered away after each washing.Zinc powder after process finish-drying under nitrogen protection, has block then to grind in mortar.Obtain zinc powder after treatment for subsequent use under nitrogen protection.
Embodiment 2
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of tetramethylene sulfone (industrial goods under nitrogen protection, Liaoyang Guanghua Chemical Co., Ltd.), the zinc powder activated 113 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 3.0 grams of V-Brite Bs, 160 DEG C of reactions, 290g bis-trifluorotrichloroethane (HCFC-122 is instilled in 2 hours, GC purity is greater than 95%), and continue reaction 3 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 60 DEG C ~ 65 DEG C, pressure is 1.1 ~ 1.3MPa, 1 is obtained after rectifying, 1-bis-fluoro-2-vinylchlorid 12g, GC purity is greater than 98%, productive rate 75%.The product obtained is chloro-2, the 2-difluoroethylenes of 1-through GC-MS, NMR Structural Identification.
MS(M
r＝98.1),m/z(％relative intensity)，EI:48.2(43),50.2(23),63.2(49),67.1(23),69.1(8)，79.1(22)，81.1(8)，98.1(100)，100.1(78).
1H NMR(400MHz,CDCl
3):5.295(dd,J
1＝17.2Hz，J
2＝1.2Hz)ppm.
19F NMR(376.4MHz,CDCl
3):-86.836(dd,J
HF＝19.2Hz，J
HF＝42.7Hz),-91.084(d,J
HF＝42.9Hz，)ppm.
Embodiment 3
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 2 liter 1 under nitrogen protection, 4-dioxane (Chinese 5-linked chemical plant), the zinc powder activated 325 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 15 grams of V-Brite Bs, 100 DEG C of reactions, 580g bis-trifluorotrichloroethane (HCFC-122 is instilled in 4 hours, GC purity is greater than 95%), and continue reaction 4 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of compression rectification still is 30 DEG C ~ 33 DEG C, pressure is 0.4 ~ 0.5MPa, 1-chloro-2 is obtained after rectifying, 2-difluoroethylene 286g, GC purity is greater than 98%, productive rate 85%.
Embodiment 4
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of N under nitrogen protection, N-N,N-DIMETHYLACETAMIDE (analytical pure, Hangzhou Hui Pu Chemical Co., Ltd.), the zinc powder activated 130 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 21 grams of dibenzoyl peroxide (BPO), 80 DEG C of reactions, 300g bis-trifluorotrichloroethane (HCFC-122 is instilled in 2 hours, GC purity is greater than 95%), and continue reaction 2 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of compression rectification still is 20 DEG C ~ 23 DEG C, pressure is 0.3 ~ 0.5MPa, 1-chloro-2 is obtained after rectifying, 2-difluoroethylene 153g, GC purity is greater than 98%, productive rate 88%.
Embodiment 5
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of methyl alcohol (analytical pure under nitrogen protection, Shanghai Ling Feng chemistry chemical reagent company limited), the zinc powder activated 143 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 18 gram 1, 2-ethylene dibromide, reflux, temperature of reaction (70 DEG C), 330g bis-trifluorotrichloroethane (HCFC-122 is instilled in 2 hours, GC purity is greater than 95%, Sinochem Lantian Co., Ltd. produces the by product of HCFC-123), and continue reaction 6 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 30 DEG C ~ 33 DEG C, pressure is 0.4 ~ 0.5MPa, 1-chloro-2 is obtained after rectifying, 2-difluoroethylene 172g, GC purity is greater than 98%, productive rate 90%.
Embodiment 6
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of morpholine (analytical pure under nitrogen protection, Shanghai Ling Feng chemical reagent company limited), the zinc powder activated 103 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited), in 120 DEG C of reactions, mixture (the HCFC-122 of 10 grams of Diisopropyl azodicarboxylates and 340g bis-trifluorotrichloroethane is instilled in 2 hours, GC purity is greater than 95%), and continue reaction 5 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 30 DEG C ~ 33 DEG C, pressure is 0.4 ~ 0.5MPa, 1-chloro-2 is obtained after rectifying, 2-difluoroethylene 140g, GC purity is greater than 98%, productive rate 90%.
Embodiment 7
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of diglyme (analytical pure under nitrogen protection, Chemical Reagent Co., Ltd., Sinopharm Group) and zinc powder 213 grams of (analytical pure of activating, Shanghai Shen Xiang chemical reagent company limited), in 90 DEG C of reactions, mixture (the HCFC-122 of 25 grams of iodine and 630g bis-trifluorotrichloroethane is instilled in 3 hours, GC purity is greater than 95%), and continue reaction 3 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 30 DEG C ~ 33 DEG C, pressure is 0.4 ~ 0.5MPa, 1-chloro-2 is obtained after rectifying, 2-difluoroethylene 291g, GC purity is greater than 98%, productive rate 92%.
Embodiment 8
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 2 liters of dehydrated alcohol (analytical pure under nitrogen protection, Hangzhou China Long March chemical reagent company limited) and zinc powder 230 grams of (analytical pure of activating, Shanghai Shen Xiang chemical reagent company limited), reflux, temperature of reaction (80 DEG C), 18 grams of Diisopropyl azodicarboxylates and 580g bis-trifluorotrichloroethane (HCFC-122 is instilled in 3 hours, GC purity about 70%), and continue reaction 5 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 10 DEG C ~ 13 DEG C, pressure is 0.2 ~ 0.4MPa, 1-chloro-2 is obtained after rectifying, 2-difluoroethylene 303g, GC purity is greater than 98%, productive rate 90%.
Embodiment 9
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 2 liters of dehydrated alcohol (analytical pure under nitrogen protection, Hangzhou China Long March chemical reagent company limited), the zinc powder activated 230 grams of (analytical pure, Shanghai Shen Xiang chemical reagent company limited) and 15 grams of V-Brite Bs, reflux, temperature of reaction (80 DEG C), 830g bis-trifluorotrichloroethane (HCFC-122 is instilled in 3 hours, GC purity about 70%), and continue reaction 5 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 10 DEG C ~ 13 DEG C, pressure is 0.2 ~ 0.4MPa, 1 is obtained after rectifying, 1-bis-fluoro-2-vinylchlorid 287g, GC purity is greater than 98%, productive rate 85%.
Comparative example 1
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of tetramethylene sulfone (industrial goods under nitrogen protection, Liaoyang Guanghua Chemical Co., Ltd.) and zinc powder 113 grams of (analytical pure of activating, Shanghai Shen Xiang chemical reagent company limited), 160 DEG C of reactions, 290g bis-trifluorotrichloroethane (HCFC-122 is instilled in 2 hours, GC purity is greater than 95%), and continue reaction 6 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 60 DEG C ~ 65 DEG C, pressure is 1.1 ~ 1.3MPa, 1 is obtained after rectifying, 1-bis-fluoro-2-vinylchlorid 67g, GC purity is greater than 98%, productive rate 40%.
Comparative example 2
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 2 liters of dehydrated alcohol (analytical pure under nitrogen protection, Hangzhou China Long March chemical reagent company limited) and zinc powder 230 grams of (analytical pure of activating, Shanghai Shen Xiang chemical reagent company limited), reflux, temperature of reaction (80 DEG C), 580g bis-trifluorotrichloroethane (HCFC-122 is instilled in 3 hours, GC purity about 70%), and continue reaction 8 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 10 DEG C ~ 13 DEG C, pressure is 0.2 ~ 0.4MPa, 1 is obtained after rectifying, 1-bis-fluoro-2-vinylchlorid 185g, GC purity is greater than 98%, productive rate 55%.
Comparative example 3
5 liters of there-necked flasks that mechanical stirrer, constant pressure funnel are housed access two-stage reflux condensing tube, wherein first step reflux condensing tube adopts tap water cooling, second stage reflux condensing tube adopts the condensation of refrigerator circulation alcohol, control the temperature of alcohol at-10 ~-20 DEG C, the product generated is derived through reflux condensing tube and is adopted the cooling of refrigerator circulation raw spirit product-collecting in steel cylinder, and the temperature of control raw spirit is at-50 ~-60 DEG C.Adopt oil bath reacting by heating bottle, adopt electronic temperature controller to control temperature of reaction.
Said apparatus is carried out nitrogen replacement, add 1 liter of methyl alcohol (analytical pure under nitrogen protection, Shanghai Ling Feng chemistry chemical reagent company limited) and zinc powder 143 grams of (analytical pure of activating, Shanghai Shen Xiang chemical reagent company limited), reflux, temperature of reaction (70 DEG C), 330g bis-trifluorotrichloroethane (HCFC-122 is instilled in 3 hours, GC purity is greater than 95%), and continue reaction 24 hours, thick product-collecting is in steel cylinder, adopt 1.0 liters of autoclave rectifying, wherein the condition of compression rectification is: the temperature of autoclave is 30 DEG C ~ 33 DEG C, pressure is 0.4 ~ 0.5MPa, 1 is obtained after rectifying, 1-bis-fluoro-2-vinylchlorid 81g, GC purity is greater than 98%, productive rate 42%.
Claims (10)
1. one kind with two trifluorotrichloroethanes for 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, it is characterized in that in the presence of solvent, under the effect of reaction promoter, two trifluorotrichloroethanes (R122) and the reaction of zinc powder generation reduction dechlorination generate 1-chloro-2,2-difluoroethylene, described reaction promoter is selected from one or more combinations in V-Brite B, iodine, glycol dibromide, Diisopropyl azodicarboxylate or dibenzoyl peroxide.
2. according to according to claim 1 with two trifluorotrichloroethanes for 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, it is characterized in that the mol ratio of described reaction promoter and two trifluorotrichloroethanes is 0.01 ~ 0.2:1, the mol ratio of described zinc powder and two trifluorotrichloroethanes is 0.8 ~ 3.0:1.
3. prepare 1-chloro-2 according to according to claim 2 with two trifluorotrichloroethanes, the method of 2-difluoroethylene, it is characterized in that the mol ratio of described reaction promoter and two trifluorotrichloroethanes is 0.01 ~ 0.06:1, the mol ratio of described zinc powder and two trifluorotrichloroethanes is 0.8 ~ 1.5:1.
4. according to according to claim 1 with two trifluorotrichloroethanes for 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, it is characterized in that described solvent is alcohols, amides, ethers, anhydrides, containing oxygen-nitrogen compound or sulfocompound, the volume ratio of described solvent and two trifluorotrichloroethanes is 10 ~ 1:1.
5. according to according to claim 4 with two trifluorotrichloroethanes for 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, it is characterized in that described alcohols is selected from methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol or glycerine, described amides is N, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE, described ethers is selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, diglyme, diethyl carbitol, tetrahydrofuran (THF) or 1, 4 dioxane, described anhydrides is diacetyl oxide, described oxygen-the nitrogen compound that contains is selected from acetone, acetonitrile, morpholine or N-methylmorpholine, described sulfocompound is selected from dimethyl sulfoxide (DMSO) or tetramethylene sulfone, the volume ratio of described solvent and two trifluorotrichloroethanes is 2 ~ 5:1.
6. according to according to claim 1 with two trifluorotrichloroethanes for the method for chloro-2, the 2-difluoroethylenes of 1-prepared by raw material, it is characterized in that temperature of reaction is 50 ~ 200 DEG C, the reaction times is 5 ~ 10 hours.
7. according to according to claim 1 with two trifluorotrichloroethanes for the method for chloro-2, the 2-difluoroethylenes of 1-prepared by raw material, it is characterized in that temperature of reaction is 80 ~ 160 DEG C.
8. according to according to claim 1 with two trifluorotrichloroethanes for 1-chloro-2 prepared by raw material, the method of 2-difluoroethylene, is characterized in that adopting pressure distillation to purify to chloro-2, the 2-difluoroethylenes of 1-, pressure distillation temperature is 0 ~ 80 DEG C, and pressure is 0.2 ~ 1.8MPa.
9. according to according to claim 8 with two trifluorotrichloroethanes for the method for chloro-2, the 2-difluoroethylenes of 1-prepared by raw material, it is characterized in that described pressure distillation temperature is 10 ~ 65 DEG C, pressure is 0.2 ~ 1.3MPa.
10. according to according to claim 1 with two trifluorotrichloroethanes for the method for chloro-2, the 2-difluoroethylenes of 1-prepared by raw material, it is characterized in that zinc powder before reactions through acid activation process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0556893A1 (en) * | 1992-02-17 | 1993-08-25 | SOLVAY (Société Anonyme) | Process for the preparation of 1,1-difluoro-2-chloroethylene from 1,1-difluoro-1,2,2-trichloroethane |
| CN1986512A (en) * | 2005-12-22 | 2007-06-27 | 索尔维索莱克西斯公司 | Process for preparing fluorohalogenethers |
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| US7723552B2 (en) * | 2008-08-08 | 2010-05-25 | Honeywell International Inc. | Process for making chlorotrifluoroethylene from 1,1,2-Trichlorotrifluoroethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0556893A1 (en) * | 1992-02-17 | 1993-08-25 | SOLVAY (Société Anonyme) | Process for the preparation of 1,1-difluoro-2-chloroethylene from 1,1-difluoro-1,2,2-trichloroethane |
| CN1986512A (en) * | 2005-12-22 | 2007-06-27 | 索尔维索莱克西斯公司 | Process for preparing fluorohalogenethers |
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