CN1212679A - Process for producing 1,1-difluoroethane - Google Patents

Abstract

This invention is a process for the selective and high yield preparation of 1,1-difluoroethane (CHF2-CH3, HFC-152a) from chloroethene while minimizing formation of oligomeric and polymeric byproducts. This process comprises providing a liquid phase mixture containing chloroethene, HF, a tin catalyst, and one or a combination of compounds from the families of oxygen, nitrogen, and phosphorus-containing organic compounds, heating the mixture, and isolating the HFC-152a formed.

Description

1, the production method of 1-C2H4F2 C2H4F2

Invention field

The present invention relates to prepare 1 optionally and with high yield, the method for 1-C2H4F2 C2H4F2 and more particularly, this method that relates to comprise vinylchlorid and hydrogen fluoride in liquid phase, simultaneously at tin catalyst with contain in the presence of the additive of oxygen, nitrogen or phosphorus and react.

Background of invention

Komatsu etc. are at United States Patent (USP) 4, in 766,258, the method for a kind of production hydrofluoric ether (HFCs) and chlorine hydrofluoric ether (HCFCs) is disclosed, this method is included in tin catalyst and a kind of additive that contains oxygen or nitrogen compound that is selected from exists down, makes hydrochloric ether (HCCs) and hydrogen fluoride (HF) reaction.In most of the cases, embodiment shows that additive has reduced the activity of tin catalyst, thereby has reduced the efficient that this method forms the useful yield of higher hydrofluoric ether.

Komatsu etc. disclose the method for a kind of HFCs of production and HCFCs in Japanese publication clear 62 (1987)-246528, it is characterized in that the reaction product of conjugate base, tin catalyst and the HF of HF exists down, and hydrogeneous halohydrocarbon and HF are reacted in liquid phase.Komatsu proposes vinyl trichloride and HF are reacted in the presence of tin tetrachloride and Sodium Fluoride in an independent embodiment of this invention.Interrupter method is adopted in reaction, carries out 3 hours under 90-98 ℃ and 980kPa, and the reinforced mol ratio of reactant is vinyl trichloride (16.7): HF (33.3): SnCl ₄(1.0): NaF (1.0).Isolating in this embodiment product mixtures is 32% (weight) 1,2-two chloro-1-fluoroethanes (HCFC-141), and 1%1-chloro-1,2-C2H4F2 C2H4F2 (HCFC-142a) and 67% parent material (vinyl trichloride) that reclaims are not observed dimer.Based on this independent embodiment, all additives of discussing in this publication, these additives also are used for being concluded the benefit that provides similar in the same quadrat method of the United States Patent (USP) 4,766,258 that these same authors publish.

Franklin etc. are at United States Patent (USP) 4,968, in 850, disclose the method for a kind of HFCs of preparation and HCFCs, and this method is included under the existence of tin catalyst and organophosphorus additive unsaturated HCC and HF are reacted in liquid phase.These additives are described to help the carrying out of halogen exchange process, comprising the stability that increases the active of catalyst system therefor and/or improvement additive, and form less oligopolymer, valuable product selectivity height.But although reduced the amount that oligopolymer forms, embodiment shows that the selectivity that forms higher hydrofluoric ether in its method has reduced or can having ignored the variation of mode.

1,1-C2H4F2 C2H4F2, this paper are called HFC-152a or 152a, are the very wide compounds of a kind of application.It both can use separately also and can use as refrigeration agent, whipping agent, propelling agent, clean-out system or as other fluorocarbons, as the intermediate of vinyl fluoride with the other materials blending.HFCs such as HFC-152a are the surrogates of Chlorofluorocarbons (CFCs) (CFCs) environmentally compatible, because do not find that also they are influential to the stratospheric ozone of the earth.

Find to have the wide industrial meaning by HCCs and HF by the method that metal intervention halogen exchange prepares HFCs and HCFCs.Total process is that the C-Cl key of HCC disconnects, and forms the C-F key in position.The katalysis of metal is to make the exchange process that requires mild reaction conditions obtain higher productivity.HFC-152a produces with the liquid and gas method by this way.The method for making of the HFC-152a that document is revealed is in the presence of the salt of the metal of various oxidations such as tin (IV), titanium (IV), antimony (III) and antimony (V), makes vinylchlorid and HF reaction.

In the ordinary method by vinyl chloride production HFC-152a, intermediate product contains and comprises 1-chloro-1-fluoroethane (HCFC-151a or 151a) and 1,1-ethylene dichloride (HCC-150a or 150a).The by product of this ordinary method comprises various oligomeric and polymeric materials: to the high-molecular weight halogenated polymer, the form of being got is the carbon solid of oily matter, tar and black from low-molecular-weight halogenation dimer and oligomer.These by products are higher molecular weight normally, and for example, the standard weights score distribution of number-average molecular weight is 2,000-75,000 but be main with 50,000, branching, the polymeric halohydrocarbon, if wherein exist, can contain metal object from catalyzer and other additives.These higher molecular weight materials can form by low-molecular-weight dimer, tripolymer and oligomer and himself or with halogenated carbonaceous agent and their the adducts polymerization of fluoridizing.These by products are unfavorable to exchange process, because they influence activity of such catalysts, reduce the volume of reactor, reduce the yield of HFC-152a, and are difficult to dispose.

The modification of the compound that metal catalyst can react by adding fluoridizing inertia but with the metal object among the HF can cause catalyzer to have the performance different with its parent.Exchange process ideal additive requires the by product of formation minimum, can improve speed of reaction and increase simultaneously to required product selectivity.

So the ordinary method of preparation HFC-152a is worthless because produce a large amount of tar.Method of the present invention has solved this problem in the ordinary method by the formation speed that reduces tar.

Summary of the invention

The present invention is a kind of optionally by vinyl chloride production HFC-152a, and oligomeric and polymeric by product forms minimum method simultaneously.This method comprises provides one to contain vinylchlorid, HF, at least a tin catalyst and at least a liquid phase mixture that is selected from the compound of the compound that contains oxygen, nitrogen or phosphorus; The heating said mixture; With the HFC-152a that separates formation.

Reactive component can any order be added in the reactor, but the preferred additive that in reactor, at first adds tin catalyst, HF and contain oxygen, nitrogen or phosphorus.The temperature of this mixture remains on 20-160 ℃ between the reaction period.During this, add vinylchlorid, and under reaction conditions, be transformed into 1-chloro-1-fluoroethane (HCFC-151a).This HCFC-151a carries out the exchange of fluoro-chlorine halogen then under reaction conditions, product HFC-152a steams from reaction mixture.

Method of the present invention can be operated with interrupter method.Preferably with continuous processing operation, comprise in reactor successive adding HF, tin catalyst and contain the additive and the vinylchlorid of oxygen, nitrogen or phosphorus, follow simultaneously and remove HFC-152a and HCl.The analysis revealed of this method, vinylchlorid are high and have a selectivity to the transformation efficiency of HFC-152a, and be oligomeric simultaneously and the polymeric by product is minimum.

The accompanying drawing summary

Fig. 1 is the synoptic diagram that continuous processing is produced HFC-152a.

Detailed Description Of The Invention

The present invention be a kind of selective and with high yield by the synthetic HFC-152a of vinyl chloride simultaneously accessory substance form minimum method. This method comprises provides a kind of vinyl chloride, HF, at least a tin catalyst and at least a liquid phase mixture that is selected from the compound that contains oxygen, nitrogen or phosphorus compound of containing, and heats this mixture, with the HFC-152a that separates formation. What this research obtained the results are shown in the table 1, and the result showed in being synthesized in the HFC-152a method with the benefit that contains oxygen, nitrogen or phosphorus compound by vinyl chloride and HF that tin (IV) is got involved. Cause forming HFC-152a optionally obviously increasing than HCFC-151a with method of the present invention; Increase HFC-152a by the molar yield of vinyl chloride and reduced amount oligomeric and accessory substance polymerization.

Table 1 combines in being synthesized by vinyl chloride and HF of tin (IV) intervention and uses at least a typical consequence that oxygen, nitrogen or compounds of phosphorus obtain that contains in the HFC-152a method. Keep every other technological parameter constant and the mol ratio of nitrogenous additive and tin catalyst is increased to 6 until add nitrogen-containing compound fully from 0, cause that product HFC-152a/HCFC-151a mol ratio correspondingly increases, this increase is with the amount of used nitrogenous additive and precise chemical structure composition and nonlinear variation. In addition, this nitrogenous additive is to the increase of tin catalyst mol ratio, in all cases, all is accompanied by the minimizing of accessory substance mass percent of formation and/or the increase of HFC-152a molar yield. Also find, synthesize application oxygenated additive such as ethanol (C in the HFC-152a method what tin (IV) was got involved by vinyl chloride and HF₂H ₅Or phosphor-included additive such as triethyl phosphite (PO (C OH),₂H ₅) ₃) can obtain same benefit. Increase the selective of HFC-152a and increase yield (reducing the formation of tar), and the synergy of using the possibility of various additive causes forming a valuable technique.

The tin catalyst that is used for the inventive method is the compound that is selected from tin halide, tin oxyhalogenation thing and organic tin family. In three compounds, tin halide preferably, in tin halide, stannic chloride (IV) (SnCl₄) be most preferred. Other available tin halides (IV) comprise SnBr₄And SnCl₃F、SnCl ₂F ₂、SnClF ₃And SnF₄Series, this serial compound is to allow SnCl₄Produce with HF reaction. In tin oxyhalogenation thing such as SnCl₂O、SnF ₂The compound of O and SnClFO is available. From viewpoint of the present invention, organotin is that tin atom is bonded to one to the compound of four carbon atom. Organo-tin compound such as tetramethyl tin (Sn (CH₃) ₄), oxygen tin diethyl (OSn (C₂H ₅) ₂) and dimethyl tin dichloride (SnCl₂(CH ₃) ₂) be that the inventive method can be used.

The following additive that contains oxygen, nitrogen and phosphorus can use separately in the method for the invention or use with the form of any composition or mixture.Nitrogenous compound of the present invention is ammonia (NH ₃) and nitrogenous primary, second month in a season and uncle's organic compound such as amine.The example of available amine comprises heterocyclic amine such as pyridine, 2-picoline; Saturated and undersaturated aliphatic amine such as Trimethylamine 99, triethylamine, sec-butylamine, hexanediamine; Arylamine such as aniline, Tolylamine; And trolamine, wherein alkyl amine such as Trimethylamine 99 and triethylamine are preferred.Can be used for oxygenatedchemicals of the present invention and comprise H ₂O, H ₂O ₂Generate compound and oxygen containing organic compound such as alcohols, ethers, aldehydes, ketone, carboxylic-acid, ester class, sulfone class and the epoxy compounds of oxygen with other.How oxygen containing oxygenatedchemicals can be and also can contain be selected from hydroxyl, carbonyl, carboxyl, ester group, ether and epoxy group(ing) different and contain the oxygen functional group.Preferably containing the oxygen compounds is fatty alcohol such as ethanol.Can be used for P contained compound of the present invention is the compound that is selected from organophosphite, phosphuret-(t)ed hydrogen and phosphoric acid ester.Preferred this compounds is tricresyl phosphite lower alkyl esters such as triethyl-phosphite, trimethyl phosphite, tri-n-butylphosphite and triisopropyl phosphite; With Phenylphosphine such as chlorodiphenyl base phosphine and triphenylphosphine oxide.

The used tin catalyst of the about usually 0.1-1.5 moles/mole of amount that is used for the oxygenated additive of the inventive method.Preferred this method of implementing adopts 0.6-0.9 mole oxygenated additive/mole tin catalyst.The consumption of used nitrogenous additive is generally the used tin catalyst of about 0.1-6.0 moles/mole in the inventive method.Preferred this method of implementing adopts about 0.6-0.9 mole nitrogenous additive/mole tin catalyst.The used tin catalyst of the about usually 0.05-0.5 moles/mole of amount that is used for the phosphor-included additive of the inventive method.Preferred this method of implementing adopts 0.2-0.35 mole phosphor-included additive/mole tin catalyst.

In one aspect of the invention, the additive that contains oxygen, nitrogen or phosphorus that one or more are above-mentioned and tin catalyst can with mix before vinylchlorid contacts.For example, ethanol and SnCl ₄Can pre-mixing formation contain ethanol/SnCl ₄Mixture.Premixed mixture can be used for any suitable intermittence as herein described or continuation method.

In one aspect of the invention, this method is finished with periodical operation.Any suitable autoclave, 450 milliliters of Parr  series 4560 microreactors making as Hastelloy C  all can use.The 0.25 inch cast reflux exchanger of diameter and the indirect heating chuck of the strap clamp cover of sampling valve port is equipped with at valve port, the top that autoclave disposes the turbine high speed agitator of agitated autoclave liquid contents usually, import liquid or extract out barrier film mouth, importing or the withdrawing gas of autoclave or fluent material by syringe or telescopic method.Discontinuous method of the present invention can any desired scale carry out.Equipment and relevant charge line, discharging pipeline and relevant device should be with the material manufacturings of anti-HF and HCl.The well-known typical manufactured materials in fluorination technology field comprises stainless steel and Langaloy, as Monel  nickel-copper alloy, Hastelloy  nickel-base alloy and Inconel  nickel-chromium alloy.

The autoclave of doing is transferred in the dried case at least a tin catalyst, at least a compound that contains oxygen, nitrogen and phosphorus compound that is selected from of adding aequum in the autoclave.Tin catalyst added autoclave normally carries out in dried case, so that reduce any reaction between tin compound and the airborne moisture as far as possible.

With the autoclave sealing, and from dried case, take out.Autoclave outlet links to each other with vacuum pump then, and the bottom places liquid nitrogen to cool off, and autoclave is vacuumized.After autoclave reaches vacuum, removed potential deleterious air, feasible more effectively gas transfer HF.Liquid nitrogen helps to shift HF by the method for condensed gas HF in autoclave.Then autoclave is linked to each other with the HF jar, the HF vacuum transfer of requirement is in autoclave.

Vinylchlorid, HF and the tin catalyst amount in autoclave can change in very wide valid function scope.The used quantity of material of the inventive method is generally about 0.1 to (vinylchlorid that kilogram adds/hour)/kilogram catalyzer at least about 10, when tin catalyst contains SnCl ₄The time, usually about 0.2 (vinylchlorid that kilogram adds/hour)/the kilogram catalyzer.The initial add-on of catalyzer of band HF is generally about 5 at least 35% (weight), for example, and SnCl ₄In HF, the tin catalyst among the HF is about 10-20% (weight) usually.

All add the autoclave of sealing at parent material after, then autoclave and vacuum system and HF source are thrown off, make it be heated to room temperature.Make autoclave be heated to about 20-160 ℃ then, be preferably about 50-95 ℃, the total pressure in the autoclave is maintained at about 60-3000kPa, is preferably about 350kPa.Pressure in the autoclave can keep by any suitable method such as back pressure regulator.

Then gas vinylchlorid is added autoclave, adding speed becomes with the amount of HF in the autoclave and tin catalyst, and for example the speed with about 10-100sccm (about 0.01-0.5 kilogram/hour/kilogram catalyzer) adds vinylchlorid.Collect and the overflow gaseous effluent of the reflux exchanger that is communicated with autoclave fluid of monitoring by condensation.The composition of effluent is monitored with online gas chromatograph (GC).After interpolation vinylchlorid stopped, autoclave was discharged excessive gas and fluent material by nitrogen purging.Take out the solids in the autoclave then, water submergence and filtration.Filtrate is with 10% aqueous hydrochloric acid, water rinse, in vacuum oven to constant weight.Also analyze the amount of the composition of dry thing with definite tar that forms.

Although can be with above-mentioned interrupter method, be particularly preferred from the viewpoint continuous processing of industry.Referring now to Fig. 1,, Fig. 1 is the synoptic diagram of successive HFC-152a working system.Reactor 1 is that fluid is communicated with reflux tower 2.Usually, when working pressure was about 50-150 ℃ for about 340-3000kPa and temperature, the reflux ratio of reflux tower 2 was about 2-20.The HF of predetermined amount (with the ratio of front interrupter method discussion), at least a tin catalyst, at least a compound that is selected from the compound that contains oxygen, nitrogen and phosphorus are added reactor 1.The content of reactor 1 stirs with two paddle stirrers 3 of having the effect of bleeding, heats and refluxes under required service temperature/pressure.After required operational condition reaches, HF and vinylchlorid are added in the reactor continuously via one or several charge line 4.The gas that comes out from reactor 1 enters reflux tower 2 via one or several charge line 5.Leave the gas stream of reflux tower 2 and form by HFC-152a and HCl basically, the HFC-152a of for example about 60-70% (weight).The bottom of reflux tower 2 is connected with liquid return pipeline 6.High boiling intermediate as 1,1 ethylene dichloride and HCFC-151a together with any HF via pipeline 6 Returning reactors.Staying the gas stream of reactor 1 or reflux tower 2 can purify as the distilation steps (not shown in figure 1) with two routines by any suitable manner.First distilation steps is removed HCl.Second distilation steps removed any unreacted intermediate and FCl, and FCl can reclaim, and be also capable of circulation if desired to reactor 1.

As the operation discussion of front interrupter method, the production unit of continuous processing and relevant charge line thereof, effluent pipeline and any treatment unit all should be with the material preparations of anti-HF and HCl.

Though the description of front is lay special stress on and prepares the product logistics that HFC-152a is a main component that the inventive method also can be produced the mode of other required compounds and be operated.That is to say, the inventive method can be produced HFC-152a individually or especially for example be produced one or more HCFC-141b (1,1-two chloro-1-fluoroethanes), HCFC-142b (1-chloro-1 altogether from chloro-hydrocarbons such as vinylidene chloride, the 1-C2H4F2 C2H4F2), HFC-143a (1, the 1-Halothane).The product of producing can reclaim altogether, uses as useful mixture, or is separated into its independent composition.

The embodiment that provides below further sets forth the present invention, is not the restriction to the defined invention of appended claim.In the following embodiments, vinylchlorid is by Fluka limited-liability company, Ronkonkoma, and NY. provides, and (Allentown PA.) provides HF by air products company.The compound of all application all is commercially available among the following embodiment.

Embodiment

Embodiment 1-triethylamine is made additive

With tin tetrachloride (SnCl ₄, 37.5g 0.144mol) is added in 450 milliliters of Parr  series of Hastelly C , 4560 microreactors that are contained in the dried case.The top and the reactor that dispose 0.25 inch cast reflux exchanger are joined, from dried case, take out reactor, link to each other with the stainless-steel vacuum pipeline.Reactor bottom immerses in the liquid nitrogen, and (150g, 7.5mol) vacuum transfer is in reactor with HF.Remove cooled with liquid nitrogen and bathe, use the method for injecting triethylamine (N (C by the barrier film mouth ₂H ₅) ₃, 8.71g 0.861mol) is added in the reactor.With outer heating reactor is heated up, until 25 ℃ of interior Wen Weiyue, water coolant (3.7 ℃) begins to circulate by condenser.Heating jacket is encircled reactor, and temperature rise to 50 ℃ in the reactor is pressed in about 350kPa in keeping with back pressure regulator simultaneously.This moment vinylchlorid (50.1 standard cubic centimeters/minute or sccm, 8.4 * 10 ^-7Cube meter per second) and interior mark methane (9.5sccm, 1.6 * 10 ^-7Cube meter per second) beginning inflow reactor.In the reinforced process of about 17 hours vinylchlorid, gaseous effluent is per hour monitored once.HFC-152a molar yield in adding vinylchlorid is 85% after measured.On-line gas chromatography (GC) analysis finds that HFC-152a is 98% in effluent.The ratio (the 4th to the 17th hour mean value in the experiment) that GC measures HFC-152a/HCFC-151a is 58.Reaction finishes, and volatile matter (HF and organism) is discharged in reactor emptying.Further remove volatile matter by nitrogen purging.Remain in the interior solid immersion of autoclave in water, and on Teflon  PTFE film filter, filter.Filtrate washes with water then with the 10%HCl washing, is dried to constant weight again in vacuum drying oven.The every 100g of the tar that forms in this experiment adds the average 0.36g of vinylchlorid.

Comparative example 1-is additive-free

Used equipment, method and the material of this comparative example basically with front embodiment 1 discussed identical, exception is without the triethylamine additive.Below discussion write down different with the method for embodiment 1 of result that present embodiment obtains.

The on-line gas chromatography analysis finds that HFC-152a is 98% in effluent.The ratio (the 4th to the 17th hour mean value in the experiment) that GC measures HFC-152a/HCFC-151a is 40.After operation 18 hours, reaction finishes, and handles as embodiment 1.The every 100g of the tar that forms in this experiment adds vinylchlorid average out to 2.30g.

Table 1-embodiment 1-15 and comparative example 1-3

The essentially identical method that embodiment 2-13 adopts embodiment 1 to be discussed.Comparative example 2 adopts comparative example 1 essentially identical method.Reaction product and list in table 1 with the processing parameter of the standard method of embodiment change or change.During table 1 below maintenance constant processing parameter is listed in whole experiment is annotated.

Table 1 contains the additive of oxygen, nitrogen or phosphorus

Embodiment a	Additive (used mole number is with the mol ratio of tin catalyst)	Reaction times (hour)	The mole % yield of 152a	152a/151a product mol ratio	Gram tar/100g adds vinylchlorid
						Comparative example 1	Do not have	????18	????85	????40	????2.30
Comparative example 2	Do not have	????16.3	????87	????44	????2.03
						?1	????N(C 2H 5)3(0.86,6.0)	????17	????85	????58	????0.36
?2	N(C 2H 5) 3xHF(0.864,6.0 ????)	????16	????97	????76	????0.45
						?3	N(C 2H 5) 3(0.043,0.30)	????16	????89	????52	????0.57
?4	?N(C 3H 5) 3(0.144,1.0)	????15	????84	????41	????0.29
						?5	2-picoline (2-picoline) (0.086,0.60)	????16	????87	????69	????0.56
?6	?P(OC 2H 5) 3(0.437,3.0)	????16	????84	????50	????0.13
						?7	P(OC 2H 5) 3(0.087,0.60)	????14	????83	????28	????0.05
?8	?C 2H 5OH(0.13,0.90)	????14	????88	????55	????0.14
						?9	Acetone (0.144,1.0)	????16	????87	????63	????0.49
?10	?N(CH 3) 3(0.096,0.67)	????16.5	????89	????75	????0.49
						?11	?N(CH 3) 3(0.144,1.0)	????16.3	????87	????50	????0.30
?12	NH(C 2H 5) 2(0.144,1.0)	????16.5	????90	????66	????0.14
						?13	Tetramethylene sulfone (0.144,1.0)	????15.8	????85	????91	????0.74

Below three embodiment implementing on the big 1.4 times equipment of comparative example 1, comparative example 2 and embodiment 1-13 and under the operational condition in stable state continuously
						14 b	?C 2H 5OH(0.12,0.3)	…	96.7% purity 152a	????44	????4.6
15 b	?C 2H 5OH(0.23,0.6)	…	95.2% purity 152a	????24	????4.6
						Comparative example 3 b	Do not have	…	89.6% purity 152a	????11	????7.1

Table 1 is annotated

A: identical with embodiment 1, embodiment 2-13, comparative example 1 and 0.144 mole of SnCl of comparative example 2 usefulness ₄, 7.5 moles of HF and being reflected under 50 ℃ and the 350kPa carry out.

B: these embodiment are with 0.383 mole of SnCl ₄, 15 moles of HF and being reflected under 80 ℃ carry out.Detailed description referring to following embodiment 14,15 and comparative example 3 processes.

Embodiment 14-ethanol is made additive

With tin tetrachloride (SnCl ₄, 100g, 0.383mol) and Potassium monofluoride (KF, 13.4g 0.230mol) are added in 600 milliliters of Parr  of the HastelloyC  microreactor that is contained in the dried case.Two of reactor head configurations are used for material mouth reinforced or sampling, and one has reflux tower and agitator of collecting effusion steam material mouth.With reactor sealing, the bottom of cooling reactor, and with HF (300g, 15mol) and ethanol subsequently (5.3g 0.12mol) is added in the reactor.The liquid mixture that obtains was kept about 15 hours.Then reactor content is heated to about 80 ℃, stirs and begin to add vinylchlorid.HF is added reactor, add rate adaptation to making the material in the reactor keep the constant gross weight heavy.In case this condition reaches,, can think that process has reached stable state in case the continuous online GC of reflux exchanger effluent analyzes within experimental error.Vinylchlorid feed rate at 19.6g/hr (0.31mol/hr), following stable state result can analyze with the online GC of reflux exchanger effluent and obtain: HFC-152a (is 96.7% by GC peak area integration), vinylchlorid (0.04%), HCFC-151a (2.2%) and 1,1-ethylene dichloride (0.5%).The relative proportion of HFC-152a/HCFC-151a is defined as 44 by GC.

After experiment finished, reaction mixture was with handling as embodiment 1 described method.The every 100g of the tar that forms in this experiment adds vinylchlorid average out to 4.6g.

Embodiment 15-ethanol additive

Used equipment, method and the material of present embodiment basically with front comparative example 14 discussed identical.Below discussion write down different with the method for embodiment 14 of result that present embodiment obtains.The alcoholic acid feeding quantity is 10.6g (0.23mol).Vinylchlorid feed rate at 19.6g/hr (0.31mol/hr), following stable state result can analyze with the online GC of reflux exchanger effluent and obtain: HFC-152a (is 95.2% by GC peak area integration), vinylchlorid (0.0%), HCFC-151a (3.9%) and 1,1-ethylene dichloride (1.0%).The relative proportion of HFC-152a/HCFC-151a is defined as 24 by GC.After experiment finished, reaction mixture was with handling as embodiment 1 described method.The every 100g of the tar that forms in this experiment adds vinylchlorid average out to 4.6g.

Comparative example 3-is additive-free

Present embodiment is except without the ethanol additive, and it is identical that used equipment, method and material and front embodiment 14 are discussed.Below discussion write down different with the method for embodiment 14 of result that present embodiment obtains.

SnCl ₄Feeding quantity be that 140g (0.54mol) is reflected under 76 ℃ and carries out.Vinylchlorid feed rate at 18.2g/hr (0.29mol/hr), following stable state result can analyze with the online GC of reflux exchanger effluent and obtain: HFC-152a (is 89.6% by GC peak area integration), vinylchlorid (0.0%), HCFC-151a (7.8%) and 1,1-ethylene dichloride (2.4%).The relative proportion of HFC-152a/HCFC-151a is defined as 11 by GC.After experiment finished, reaction mixture was with handling as embodiment 1 described method.The every 100g of the tar that forms in this experiment adds vinylchlorid average out to 7.1g.

Claims (11)

1. produce 1 for one kind, the method for 1-C2H4F2 C2H4F2 comprises:

A) provide a kind of liquid phase first kind of mixture, this mixture contains vinylchlorid, hydrogen fluoride, at least a tin catalyst and at least a additive that is selected from the compound that contains oxygen, nitrogen or phosphorus;

B) heating described first kind of mixture and

C) reclaim and to contain 1, second kind of mixture of 1-C2H4F2 C2H4F2, wherein said first kind of mixture do not conform to oligomeric and polymeric compounds on substantially.

2. the described method of claim 1, wherein said tin catalyst contains at least a following compounds: SnCl ₄, SnBr ₄, SnCl ₃F, SnCl ₂F ₂, SnClF ₃, SnF ₄, SnCl ₂O, SnF ₂O, SnClFO, Sn (CH ₃) ₄, OSn (C ₂H ₅) ₂And SnCl ₂(CH ₃) ₂

3. the process of claim 1 wherein that described additive is selected from H ₂O, superoxide, alcohols, ethers, aldehydes, ketone, carboxylic-acid, ester class, sulfone class, epoxy compounds, ammonia, amine, phosphorous acid esters, phosphorus hydrogen type and phosphoric acid ester.

4. the described method of claim 3, wherein said additive is selected from H ₂O, H ₂O ₂, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, tetramethylene sulfone, pyridine, 2-picoline, Trimethylamine 99, triethylamine, tri-isopropyl amine, Tributylamine, sec-butylamine, hexanediamine, aniline, Tolylamine, trolamine, triethyl-phosphite, trimethyl phosphite, tri-n-butylphosphite, triisopropyl phosphite, chlorodiphenyl base phosphine and triphenylphosphine oxide.

5. the described method of claim 1, the mol ratio of wherein said oxygenatedchemicals and described tin catalyst is about 0.1-0.5.

6. the described method of claim 1, the mol ratio of wherein said nitrogenous compound and described tin catalyst is about 0.1-6.

7. the described method of claim 1, the mol ratio of wherein said P contained compound and described tin catalyst is about 0.05-0.5.

8. the described method of claim 1, wherein said heating is carried out under about 2-160 ℃.

9. the described method of claim 1, wherein said method is a continuous processing.

10. the described method of claim 1, wherein said tin catalyst is SnCl ₄And described additive is at least a compound that is selected from ethanol, Trimethylamine 99, triethylamine and triethyl-phosphite.

11. the described method of claim 1 wherein forms oligomeric and polymeric compounds is less than 0.5% (weight) that adds vinylchlorid.

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