CN101495431A - Method for producing fluorinated organic compounds - Google Patents

Abstract

Disclosed is a method for producing fluorinated organic compounds, including hydrofluoropropenes, which preferably comprises converting at least one compound of formula (I): CF3CFnCHmXa-m to at least one compound of formula (II) CF3CZCHZ where each X is independently Cl, I or Br; each Z is independently H or F; n is 1 or 2; m is 1, 2 or 3, provided that when n is 1, m is 1 or 2; a is 2 or 3, and a-m = 0. Certain embodiments include the step of reacting fluorinated C2 olefin, such as tetrafluoroethylene, with a C1 addition agent under conditions effective to produce a compound of formula (I).

Description

The preparation method of fluorinated organic compounds

Background of invention

(1) invention field

The present invention relates to the novel preparation method of fluorinated organic compounds, relate more specifically to the preparation method of fluorinated olefin.

(2) description of Related Art

The hydrogen fluorohydrocarbon (HFC ' s), HF hydrocarbon particularly, for example tetrafluoeopropene (comprises 2,3,3,3-tetrafluoro-1-propylene (HFO-1234yf) and 1,3,3,3-tetrafluoro-1-propylene (HFO-1234ze)) be disclosed as effective refrigeration agent, fire-fighting medium, heat transmission medium, propelling agent, whipping agent, pore forming material, gaseous dielectric, sterilization carrier, polymerisation medium, particulate removal liquid, carrier fluid, polishing abrasive, replace siccative and power cycle working fluid.Be different from chlorofluorocarbon (CFCs) and Hydrochlorofluorocarbons (HCFCs) (both all may destroy the ozonosphere of the earth), HFCs does not conform to chlorine, therefore ozonosphere is not constituted a threat to.

More known prepare the method for hydro fluoroalkanes.For example United States Patent (USP) 4,900, and 874 (Ihara etc.) have described a kind of by making the method for hydrogen and fluorinated alohol contact preparation Fluorine containing olefine.Though this it seems is a kind of method of relative high yield, with regard to industrial-scale production, at high temperature handle the safety-related problem that hydrogen can cause difficulty.And in many cases, the cost (for example build on-site hydrogen factory) of producing hydrogen may play interception.

U.S. Patent No. 2,931,840 (Marquis) have described a kind of method for preparing Fluorine containing olefine by decomposition of methyl chlorine and tetrafluoroethylene or monochlorodifluoromethane.This method is a kind of method of relative low-yield, and in the method, has very big per-cent to be converted to useless and/or unessential by product in the organic raw material, comprises a large amount of carbon blacks.Carbon black is not only useless, and tends to make used in the method catalyst deactivation.

Preparing R-1234yf by trifluoroacetylacetone and sulfur tetrafluoride has obtained describing.See Banks etc., Journalof Fluorine Chemistry, Vol.82, Iss.2, p.171-174 (1997).U.S. Patent No. 5,162,594 (Krespan) also disclose a kind of method, and tetrafluoroethylene and another kind of ethylene fluoride are reacted in liquid phase to prepare poly-fluoroolefins product.

Summary of the invention

The applicant has found the preparation method of fluorinated organic compound (comprising hydrogen fluorine propylene).In the main aspect of the present invention, described method comprises makes halogenation alkane (preferred fluorinated alkane) change into the fluorinated olefin with unsaturated ends carbon, and described unsaturated ends carbon has halogenic substituent, preferred fluoro substituents.In some preferred embodiment, described method comprises makes at least a formula (I) compound:

CF ₃[C(R _a ¹R _b ²)] _nC(R _c ³R _d ⁴)(I)

Change at least a formula (II) compound

CF ₃[C(R _a ¹R _b ²)] _n-1CZ＝CHZ(II)，

R wherein ¹, R ², R ³And R ⁴Be hydrogen atom or the halogen that is selected from fluorine, chlorine, bromine and iodine independently of one another, condition is at least one R ¹, R ², R ³And R ⁴Be halogen; A and b equal 0,1 or 2 independently, and condition is (a+b)=2; B and c equal 0,1,2 or 3 independently, and (c+d)=3, n is 1,2,3 or 4, and each Z is H or halogen independently, and when Z is halogen, is preferably F, and condition is that the Z on the end carbon is a halogen, and the Z on the preferred end carbon is F.

In some preferred embodiment, each Z is all inequality, and in the particularly preferred embodiment, each Z is all inequality, and the Z on the end carbon is F, and the compound that promptly is used for embodiment comprises (HFO-1234ze), and wherein n is 1.

In some embodiment, formula (I) compound also preferably includes wherein R ¹And R ²H and R respectively do for oneself ³Or R ⁴In at least one be the compound of H.For its Chinese style I compound is some this type of embodiment of C3compounds, preferred formula (IA) compound

CF ₃CH ₂CH _mX _3-m(IA)

Wherein each X is F, Cl, I or Br independently; Each Z in the formula (II) is H or halogen independently, when Z is halogen, is preferably F; M is 1 or 2.In formula (IA) compound, preferably use pentachloropropane (HCC-240); Tetrachloro fluoro-propane (HCFC-241); Trichlorine difluoropropane (HCFC-242); Dichloro trifluoro propane (HCFC-243); Chlorine trifluoro propane (HCFC-244) and pentafluoropropane (HFC-245) comprise in these compounds each all isomer, but preferred HCFC-244fa and HFC-245fa.

Preferred step of converting of the present invention is included in gas phase or the liquid phase (or mixed phase of these phases), makes formula (I) compound (more preferably formula (IA) compound) be catalytically converted into one or more formulas (II) compound.In preferred embodiments, this catalytic conversion step is included under the condition of effective conversion, and described formula (I) compound is introduced in the reaction system, and described condition optimization makes at least about 50%, more preferably at least about 70%, even more preferably transform at least about described (I) compound of 90%.General also preferred described step of converting preparation feedback product, in this reaction product, the selectivity of formula (II) compound (be preferably tetrafluoeopropene, even more preferably HFO-1234ze) is at least about 60%, more preferably at least about 80%, even more preferably at least about 95%.

DESCRIPTION OF THE PREFERRED

A useful aspect of the present invention is that it can adopt high relatively transformation efficiency and relative high selective reaction to prepare desirable fluoroolefins (preferred C3 fluoroolefins).In addition, in some preferred embodiment, the inventive method allows by the desirable fluoroolefins of attractive relatively feedstock production.For example, respectively to do for oneself can be formula (I) compound of useful raw material in certain embodiments for five fluorine propylene (especially 1,1,3,3,3-pentafluoropropane (HFC-245fa)) or chlorine tetrafluoropropane (1-chlorine especially, 1,3,3,3-tetrafluoropropane (HCFC-244fa)).For example, can think that such product relatively easily handles, obtain or easily by other feedstock production that is easy to get general easily with commodity amount.

Preferably formula (I) compound is exposed under the reaction conditions of effective preparation feedback product, described reaction product contains one or more required fluoroolefins (preferably one or more formulas (II) compound).A preferred aspect of the present invention, described step of converting comprises a kind of reaction, it is restrictive being not for convenience's sake, sometimes this reaction is called de-hydrogen halide herein, perhaps more specifically is called dehydrofluorination in certain embodiments.Below some preferred embodiment of the present invention is described, (but needing not to be restrictive) for convenience's sake uses the title of title as these steps.

The formation of I, formula II compound

In some preferred embodiment, in that being reached at least about 40% under the condition of (more preferably at least about 55%, even more preferably at least about 70%), formula (I) conversion of compounds rate implements this step of converting.In some preferred embodiment, this transformation efficiency is at least about 90%, and more preferably about 100%.In addition in some preferred embodiment, effectively reach at least about 85% (more preferably at least about 90% in the selectivity that makes formula (II), more preferably at least about 95%, even more preferably from about 100%) condition under, enforcement formula (I) compound transforms production (II) compound.

Preferred reactions steps comprises gas-phase reaction (perhaps may be gas phase and liquid reactive combination), expects that the mode of carrying out of this reaction can be the combination of intermittent mode, continuous mode or these modes.

A, gas phase dehydrohalogenation

Highly preferred reactions steps according to the invention can be reacted by following these and be described, and its Chinese style (IB) compound comprises that m wherein is 1 compound, and it is formula (IB) compound

CF ₃CH ₂CHX ₂(IB)。

For example a kind of preferred formula (IB) compound is the chlorine tetrafluoropropane, is in particular 1-chlorine, 1,3,3, and 3-tetrafluoropropane (244fa).In some preferred embodiment, the logistics (stream) that will contain formula (I) compound (preferred formula (IA) and/or (IB) compound) is preheated to about 150 ℃～about 300 ℃ temperature, preferably is preheated to about 250 ℃, and introduces in the reaction vessel.Reactor remains on temperature required following, preferably under about 400 ℃～about 700 ℃, more preferably under about 450 ℃～about 600 ℃.

Preferred described container comprises corrosion resistant material, as hastelloy, inconel, Monel metal and/or fluoropolymer liner.Preferred described container contains catalyzer, for example stationary catalyst bed or fluid catalyst beds, and it is filled with suitable dehydrohalogenation catalyzer, has the appropriate device that reaction mixture is heated to required temperature of reaction.

Therefore, expection can use the various processing parameters of comprehensive instruction of considering that this paper comprises and processing condition to implement the de-hydrogen halide step.But preferred this reactions steps comprises gas-phase reaction in some embodiment, preferably carries out gas-phase reaction in the presence of catalyzer.

Though expection can be used various catalyzer and catalyst type according to the present invention, the applicant finds, when using the catalyzer of the metal catalyst that comprises neutral charge (charge neutral), can reach remarkable result.Term used herein " metal catalyst of neutral charge " refers to comprise the catalyzer of the basic neutral atoms metal of electric charge.For convenience's sake, in this article, we are called " M with the metal catalyst of such neutral charge ⁰" or " M ⁰Catalyzer ".For the catalyzer that comprises concrete metal, use similar title, for example use " Ni ⁰Catalyzer " expression contains the catalyzer of basic neutral nickle atom.In some preferred embodiment, this method for transformation comprises provides carbon-supported catalysts and/or metal-based catalyst, and M more preferably is provided ⁰Catalyzer (loading type (supported) or non-loading type (unsupported)).During use, M ⁰Catalyzer preferably comprises Ni ⁰Catalyzer or Pd ⁰Catalyzer, Fe ⁰Catalyzer, and the combination of these catalyzer.In some preferred embodiment, catalyzer is substantially by M ⁰Catalyzer is formed, M ⁰Catalyzer is preferably selected from Ni ⁰Catalyzer, Pd ⁰Catalyzer, Fe ⁰Catalyzer, and the combination of two or more aforementioned catalyzer.When such catalyzer was loading type Catellus, in certain embodiments, carrier was preferably carbon and/or gac.Certainly expection can be used other catalyzer and support of the catalyst, comprises palladium carbon, palladium-based catalyst (comprising the carrying alumina palladium), considers the instruction that this paper comprises, and according to the requirement of specific embodiments, expection can be used many other catalyzer.Certainly, in these catalyzer of use capable of being combined or this paper other catalyzer of not naming any two or more.

For the nickel-base catalyst of loading type, even more preferably Ni ⁰Catalyst based (in many embodiments, be included in that its Chinese style (I) compound comprises the compound of one or more formulas (IA) and/or formula (IB) or many embodiments of substantially forming by described compound in, preferred Ni ⁰Catalyst based), general preferably at first acetylacetonate nickel (II) precursor and Tetrabutyl amonium bromide are mixed to form primary catalyst makes it then to be exposed under the reaction conditions and (for example is exposed in the hydrogen), and Ni (II) is changed into Ni (0).Generally also preferably before use catalyzer is carried out drying and fluoridation.The preferred method that forms this type preferred catalyst is disclosed among the embodiment of this paper.

For activated-carbon catalyst, in many embodiments, be included in that its Chinese style (I) compound comprises the compound of one or more formulas (IA) and/or formula (IB) or many embodiments of substantially forming by described compound in also preferred this catalyzer, generally preferably before use gac is carried out drying and fluoridation.The preferred method that forms this type preferred catalyst is disclosed among the embodiment of this paper.

General preferred catalyzer (especially activated-carbon catalyst) is fluoridized, the time of fluoridizing preferably continues a few hours (for example 6 hours) approximately.In the preferred embodiment, fluoridizing of catalyzer is included under the temperature that is about temperature of reaction, under slight pressure (for example about 35psia), catalyzer contacted with HF stream.

For example can implement the gas phase de-hydrogen halide by formula (I) compound (preferred formula (IA) compound) of gas form is introduced in suitable reaction vessel or the reactor.Preferred described container comprises corrosion resistant material, as hastelloy, inconel, Monel metal and/or fluoropolymer liner.Preferred described container contains catalyzer, for example stationary catalyst bed or fluid catalyst beds, and it is filled with suitable dehydrohalogenation catalyzer (preferred catalyzer described herein), has the appropriate device that reaction mixture is heated to required temperature of reaction.

Though according to related factors (for example employed catalyzer and the reaction product of wanting most), can expect and use various temperature of reaction, but generally preferably, be used for the dehydrohalogenation step, being particularly useful for the temperature of reaction that formula (I) compound comprises the situation of formula (IA) and/or formula (IB) compound (even more preferably being made up of formula (IA) and/or formula (IB) compound substantially) is about 400 ℃～about 800 ℃, is preferably about 400 ℃～about 700 ℃.

Generally, also can expect and use various reaction pressures according to related factors (for example employed concrete catalyzer and the reaction product of wanting most).Reaction pressure can in some preferred embodiment, be about 1～about 120psia for for example super-atmospheric pressure, normal atmosphere or negative pressure (under vacuum).

In some embodiment, inert diluent gas (for example nitrogen) and other reactor feed can be used in combination.When using such thinner, generally be preferably based on the gross weight meter of thinner and formula (I) compound, formula (I) compound accounts for about 50 weight % extremely greater than 99 weight %.

The expection catalyst consumption will change along with existing concrete parameter in each embodiment.In some preferred embodiment, be about 0.1 second～about 1000 seconds duration of contact, is preferably about 3 seconds～about 50 seconds.

For such embodiment, its Chinese style (I) compound comprises formula (IA) and/or formula (IB) compound or is made up of formula (IA) and/or formula (IB) compound substantially, especially wherein required formula (II) product is HFO-1234ze, and the applicant finds that the catalyzer that preferably uses is M ⁰Catalyzer, catalyzer preferably comprise basic neutral palladium, nickel, iron and/or carbon, for example palladium-carbon catalyst or nickel C catalyst.

In described this type of dehydrofluorination embodiment in this part, formula (I) conversion of compounds rate is preferably at least about 50%, more preferably at least about 65%, even more preferably at least about 90%.Preferably in this type of embodiment, the selectivity of HFO-1234ze is preferably at least about 70%, more preferably at least about 80%, more preferably at least about 95%.

B, liquid-phase reduction

A kind of possible reactions steps relates to wherein makes formula (I) compound (1-chlorine for example, 1,3,3,3-tetrafluoropropane (HCFC-244fa)) contact to form the reaction of formula (II) compound with dehydrohalogenating agent (for example potassium hydroxide (KOH)).By following reaction formula, with illustrative but nonrestrictive mode this reaction is described:

CF ₃CH ₂CHFCl+KOH→CF ₃CH＝CHF+KCl+H ₂O

Aspect this type of embodiment preferred, in reaction mixture, comprise consisting of phase-transferring agent (for example hat-18-ether), preferably provide KOH with aqueous solution form, this aqueous solution contains the KOH of the 10 weight %～about 50 weight % that have an appointment, more preferably contains the 20 weight % that have an appointment～about 30 weight %KOH.

In some preferred embodiment, under cool relatively temperature, preferably under-10 ℃～about 10 ℃ approximately (preferred about 0 ℃).KOH solution is introduced in the reaction vessel.In reaction vessel, add an amount of formula (I) compound then, every mole of KOH meter, its add-on is preferably about 0.1～about 100 moles (preferred about 0.9～about 10 moles).Reaction mixture progressively is heated to about 40 ℃～about 80 ℃,, preferably under the condition that adds kinetic energy (stir or stir), heats more preferably to about 50 ℃～about 60 ℃.Because preferred reaction is heat release, can allow the temperature of reaction mixture to be elevated to the temperature of about 60 ℃～about 95 ℃ (more preferably to about 65 ℃～about 75 ℃).Concrete processing parameter during reaction pressure in this type of embodiment can be used according to each changes, but in certain embodiments, the pressure during the reaction process is about 0～about 200psig.In some embodiment, from reaction mixture, remove the heat (for example by cooling) that dereaction discharges, so that temperature of reaction remains on the above scope of mentioning first.In some preferred embodiment, total reaction time is about 1～about 40 hours, more preferably about 1～about 10 hours, even more preferably about 2～about 6 hours.

After the specified reaction times, for the ease of collecting reaction product, preferred reaction mixture is to for example about 20 ℃～about 40 ℃.Preferably, transformation efficiency and to the selectivity of HFO-1234ze be at least about 70% separately～about 100%, more preferably at least about 90%～about 100%, preferred productive rate is about 35%～about 95%.

The formation of II, formula I compound

Provide the known of formula of the present invention (I) compound and the expection of can originating to have multiple.For example, in some embodiment, can preferably provide pentachloropropane (HCC-240), this compound is carried out one or more reactions.To prepare one or more formulas (I) compound.Other the whole bag of tricks of preparation formula (I) compound is described in United States Patent(USP) Nos. 5,710,352; In 5,969,198 and 6,023,004, incorporate each patent into this paper by reference.U.S. Patent No. 5,728, the another kind of method of describing in 904 are considered to economical, are suitable for large-scale application and the use raw material that is easy to get.The method of this patent is used following three steps: 1) by making CCl ₄Form CCl with the vinylidene chloride reaction ₃CH ₂CCl ₃2) be selected from TiCl ₄, SnCl ₄Or under the existence of the fluorination catalyst of its mixture,, make CCl by reacting with HF ₃CH ₂CCl ₃Change into CF ₃CH ₂CF ₂Cl; And 3) with CF ₃CH ₂CF ₂Cl is reduced into CF ₃CH ₂CF ₂H.In addition, can be from Honeywell Int Inc (Honeywell International Inc., Morristown, N.J.) buy the HFC-245fa of commodity amount, as the raw material of the inventive method, according to methods described herein, by dehydrofluorination, it is directly changed into fluoroolefins (CF for example ₃CH=CHF).

Embodiment

In following examples other feature of the present invention is described, should think that embodiment limits claim by any way.

Embodiment 1～21

These embodiment have illustrated CF ₃CH ₂CHF ₂(HFC-245fa) the gas phase dehydrohalogenation becomes CF ₃CH=CHF (HFO-1234ze).In 22 inches (1/2 inch of diameter) Monel tubular reactors, be filled with the catalyzer of defined in the 50cc following table 1.This reactor is installed in have three districts well heater at (top, the neutralization end).The import of reactor is connected with pre-heaters, makes pre-heaters be maintained at about 250 ℃ by electrically heated.Send into organism (HFC-245fa) from barrel (cylinder) (remaining on 65 ℃).Remain inert nitrogen stream (20sccm).Make temperature of reactor reach temperature displayed in the table.HFC-245fa enters pre-heaters via gas flow controller, and temperature remains about 250 ℃.The air-flow that comes out from pre-heaters passes through catalyst bed through certain period of time under the pressure of temperature required and about 2.5～5.3psig.Use online GC and GCMS analytic sample, in reactor outlet pipeline (exit line), take a sample with regular time intervals.At last, the effluent of reactor is introduced in 20～60%KOH scrubbing solution, then the effluent from scrubbing solution is carried out condensation, collect product.From mixture, separate required product C F by distillation subsequently ₃CH=CFH (HFO-1234ze).According to reaction conditions, the transformation efficiency of HFC-245fa be about 50%～about 100%, be about 60%～about 100% to the selectivity of HFO-1234ze.Resulting trace by product is CHF ₃And CH ₂=CHF.

The results are shown in the following table 1.

Table 1:HFC-245fa → CF ₃CH=CHF (HFO-1234ze)

Embodiment number/catalyzer	HFC-245fa gm/ hour	T (℃)	The transformation efficiency of 245fa (%)	Selectivity (%) to 1234ze
					Embodiment 1/A	15	495	30	100
Embodiment 2/A	15	525	68	100
					Embodiment 3/A	15	565	100	85
Embodiment 4/B	15	515	82	100
					Embodiment 5/C	15	515	86	100
Embodiment 6/D	15	515	91	100
					Embodiment 7/E	15	515	100	100
Embodiment 8/F	15	475	78	45
					Embodiment 9/G	15	475	82	43
Embodiment 10/H	15	475	85	43
					Embodiment 11/l	15	475	85	44
Embodiment 12/J	15	515	68	100
					Embodiment 13/K	15	515	76	100
Embodiment 14/L	15	515	88	98
					Embodiment 15/M	15	515	100	96
Embodiment 16/A	15	515	68	100
					Embodiment 17/AA	15	515	76	100
Embodiment 18/A	15	515	88	98
					Embodiment 19/AA	15	515	100	96
Embodiment 20/C	520	96	80	60
					Embodiment 21/G	500	63	100	73

Catalyzer (100cc): A is a gac; AA is the gac of acid treatment; B is 0.2wt%Ni/C; C is 0.8wt%Ni/C; D is 1.1wt%Ni/C; E is 1.8wt%Ni/C; F is 0.4wt%Ni/Cr ₂O ₃G is 0.6wt%Ni/Cr ₂O ₃H is 0.7wt%Ni/Cr ₂O ₃I is 1wt%Ni/Cr ₂O ₃J is 0.4wt%Ni/Al ₂O ₃K is 0.6wt%Ni/Al ₂O ₃L is 0.7wt%Ni/Al ₂O ₃M is 1wt%Ni/Al ₂O ₃Product: the 1234ze that obtains be suitable-1234ze (2～5mol%) with anti--1234ze (mixture of 95～98mol%).

Embodiment 22～24

These embodiment have illustrated CF ₃CH ₂CHFCl (HCFC-244fa) gas phase dehydrohalogenation becomes CF ₃CH=CHF (HFO-1234ze).Except using HCFC-244fa to replace HFC-245fa, repeat the operation of embodiment 1～21.The trace by product of identifying through GC/MS (total amount is less than 0.5%) is CF ₃Cl and CF ₃CH ₂Cl.

The results are shown in the following table 2.

Table 1:HFC-244fa → CF ₃CH=CFH (HFO-1234ze)

Embodiment number/catalyzer	HFC-244fa gm/ hour	T (℃)	The transformation efficiency of 244fa (%)	Selectivity (%) to 1234ze
					Embodiment 19/AA	15	515	100	96
Embodiment 20/C	520	96	80	60
					Embodiment 21/G	500	63	100	73

Catalyzer (as defined in Table 1): A is a gac; AA is the gac of acid treatment; B is 0.2wt%Ni/C; C is 0.8wt%Ni/C; D is 1.1wt%Ni/C; E is 1.8wt%Ni/C; F is 0.4wt%Ni/Cr ₂O ₃G is 0.6wt%Ni/Cr ₂O ₃H is 0.7wt%Ni/Cr ₂O ₃I is 1wt%Ni/Cr ₂O ₃J is 0.4wt%Ni/Al ₂O ₃K is 0.6wt%Ni/Al ₂O ₃L is 0.7wt%Ni/Al ₂O ₃M is 1wt%Ni/Al ₂O ₃

Embodiment 25

Present embodiment has illustrated CF ₃CH ₂CHFCl (HCFC-244fa) liquid phase dehydrochlorination becomes CF ₃CH=CHF (HFO-1234ze).The about 150g 20%KOH of impouring solution, 1g hexaoxacyclooctadecane-6 and 10g CF in the 300ml of liner teflon autoclave ₃CHClCH ₂F.Stirred the mixture under 50 ℃ 6 hours.By collecting sample and its mode of analyzing monitored reaction process with GC and MS every 30 minutes.After the reaction period of regulation, cat head is distillated gaseous mixture be transferred in the collection barrel under-70 ℃.Analysis and overall material balance have confirmed that productive rate is 55%.

Specific embodiments more of the present invention have been described like this, those skilled in the art will easily make various changes, modification and improvement, these changes, modification and improvement become apparent because of present disclosure, though clearly do not point out in this article, but it is intended to become a part of the present invention, and is intended to fall in the spirit and scope of the present invention.Therefore, more than describing only is as an example, and nonrestrictive.Only the definition with enclose claim and Equivalent thereof limits the present invention.

Claims (19)

1. the preparation method of fluorinated organic compounds, it comprises makes at least a following first formula compound:

CF ₃CH ₂CH _mX _3-m

Change at least a following second formula compound

CF ₃CZ＝CHF

Wherein each X is Cl, I or Br independently; Z is H or F independently; M is 1,2 or 3.

2. the described method of claim 1 is wherein implemented described step of converting under the conversion of compounds rate that effectively makes at least a first formula reaches at least about 40% condition.

3. the described method of claim 1 is wherein implemented described step of converting under the conversion of compounds rate that effectively makes at least a first formula reaches at least about 80% condition.

4. the described method of claim 1 is wherein implemented described step of converting under the conversion of compounds rate that effectively makes at least a first formula reaches at least about 90% condition.

5. the described method of claim 1 is wherein implemented described step of converting under the selectivity to the compound of at least a second formula effectively reaches at least about 95% condition.

6. the described method of claim 1 is wherein implemented described step of converting under the selectivity to the compound of at least a second formula effectively reaches at least about 90% condition.

7. the preparation method of fluorinated organic compounds, it comprises makes at least a formula (I) compound:

CF ₃[C(R _a ¹R _b ²)] _nC(R _c ³R _d ⁴)(I)

Change at least a formula (II) compound

CF ₃[C(R _a ¹R _b ²)] _n-1CZ＝CHZ(II)，

R wherein ¹, R ², R ³And R ⁴Be hydrogen atom or the halogen that is selected from fluorine, chlorine, bromine and iodine independently of one another, condition is at least one R ¹, R ², R ³And R ⁴Be halogen; A and b equal 0,1 or 2 independently, and condition is (a+b)=2; B and c equal 0,1,2 or 3 independently, and (c+d)=3, n is 1,2,3 or 4, and each Z is H or halogen independently, and further condition is that the Z on the end carbon is a halogen.

8, the described method of claim 7 wherein effectively makes at least a formula (I) conversion of compounds rate implement described step of converting under reaching at least about 40% condition.

9, the described method of claim 7 wherein effectively makes at least a formula (I) conversion of compounds rate implement described step of converting under reaching at least about 90% condition.

10, the described method of claim 7 is wherein implemented described step of converting under the selectivity at least a formula (II) compound effectively reaches at least about 90% condition.

11, the described method of claim 7, wherein the Z on the end carbon is a fluorine.

12, the described method of claim 13, wherein n is 1.

13, the described method of claim 14, wherein said formula (II) compound comprises HFO-1234ze.

14, the described method of claim 7, wherein said formula (I) compound is selected from pentachloropropane (HCC-240); Tetrachloro fluoro-propane (HCFC-241); Trichlorine difluoropropane (HCFC-242); Dichloro trifluoro propane (HCFC-243); Chlorine trifluoro propane (HCFC-244); Pentafluoropropane (HFC-245), and each all isomer and combination in these compounds.

15, the described method of claim 7, wherein said formula (I) compound comprises HCFC-244fa.

16, the described method of claim 7, wherein said formula (I) compound comprises HCFC-245fa.

17, the described method of claim 7, wherein said step of converting comprise makes formula (I) compound for catalysis change into one or more formulas (II) compound.

18, the described method of claim 17, wherein said catalyzed conversion formula (I) compound step comprise makes described formula (I) compound contact with the metal catalyst of neutral charge.

19, the described method of claim 17, wherein said catalyzed conversion formula (I) compound step comprises makes described formula (I) compound and Ni ⁰The catalyzer contact.