CN105143155A - Process for producing (e)-1-chloro-3,3,3-trifluoropropene - Google Patents
Process for producing (e)-1-chloro-3,3,3-trifluoropropene Download PDFInfo
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- CN105143155A CN105143155A CN201480023284.4A CN201480023284A CN105143155A CN 105143155 A CN105143155 A CN 105143155A CN 201480023284 A CN201480023284 A CN 201480023284A CN 105143155 A CN105143155 A CN 105143155A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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Abstract
A process for producing (E)-1-chloro-3,3,3-trifluoropropene (R-1233zd (E-isomer)) is provided by which high-purity R-1233zd (E-isomer) is highly selectively obtained in a simple manner. The R-1233zd (E-isomer) production process comprises: purifying a first composition comprising 1,1-dichloro-3,3,3-trifluoropropane and 1,3-dichloro-1,3,3-trifloropropane to give a second composition in which the content of 1,3-dichloro-1,3,3-trifloropropane is 5 mol% or less with respect to the total amount of the 1,1-dichloro-3,3,3-trifluoropropane and the 1,3-dichloro-1,3,3-trifloropropane; and subsequently making the 1,1-dichloro-3,3,3-trifluoropropane contained in the second composition undergo a dehydrochlorination reaction to thereby obtain R-1233zd (E-isomer).
Description
Technical field
The present invention relates to the manufacture method of (E)-1-chloro-3,3,3 ,-trifluoropropene (hereinafter also referred to R-1233zd (E body)).
In addition, in this specification sheets, cis-trans isomer Z-E represents, cis body Z body surface shows, trans body E body surface shows, the mixture of Z body and E body and do not distinguish Z body and E body be called EZ body.
Background technology
In this specification sheets, sometimes for halon, the abbreviation (refrigeration agent numbering etc.) of its compound is remembered in the parantheses after compound name, but in this manual, sometimes also use it to be called for short to replace compound name as required.
Greenhouse gases 1 as an alternative, 1,1,2-Tetrafluoroethane (hereinafter also referred to R-134a), 1,1,1,3, the starting monomer being used as refrigeration agent, whipping agent, clean-out system, solvent and aerosol and functional material of 3-pentafluoropropane (hereinafter also referred to R-245fa) and synthesis intermediate, R-1233zd (E body) is expected in recent years.
As the method manufacturing this R-1233zd (E body), such as propose under the existence of the pentachloropropane as catalyzer, carry out fluoridizing with hydrogen fluoride and after making dichloro trifluoro propane, the dichloro trifluoro propane obtained is carried out to the method (for example, referring to patent documentation 1) of dehydrochlorination in alkali alcosol.In addition, propose and make chloro-3,3, the 3-trifluoro propane (also claiming R-243fa below) of 1,1-bis-contact the method (for example, referring to patent documentation 2) of carrying out dehydrochlorination reaction with alkali aqueous solution.
In these techniques, disclose and can manufacture R-1233zd (E body) by R-243fa.
R-1233zd (E body) uses from the viewpoint of the starting monomer and synthesis intermediate that can be used as functional material, preferably obtains with high purity.In addition, in the use of refrigeration agent, whipping agent, clean-out system, solvent, aerosol etc., consider various decree, indicate obligation, close rule etc., preferably obtain with high purity.
But in the technology of above-mentioned proposition, existence can not obtain the problem of R-1233zd (E body) with high purity.
Therefore, present situation is that requirement provides a kind of by easy method, the manufacture method obtaining the R-1233zd (E body) of highly purified R-1233zd (E body) with highly selective, and the composition obtained by this manufacture method.
In addition, the known method (for example, referring to patent documentation 3) industrially manufacturing dichloro trifluoro propane with easy method.But in the method, known together with R-243fa, chloro-1,3, the 3-trifluoro propane (hereinafter referred to as R-243fb) of 1,3-bis-produces as by product.
Prior art document
Patent documentation
Patent documentation 1: Chinese patent discloses No. 101168494 publications
Patent documentation 2: International Publication No. 2012/145188 text
Patent documentation 3: Japanese Patent Laid-Open 8-73385 publication
Summary of the invention
Invent technical problem to be solved
In the method for patent documentation 1 and 2, think and simultaneously create (E)-3-chloro-1 as by product with R-1233zd (E body), 3,3-trifluoro propene (hereinafter referred to as R-1233ze (E body)) and (Z)-3-chloro-1,3,3-trifluoro propene (hereinafter referred to as R-1233ze (Z body)).The present inventor finds, is difficult by R-1233zd (E body) and R-1233ze (E body) and R-1233ze (Z body) fractionation by distillation.That is, there is the problem that can not be obtained highly purified R-1233zd (E body) by the method for patent documentation 1 and 2.
In addition, the present inventor finds when being manufactured R-1233zd (E body) by R-243fa, if be present in reaction system as the R-243fb of the isomer of R-243fa, then R-243fb becomes R-1233ze (E body) and R-1233ze (Z body).
Problem of the present invention is to provide a kind of manufacture method obtaining the R-1233zd (E body) of highly purified R-1233zd (E body) by easy method with highly selective.
The technical scheme that technical solution problem adopts
The present inventor finds, in the manufacture method of R-1233zd (E body), first composition of R-243fa and R-243fb is contained by purifying, after obtaining being second composition of less than 5 % by mole relative to the total amount of R-243fa and R-243fb, the content of R-243fb, carry out the dehydrochlorination reaction of the R-243fa in the second composition, obtain R-1233zd (E body), thus by easy method, obtain highly purified R-1233zd (E body) with highly selective, thus complete the present invention.
(E) of the present invention-1-chloro-3, 3, the feature of the manufacture method of 3-trifluoro propene (R-1233zd (E body)) is, will containing 1, 1-bis-chloro-3, 3, 3-trifluoro propane (R-243fa) and 1, 3-bis-chloro-1, 3, first composition purifying of 3-trifluoro propane (R-243fb), make relative to 1, 1-bis-chloro-3, 3, 3-trifluoro propane (R-243fa) and 1, 3-bis-chloro-1, 3, the total amount of 3-trifluoro propane (R-243fb), 1, 3-bis-chloro-1, 3, the content of 3-trifluoro propane (R-243fb) is second composition of less than 5 % by mole, then, make 1 in the second composition, 1-bis-chloro-3, 3, 3-trifluoro propane (R-243fa) dehydrochlorination reaction, obtain (E)-1-chloro-3, 3, 3-trifluoro propene (R-1233zd (E body)).
The effect of invention
If employing the present invention, then can provide a kind of manufacture method obtaining the R-1233zd (E body) of highly purified R-1233zd (E body) by easy method with highly selective.
Accompanying drawing explanation
Fig. 1 is the figure of the behavior of the purifying represented in embodiment 3.
Fig. 2 is the figure of the behavior of the purifying represented in comparative example 3.
Embodiment
Below the operation of " by the first composition purifying, obtaining the second composition " in manufacture method of the present invention is called " purification procedures (1) ".In addition, the operation of " carry out the dehydrochlorination reaction of the R-243fa in the second composition, obtain R-1233zd (E body) " is called " manufacturing process (A) ".
Further, " manufacturing the operation of the first composition " is called " manufacturing process (B) ", the operation that the reaction mixture obtained manufacturing process (A) carries out purifying is called " purification procedures (2) ".
(manufacture method of R-1233zd (E body))
The manufacture method of R-1233zd of the present invention (E body) comprises purification procedures (1) and manufacturing process (A), preferably comprises at least arbitrary operation of manufacturing process (B) and purification procedures (2) further.
When the manufacture method of R-1233zd (E body) comprises manufacturing process (B), the manufacture method of R-1233zd (E body) is carried out according to the order of manufacturing process (B), purification procedures (1), manufacturing process (A) usually.
When the manufacture method of R-1233zd (E body) comprises purification procedures (2), the manufacture method of R-1233zd (E body) is carried out according to the order of purification procedures (1), manufacturing process (A), purification procedures (2) usually.
When the manufacture method of R-1233zd (E body) comprises manufacturing process (B) and purification procedures (2), the manufacture method of R-1233zd (E body) is carried out according to the order of manufacturing process (B), purification procedures (1), manufacturing process (A) and purification procedures (2) usually.
< purification procedures (1) >
Purification procedures (1) is the first composition that purifying contains R-243fa and R-243fb, and obtaining is the operation of second composition of less than 5 % by mole relative to the total amount of R-243fa and R-243fb, the content of R-243fb.Be not particularly limited as the purification process in purification procedures (1), suitably can select according to object, such as, can exemplify distillation, absorption etc.
Wherein, from the viewpoint of what can carry out easily, preferably distill.
[distillation]
Distillation can be carried out at ambient pressure, also can under elevated pressure, also can under reduced pressure carry out.Wherein, preferably carry out at ambient pressure.
When distilling, using the suitable cut in distillation as the second composition.
First composition, at least containing R-243fa and R-243fb, further as required, can contain the composition (hereinafter referred to as other compositions) beyond these.
As these other compositions, such as can exemplify the compound trichloromethane (chloroform) close with R-243fa boiling point, tetrachloromethane (tetracol phenixin), 1, 2-ethylene dichloride, 1, 1-ethylene dichloride, 1, 1, 2-tri-chloro-3, 3-C2H4F2 C2H4F2 (R-122), 1, 1, 2-trieline, 1-chloro-1, 3, 3, 3-tetrafluoropropane (R-244fa), (EZ)-1, 3-bis-chloro-3, 3-difluoropropenes (R-1232zd (EZ body)), (EZ)-3-chloro-1, 3, 3-trifluoro propene (R-1233ze (EZ body)), (Z)-1-chloro-3, 3, 3-trifluoro propene (hereinafter referred to as R-1233zd (Z body)), 3, 3-bis-chloro-1, 1, 3-trifluoro propene (R-1233zc), other chlorodifluoromethanes (hereinafter referred to as R-22), dichlorofluoromethane (hereinafter referred to as R-21), trifluoromethane (hereinafter referred to as R-23) etc.
R-243fb and other compositions manufacture in the operation of R-243fa in manufacturing process (B) etc. and generate as by product, are included in the first composition.
R-243fa in first composition contains proportional preferably more than 50 % by mole.
R-243fb in first composition contains proportional preferably less than 10 % by mole.
When the first composition contains other compositions, other compositions in the first composition containing proportional preferably less than 30 % by mole.
In second composition, relative to the total amount of R-243fa and R-243fb R-243fb containing proportional be less than 5 % by mole, preferably less than 3 % by mole, more preferably less than 1 % by mole.If the content of R-243fb is in preferred scope, then the impurity in minimizing dehydrochlorination reaction product, purifying are favourable in being easy to.
As the R-243fb in the second composition containing proportional, preferably less than 5 % by mole, preferably less than 1 % by mole further, particularly preferably less than 0.5 % by mole.
Usually by the purifying of the first composition, other compositions are also the same with R-243fb to be removed, and by this, the content of other compositions in the second composition also tails off.When there are other compositions in the second composition, the ratio of other compositions in the second composition preferably less than 1 % by mole, more preferably less than 0.1 % by mole.
From the reactive aspect of dehydrochlorination reaction after improving, and the impurity after dehydrochlorination reaction reduces, purifying is easy to aspect and considers, particularly preferably in the second composition R-243fa and R-243fb total containing proportional is 100 % by mole.
< manufacturing process (A) >
The dehydrochlorination reaction of manufacturing process (A) carries out preferably by making the second composition contact with metal hydroxide solutions.As metal hydroxide solutions, the alcoholic solution of the metal hydroxides aqueous solution and metal hydroxides can be exemplified.
Here, as metal hydroxides, alkaline-earth metal oxyhydroxide, alkali metal hydroxide etc. can be exemplified.
Dehydrochlorination reaction from the viewpoint of reaction times, reaction yield and R-1233zd (E body) optionally, preferably carries out with the method making the second composition contact with alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst.As alkaline-earth metal oxyhydroxide, such as, can exemplify magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta.As alkali metal hydroxide, such as, can exemplify lithium hydroxide, sodium hydroxide, potassium hydroxide.
As the metal hydroxides aqueous solution, such as, can exemplify aqueous sodium hydroxide solution, potassium hydroxide aqueous solution.As metal hydroxides alcoholic solution, the ethanolic soln of sodium hydroxide can be exemplified.Wherein, from the viewpoint of R-1233zd (E body) optionally, preferable alloy hydroxide aqueous solution, more preferably aqueous sodium hydroxide solution, potassium hydroxide aqueous solution.
The concentration of metal hydroxide solutions, from the viewpoint of speed of response, as the quality % of solute (metal hydroxides), preferably 0.5 ~ 40 quality %, more preferably 5 ~ 30 quality %.When metal hydroxide solutions is the metal hydroxides aqueous solution, if concentration is in above-mentioned scope, 2 layers of separation can be carried out easily.
As the usage quantity of the metal hydroxide solutions in dehydrochlorination reaction, relative to R-243fa, the alkali number of preferred 0.5 ~ 2.0 molar equivalent of metal hydroxides, the more preferably alkali number of 1.0 ~ 1.5 molar equivalents.
When using the metal hydroxides aqueous solution in dehydrochlorination reaction, in order to make reaction carry out efficiently, preferably use phase-transfer catalyst.
As phase-transfer catalyst, such as, can exemplify quaternary ammonium salt, quaternary alkylphosphonium salt, Ji Arsenic salt, sulfonium salt, crown ether etc.Wherein preferred quaternary ammonium salt.
[quaternary ammonium salt]
As quaternary ammonium salt, such as, can exemplify the compound (hereinafter sometimes referred to " compound (i) ") that following general formula (i) represents.
[changing 1]
In general formula (i), R
11~ R
14separately represent alkyl, Y
-represent negatively charged ion.
As R
11~ R
14in alkyl, such as can exemplified by alkyl groups, cycloalkyl, alkenyl, cycloalkenyl, aryl etc.Wherein, preferred alkyl, aryl.
As R
11~ R
14carbon number, with every 1 molecule R
11r
12r
13r
14n
+total carbon number meter, preferably 4 ~ 100.
R
11~ R
14can be identical group respectively, also can be different group.
R
11~ R
14can at reaction conditions replace by inert functional groups.As inert functional groups, different according to reaction conditions, such as can exemplify halogen atom, ester group, itrile group, acyl group, carboxyl, alkoxyl group etc.
As Y
-, such as, can exemplify chlorion, fluorion, bromide anion, iodide ion, sulfate ion, nitrate ion, phosphate ion, high chloro acid ion, hydrogen sulfate ion, hydroxide ion, acetato-, benzoate, Phenylsulfonic acid ion, tosic acid ion etc.Wherein, preferred chlorion, bromide anion, iodide ion, hydrogen sulfate ion, hydroxide ion.
As compound (i), from the viewpoint of the versatility of compound (i) and reactive, preferred following R
11r
12r
13r
14n
+with following Y
-combination.
R
11r
12r
13r
14n
+: tetramethyl ammonium, tetraethyl ammonium ion, four n-propyl ammonium ions, tetra-n-butyl ammonium ion, three n-octyl ammonium ion.
Y
-: fluorion, chlorion, bromide anion, iodide ion, hydroxide ion.
As the quaternary ammonium ion in quaternary ammonium salt, such as tetramethyl ammonium can be exemplified, tetraethyl ammonium ion, four n-propyl ammonium ions, tetra-n-butyl ammonium ion, three n-octyl ammonium ion, cetyltrimethylammonium ammonium ion, benzyl trimethyl ammonium ion, benzyl triethyl ammonium ammonium ion, hexadecyl benzyl dimethyl ammonium ion, cetyl pyridinium ion, dodecyl pyridinium ion, phenyl trimethicone ammonium ion, phenyl triethylammonium ammonium ion, N-benzyl methyl pyridinium ion, five first ammonium ions (Japanese: ペ Application タ メ ト ニ ウ system イ オ Application), hexamethylamine ion (Japanese: ヘ キ サ メ ト ニ ウ system イ オ Application) etc.
As quaternary ammonium salt, particularly preferably tetrabutylammonium chloride.
[quaternary alkylphosphonium salt]
As quaternary alkylphosphonium salt, the compound that following general formula (ii) represents can be exemplified.
[changing 2]
In general formula (ii), R
21~ R
24separately represent alkyl, Y
-represent negatively charged ion.
As R
21~ R
24in alkyl, such as can exemplified by alkyl groups, cycloalkyl, alkenyl, cycloalkenyl, aryl etc.Wherein, preferred alkyl, aryl.
As quaternary phosphine ion (R in general formula (ii)
21r
22r
23r
24p
+), such as can exemplify Si Yi Ji Phosphonium ion, Si Zheng Ding Ji Phosphonium ion, three n-octyl Yi Ji Phosphonium ions, hexadecyl San Yi Ji Phosphonium ion, hexadecyl San Zheng Ding Ji Phosphonium ion, normal-butyl triphenyl phosphonium ion, n-pentyl triphenyl phosphonium ion, Jia base triphenyl phosphonium ion, Bian base triphenyl phosphonium ion, tetraphenylphosphoniphenolate ion etc.
As Y
-, such as, can exemplify chlorion, fluorion, bromide anion, iodide ion, sulfate ion, nitrate ion, phosphate ion, high chloro acid ion, hydrogen sulfate ion, hydroxide ion, acetato-, benzoate, Phenylsulfonic acid ion, tosic acid ion etc.Wherein, preferred fluorion, chlorion, bromide anion.
[Ji Arsenic salt]
As Ji Arsenic salt, the compound that following general formula (iii) represents can be exemplified.
[changing 3]
In general formula (iii), R
31~ R
34separately represent alkyl, Y
-represent negatively charged ion.
As R
31~ R
34in alkyl, such as can exemplified by alkyl groups, cycloalkyl, alkenyl, cycloalkenyl, aryl etc.Wherein, preferred alkyl, aryl.
As Y
-, preferred halide-ions, more preferably fluorion, chlorion, bromide anion.
As season Arsenic salt, such as can exemplify fluoridize three phenyl methyl Arsenic salt, fluoridize four benzene base Arsenic salt, chlorinated triphenyl base first base Arsenic salt, chlorination four benzene base Arsenic salt, bromineization four benzene base Arsenic salt, their polymeric derivative etc.
As Ji Arsenic salt, particularly preferably chlorinated triphenyl base Jia Ji Arsenic salt.
[sulfonium salt]
As sulfonium salt, the compound that following general formula (iv) represents can be exemplified.
[changing 4]
In general formula (iv), R
41~ R
43separately represent alkyl, Y
-represent negatively charged ion.
As R
41~ R
43in alkyl, such as can exemplified by alkyl groups, cycloalkyl, alkenyl, cycloalkenyl, aryl etc.Wherein, preferred alkyl, aryl.
As Y
-, preferred halide-ions, more preferably fluorion, chlorion, bromide anion.
As sulfonium salt, such as, can exemplify di-n-butyl methyl sulfonium salt compounded of iodine, three normal-butyl sulfonium a tetrafluoro borates, dihexyl methyl sulfonium salt compounded of iodine, dicyclohexylmethyl sulfonium salt compounded of iodine, chlorination dodecyl methyl ethyl sulfonium salt, three (diethylamino) sulfonium halide atom hydrochlorate etc.
As sulfonium salt, particularly preferably chlorination dodecyl methyl ethyl sulfonium salt.
[crown ether]
As crown ether, such as, can exemplify 18-hat-6, dibenzo-18 crown-6 etc.
As the usage quantity of the phase-transfer catalyst in dehydrochlorination reaction, relative to 100 mass parts R-243fa, preferably 0.001 ~ 5 mass parts, more preferably 0.01 ~ 1 mass parts.
Dehydrochlorination reaction such as by importing reactor using as the second composition of raw material and alkali metal hydroxide aqueous solution and phase-transfer catalyst with the ratio suitably selected, making it fully contact, utilizing ordinary method to carry out stirring to implement.
As the temperature of reaction in dehydrochlorination reaction, from the viewpoint of reactive behavior and R-1233zd (E body) optionally, preferably 0 ~ 80 DEG C.In addition, temperature of reaction suitably can regulate according to the pressure state of reaction vessel during reaction.Such as, when carrying out dehydrochlorination reaction at ambient pressure, temperature of reaction preferably 0 ~ 60 DEG C, more preferably 20 ~ 60 DEG C.If temperature of reaction is in preferred scope, then to R-243fa with more efficient speed of response and highly selective carry out dehydrochlorination in be favourable.
In addition, also can carry out dehydrochlorination reaction in compressive reaction container, as the optimum condition in this situation, be 98000 ~ 200000Pa and 20 ~ 60 DEG C.
Dehydrochlorination reaction can batch-type carry out, and also can carry out by Continuous Flow general formula.
As the material of the reactor for dehydrochlorination reaction, such as glass, iron, nickel or using they alloys etc. as main component can be exemplified.
Wherein, the alloy containing iron such as preferred stainless steel.
< manufacturing process (B) >
As manufacturing process (B), vinylidene fluoride (vinylidene) and R-21 is preferably made to react and obtain the operation of the first composition.Below, this manufacturing process (B) is called manufacturing process (B-1).
By using manufacturing process (B-1), poor first composition of purifying in purification procedures (1) other compositions easily, beyond R-243fa and R-243fb can be obtained.
Reaction in above-mentioned manufacturing process (B-1) can represent by following reaction formula (1).In addition, the C in following reaction formula
3h
3cl
2f
3represent dichloro trifluoro propane (R-243), R-243 is the general name of the dichloro trifluoro propane isomer such as R-243fa, R-243fb.The isomer mixture of the R-243 be obtained by reacting with this normally containing R-243fa and R-243fb.
[changing 5]
CF
2＝CH
2+CHCl
2F→C
3H
3Cl
2F
3(1)
In addition, in the reaction product of reaction formula (1) except R-243 also containing chloroform, R-23,1,1,1-Halothane (hereinafter referred to as R-143a) etc.
R-243fb in the composition that above-mentioned manufacturing process (B-1) obtains containing proportional different according to reaction conditions (especially temperature of reaction and the kind of catalyzer that uses), but be more than 1 % by mole relative to R-243fa usually.
Reaction in above-mentioned manufacturing process (B-1) preferably uses catalyzer to carry out.As catalyzer, the modified chlorinated zirconium, lewis acid catalyst etc. that such as can exemplify aluminum chloride, process through trichlorofluoromethane etc.As lewis acid catalyst, such as, can exemplify the halogenide etc. of at least any one element containing Al, Sb, Nb, Ta, W, Re, B, Sn, Ga, In, Zr, Hf and Ti.
When using aluminum chloride as catalyzer in above-mentioned manufacturing process (B-1), the composition containing R-243 obtained by reaction formula (1) is mainly containing the composition of R-243fa and R-243fb as reaction product, in addition, also chloroform, R-23, R-143a etc. is contained as reaction product.Said composition can use as the first composition.
Use in the above-mentioned manufacturing process (B-1) modified chlorinated zirconium as when catalyzer (such as, with reference to Japanese Patent Laid-Open 4-253928 publication), the composition obtained by reaction formula (1) is mainly containing the composition of R-243fa and R-243fb as reaction product, in addition, also the composition such as a small amount of chloroform, R-23, R-143a is contained as reaction product.Said composition can use as the first composition.
When using lewis acid catalyst as catalyzer in above-mentioned manufacturing process (B-1), the composition obtained by reaction formula (1) is mainly containing the composition of R-243fa and R-243fb as reaction product, in addition, also the composition such as a small amount of chloroform, R-23, R-143a is contained as reaction product.Said composition can use as the first composition.
As the method obtaining the first composition, also aforesaid manufacturing process (B-1) can be replaced with using the operation (hereinafter referred to as manufacturing process (B-2)) of following methods.
< manufacturing process (B-2) >
Manufacturing process (B-2), as long as make five halogenopropanes and hydrogen fluoride reaction and obtain the operation of the first composition, is not particularly limited, suitably can selects according to object.
Reaction in manufacturing process (B-2) can represent by following reaction formula (2).In addition, the C in following reaction formula
3h
3cl
2f
3represent R-243.
[changing 6]
CCl
mF
(3-m)CH
2CHCl
2+mHF→C
3H
3Cl
2F
3(2)
In reaction formula (2), m is the integer of 1 ~ 3.
R-243fb in the composition that above-mentioned manufacturing process (B-2) obtains containing proportional different according to reaction conditions (especially temperature of reaction and the kind of catalyzer that uses), but be more than 1 % by mole relative to R-243fa usually.
< purification procedures (2) >
The composition obtained by the dehydrochlorination reaction in the present invention can be further purified as required.As purifying, distillation, absorption, cleaning etc. can be exemplified.As cleaning, the cleaning utilizing acidic aqueous solution, neutral aqueous solution or alkaline aqueous solution can be exemplified.As purifying, particularly preferably distill.
When using the metal hydroxides aqueous solution in dehydrochlorination reaction, reacted composition contains water.Therefore, when carrying out purifying, first composition being separated into organic layer and water layer, afterwards, organic layer being distilled.
In the present invention, by reducing the R-243fb in the purification procedures (1) before carrying out dehydrochlorination reaction in the first composition (feedstock composition), reduce and be difficult to be separated (such as with R-1233zd (E body), fractionation by distillation), as the R-1233ze (E body) of the isomer of R-1233zd (E body) and the content of R-1233ze (Z body), separation and purification is carried out in distillation by this by routine, obtains highly purified R-1233zd (E body).
The purposes > of <R-1233zd (E)
R-1233zd (E) alternative greenhouse gases R-134a, R-245fa of being obtained by manufacture method of the present invention and be used as starting monomer and the synthesis intermediate of refrigeration agent, whipping agent, clean-out system, solvent and aerosol and functional material.
When by R-1233zd (E) as the starting monomer of functional material and synthesis intermediate, be particularly preferably high purity (such as more than 99.0 % by mole).
Embodiment
Below, embodiments of the invention are described, but the invention is not restricted to following embodiment.
[analysis condition]
Compositional analysis uses vapor-phase chromatography.Chromatographic column uses DB-1301 (length 60m × internal diameter 250 μm × thickness 1 μm, Agilent Technologies (ア ジ レ Application ト テ Network ノ ロ ジ ー Co., Ltd.) makes).In addition, due to the structures shape that R-1233ze (E body) and R-1233ze (Z body) can't help between EZ constitutional isomer, therefore in the present embodiment, for simplicity, be labeled as by EZ constitutional isomer short for retention time in above-mentioned gc analysis condition " R-1233ze (E or Z body): isomer A ", the EZ constitutional isomer that retention time is long is labeled as " R-1233ze (E or Z body): isomer B ".
(catalyst preparation example 1)
The preparation > of the modified chlorinated Zr catalyst of <
The water cooler being connected with height 15cm on top, the four mouthfuls of 1L glass flasks having put into magnetic stick drop into zirconium tetrachloride 256.9g.Then while the water cooler and flask dry ice that are connected to top are cooled to-78 DEG C, the R-21 of 636g is slowly dropped into.While stir with magnetic-type stirrer, make the temperature of the water cooler and flask being connected to top slowly rise to 0 DEG C, after interior temperature arrives 0 DEG C, continue stirring 2.5 hours.Afterwards, stop being connected to the water cooler on top and the cooling of flask, at room temperature drying under reduced pressure 1 night.After drying terminates, reclaim 236.1g catalyzer.
(Production Example 1)
< is containing the synthesis > of R-243fa composition
Drop in hastelloy 10L autoclave as initial stage solvent containing the composition of R-243fa, (R-243fa is 40 % by mole, R-243fb is 8 % by mole, chloroform is 29 % by mole, R-22 is 2 % by mole, R-21 is 7 % by mole, other compositions are 13 % by mole) after 1000g and the catalyzer 78g prepared by catalyst preparation example 1, be cooled to till-10 ~-5 DEG C.Carry out cooling while stir, slowly drop into the R-21 of 7202g with the speed making interior temperature keep below 0 DEG C.Then, cool and stir, while interior temperature keeps below 0 DEG C, dropped into vinylidene fluoride (vinylidene) 4480g with 8 hours.Feed intake after terminating, stir 30 minutes, with nitrogen displacement gas phase portion, terminate reaction.After reaction terminates, stir the bottom extraction stoste from 10L autoclave.The amount of the reaction stoste of extracting out is 12822g.Afterwards, filter reaction stoste with the pressure filter being provided with 5 μm of footpath filter paper, obtain the even organic layer of 12470g.Recovery part organic layer, the result analyzed composition by vapor-phase chromatography (GC), the ratio of components of organic layer are as follows.
R-243fa:56 % by mole
R-243fb:9 % by mole
Chloroform: 5 % by mole
R-143a:1 % by mole
R-21:9 % by mole
Other compositions: 20 % by mole
(Production Example 2)
< is containing the distillation purifying > of R-243fa composition
In the glass distillation tower possessing the footpath 3cm height 97cm that can carry out 10L glass stove, magnetic-type reflux, reflux timer and the Di Muluo water cooler heated with mantle heater, fill HeliPackNo.1 (Zhu Zhongjinwang Co., Ltd. (Zhu Zhongjin Steel Co., Ltd.) system) (stage number measured value 43 layers), use it to distill.11000g in the organic layer obtain Production Example 1 drops into water distilling apparatus, and by reflux timer by return time/distillate the ratio of time to be adjusted to 50/1 ~ 300/1, one side is distilled at ambient pressure.
Consequently, obtain that R-243fa is more than 99.5 % by mole, R-243fb is lower than the composition 946g of 0.5 % by mole.
In addition, the composition 5646g that R-243fa is 94.0 % by mole, R-243fb is 6.0 % by mole is obtained.
(Production Example 3)
Repeatedly implement Production Example 1, Production Example 2 respectively, prepare following 4157g by the composition be mixed to get and contain R-243fa composition 3 containing R-243fa composition 1,13225g containing R-243fa composition 2,1570g.
Be 99.9 % by mole containing R-243fa composition 1:R-243fa, R-243fb is 0.1 % by mole
Be 94.0 % by mole containing R-243fa composition 2:R-243fa, R-243fb is 5.9 % by mole, and other compositions are 0.1 % by mole
Be 84.7 % by mole containing R-243fa composition 3:R-243fa, R-243fb is 15.3 % by mole
Use containing R-243fa composition 1 in following embodiment 1,2.Use containing R-243fa composition 2 in comparative example 1.Use containing R-243fa composition 3 in comparative example 2.
(embodiment 1)
The synthesis of <R-1233zd (E body): containing R-243fa composition (R-243fb is 0.1 % by mole) and the dehydrochlorination reaction > of alkali aqueous solution in phase-transfer catalyst
In hastelloy 10L autoclave, add tetrabutylammonium chloride (TBAC) 19.3g, Production Example 3 obtains, and (R-243fa is 99.9 % by mole containing R-243fa composition 1, R-243fb is 0.1 % by mole) after 3861.9g (23.1 moles), interior temperature is remained on 5 ~ 10 DEG C while drop into 20 quality % aqueous sodium hydroxide solution 6907.7g (NaOH34.7 mole).Behind nitrogen displacement gas phase portion, make interior temperature rise to 25 DEG C, stir 2 hours, then make interior temperature rise to 40 DEG C, stir 6 hours.Leave standstill 2 hours after making interior temperature be cooled to 5 DEG C, reclaim according to organic layer, water layer order from reactor lower part.Organic layer yield is 2913.1g, and water layer yield is 7832.4g.The result analyzed by vapor-phase chromatography (GC) composition to organic layer and other reaction results are shown in table 1.
(embodiment 2)
The synthesis of <R-1233zd (E body): containing R-243fa composition (R-243fb is 0.1 % by mole) the dehydrochlorination reaction > in alkali alcoholic solution
In glass 1L autoclave, add sodium hydroxide 116.8g (2.9 moles), ethanol (Junsei Chemical Co., Ltd. (Pure just chemistry) Lot.2012K2003) 270.5g and Production Example 3 obtain containing R-243fa composition 1 (R-243fa is 99.9 % by mole, and R-243fb is 0.1 % by mole) 349.5g (2.1 moles).Make interior temperature rise to 45 DEG C, stir after 9 hours, open gas phase portion valve, in the SUS316 inflator cooled with dry ice, reclaim volatile component 534.8g.Interior temperature is cooled to room temperature after reclaiming and terminating by volatile component, drops into distilled water 525.0g, stirs 24 hours.Stirring terminates rear open reactor, reclaims water layer 690.3g.Confirm not isolate organic layer from aqueous phase.The result analyzed by vapor-phase chromatography (GC) composition to volatile component and other reaction results are shown in table 1.
(comparative example 1)
The synthesis of <R-1233zd (E body): containing R-243fa composition (R-243fb is 5.9 % by mole) and the dehydrochlorination reaction > of alkali aqueous solution in phase-transfer catalyst
In hastelloy 10L autoclave, add tetrabutylammonium chloride (TBAC) 19.3g, Production Example 3 obtains, and (R-243fa is 94.0 % by mole containing R-243fa composition 2, R-243fb is 5.9 % by mole, other compositions 0.1 % by mole) after 3861.9g (23.1 moles), interior temperature is remained on 5 ~ 10 DEG C while drop into 20 quality % aqueous sodium hydroxide solution 6907.7g (NaOH34.7 mole).Behind nitrogen displacement gas phase portion, make interior temperature rise to 25 DEG C, stir 2 hours, then make interior temperature rise to 40 DEG C, stir 8 hours.Leave standstill 2 hours after making interior temperature be cooled to 5 DEG C, reclaim according to organic layer, water layer order from reactor lower part.Organic layer yield is 2835.4g, and water layer yield is 7723.7g.The result analyzed by vapor-phase chromatography (GC) composition to organic layer and other reaction results are shown in table 1.
(comparative example 2)
The synthesis of <R-1233zd (E body): containing R-243fa composition (R-243fb is 15.3 % by mole) the dehydrochlorination reaction > in alkali alcoholic solution
In the SUS316 autoclave of 200mL, add that sodium hydroxide 16.7g (0.42 mole), ethanol (Junsei Chemical Co., Ltd. Lot.2012K2003) 38.8g and Production Example 3 obtain containing R-243fa composition 3 (R-243fa is 84.7 % by mole, and R-243fb is 15.3 % by mole) 50.0g (0.30 mole).Make interior temperature rise to 45 DEG C, stir after 6 hours, open gas phase portion valve, in the SUS316 inflator cooled with dry ice, reclaim volatile component 77.0g.Interior temperature is cooled to room temperature after reclaiming and terminating by volatile component, drops into distilled water 75.3g, stirs 1 hour.Stirring terminates rear open reactor, reclaims yellow aqueous solution 97.0g.Confirm not isolate organic layer from aqueous phase.The result analyzed by vapor-phase chromatography (GC) composition to volatile component and other reaction results are shown in table 1.
Table 1
In table 1, " R-243fa transformation efficiency (%) ", " R-1233zd (E body) selection rate (%) " and " R-1233ze (E or Z): isomer A containing ratio (%) in R-1233zd (E body) " are obtained by following formula.
In addition, table 1 and following in " Et " expression " ethyl ".
(R-243fa transformation efficiency (%) (X))
X＝100×(Xa-Xb)/Xa
Xa: R-243fa amount (% by mole) in raw material
Xb: reacted R-243fa amount (% by mole)
(R-1233zd (E body) selection rate (%) (Y))
Y＝100×Ya/(Ya+Yb+Yc+Yd+Ye)
Ya: reacted R-1233zd (E body) is containing proportional (% by mole)
Yb: reacted R-1233zd (Z body) is containing proportional (% by mole)
Yc: reacted 3,3,3-trifluoropropyne are containing proportional (% by mole)
Yd:CF
3cH=CHOEt (E) is containing proportional (% by mole)
Ye:CF
3cH=CHOEt (Z) is containing proportional (% by mole)
(R-1233ze (E or Z): isomer A containing ratio (%) (Z) in R-1233zd (E body))
Z＝100×Za/(Za+Zb)
Za: reacted R-1233ze (E or Z): isomer A is containing proportional (% by mole)
Zb: reacted R-1233zd (E body) is containing proportional (% by mole)
(Production Example 4)
Implement 2 comparative examples 1, by the composition be mixed to get prepare below 5564g containing R-1233zd (E body) composition 1.
It is 86.0 % by mole containing R-1233zd (E body) composition 1:R-1233zd (E body), R-1233zd (Z body) is 6.4 % by mole, 3,3,3-trifluoropropyne is 1.0 % by mole, and R-243fa is 3.8 % by mole, R-1233ze (E or Z body): isomer A is 2.2 % by mole, R-1233ze (E or Z body): isomer B is 0.4 % by mole, R-1233zc is 0.3 % by mole
(embodiment 3)
< contains the distillation purifying > of the organic layer of the R-1233zd (E body) synthesized by embodiment 1
Possess can heat 5LSUS stove, return line, reflux timer, multitube cooling electrical condenser, nitrogen pipeline, back pressure pump and dry ice cooling low-boiling point material reclaim collector footpath 2.7cm × height 300cm (charges height 250cm) SUS distillation tower in fill HeliPackNo.3 (Zhu Zhongjinwang Co., Ltd. system) (stage number measured value 30 layers), use it to distill.(R-1233zd (E body) is 90.0 % by mole to organic layer embodiment 1 obtained, R-1233zd (Z body) is 6.4 % by mole, 3,3,3-trifluoropropyne is 1.6 % by mole, and R-243fa is 1.9 % by mole, other compositions are 0.1 % by mole) in 2900g drop in water distilling apparatus, by reflux timer, the ratio of return time/set apart is adjusted to 150/1 ~ 300/1, adjusts back pressure pump nitrogen and be pressurised into 0.2MPa, distill.Result obtains R-1233zd (E body) composition more than 99.0 % by mole of 2364g.In addition, as stove residual component, 218g composition is reclaimed.The distillation behavior of the present embodiment is shown in Fig. 1, and the composition of stove residual component is shown in table 2.
(comparative example 3)
< contains the distillation purifying > of the organic layer of the R-1233zd (E body) synthesized by comparative example 1
The water distilling apparatus identical with embodiment 3 is used to distill.
(R-1233zd (E body) is 86.0 % by mole to R-1233zd (E body) composition 1 that contains 5564g Production Example 4 obtained, R-1233zd (Z body) is 6.4 % by mole, 3, 3, 3-trifluoropropyne is 1.0 % by mole, R-243fa is 3.8 % by mole, R-1233ze (E or Z body): isomer A is 2.2 % by mole, R-1233ze (E or Z body): isomer B is 0.4 % by mole, R-1233zc is 0.3 % by mole) drop into water distilling apparatus, by reflux timer, the ratio of return time/set apart is adjusted to 300/1 ~ 600/1, adjust back pressure pump while be pressurised into 0.2MPa with nitrogen, distill.Result does not obtain R-1233zd (E body) composition more than 99.0 % by mole, but obtains R-1233zd (E body) and R-1233ze (E or Z body): the blend compositions of isomer A.The receipts amount of blend compositions (R-1233zd (E body)+R-1233ze (E or Z body): isomer A is more than 99.0 % by mole) is 3630g, it consists of R-1233zd (E body) 98.3 % by mole, and R-1233ze (E or Z body): isomer A1.7 % by mole.In addition, as stove residual component, 559g composition is reclaimed.The distillation behavior of this comparative example is shown in Fig. 2, and the composition of stove residual component is shown in table 2.
Table 2
The possibility that industry utilizes
The manufacture method of R-1233zd of the present invention (E body), due to by easy method, obtain highly purified R-1233zd (E body) with highly selective, is therefore applicable to the manufacture of highly purified R-1233zd (E body).
In addition, the announcement of all the elements as specification sheets of the present invention of the specification sheets of No. 2013-092488, the Japanese patent application that on April 25th, 2013 files an application, claims, accompanying drawing and summary is quoted here.
Claims (12)
1. a manufacture method for (E)-1-chloro-3,3,3 ,-trifluoropropene, is characterized in that,
Will containing chloro-3,3, the 3-trifluoro propane of 1,1-bis-and 1, first composition purifying of chloro-1,3, the 3-trifluoro propane of 3-bis-, make chloro-relative to 1,1-bis-3,3,3-trifluoro propane and 1,3-bis-chloro-1,3, the total amount of 3-trifluoro propane, 1,3-bis-chloro-1, second composition of content below 5 % by mole of 3,3-trifluoro propane
Then, make in the second composition 1,1-bis-chloro-3,3,3-trifluoro propane carry out dehydrochlorination reaction, obtain (E)-1-chloro-3,3,3 ,-trifluoropropene.
2. manufacture method as claimed in claim 1, is characterized in that, chloro-relative to 1,1-bis-3 in the second composition, 3,3-trifluoro propane and 1,3-bis-chloro-1,3, the content of 1,3-bis-chloro-1,3,3-trifluoro propane of the total amount of 3-trifluoro propane is below 1 % by mole.
3. manufacture method as claimed in claim 1 or 2, it is characterized in that, the purifying of the first composition is undertaken by distillation.
4. the manufacture method according to any one of claims 1 to 3, is characterized in that, dehydrochlorination reaction is undertaken by making the second composition contact with metal hydroxide solutions.
5. manufacture method as claimed in claim 4, it is characterized in that, metal hydroxide solutions is the metal hydroxides aqueous solution.
6. the manufacture method as described in claim 4 or 5, is characterized in that, metal hydroxides is alkali metal hydroxide.
7. the manufacture method according to any one of claim 4 ~ 6, is characterized in that, dehydrochlorination reaction carries out in the presence of a phase transfer catalyst.
8. manufacture method as claimed in claim 7, it is characterized in that, phase-transfer catalyst is quaternary ammonium salt.
9. the manufacture method according to any one of claim 1 ~ 8, is characterized in that, vinylidene fluoride and dichlorofluoromethane is reacted, obtains the first composition.
10. manufacture method as claimed in claim 9, is characterized in that, under the existence of catalyzer being selected from aluminum chloride, modified chlorinated zirconium and lewis acid catalyst, vinylidene fluoride and dichlorofluoromethane are reacted.
11. manufacture method according to any one of claim 1 ~ 8, is characterized in that, five halogenopropanes and hydrogen fluoride are reacted, obtains the first composition.
12. manufacture method according to any one of claim 1 ~ 11, be is characterized in that, carry out purifying to the composition obtained by dehydrochlorination reaction.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013092488 | 2013-04-25 | ||
| JP2013-092488 | 2013-04-25 | ||
| PCT/JP2014/061631 WO2014175403A1 (en) | 2013-04-25 | 2014-04-24 | Process for producing (e)-1-chloro-3,3,3-trifluoropropene |
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| CN115304449A (en) * | 2017-01-23 | 2022-11-08 | 墨西哥氟石股份公司 | Process for removing haloalkyne impurities from (hydro) halohydrocarbon compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPWO2015186556A1 (en) * | 2014-06-06 | 2017-04-20 | 旭硝子株式会社 | Process for producing 1,1-dichloro-3,3,3-trifluoropropane |
| JP2016124847A (en) * | 2015-01-07 | 2016-07-11 | 旭硝子株式会社 | Method for producing trifluoroethylene |
| US9764998B2 (en) | 2015-05-12 | 2017-09-19 | Honeywell International Inc. | Process for making HCFO-1233zd |
| US20160332935A1 (en) * | 2015-05-12 | 2016-11-17 | Honeywell International Inc. | Integrated Process for Making HCFO-1233zd and HFC-245fa |
| JP6635118B2 (en) | 2015-09-04 | 2020-01-22 | Ａｇｃ株式会社 | Solvent composition, cleaning method and method for forming coating film |
| CN107922294A (en) * | 2015-09-11 | 2018-04-17 | 科慕埃弗西有限公司 | The dehydrohalogenation of hydrochlorofluorocarbons |
| MX2019006410A (en) * | 2016-12-02 | 2019-09-04 | Honeywell Int Inc | Process for drying hcfo-1233zd. |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101168494A (en) * | 2007-11-27 | 2008-04-30 | 常熟三爱富中昊化工新材料有限公司 | Preparation method for chlorotrifluoropropylene |
| WO2012145188A2 (en) * | 2011-04-20 | 2012-10-26 | Honeywell International Inc. | PROCESS FOR PRODUCING TRANS-1233zd |
| RU2476417C1 (en) * | 2011-10-20 | 2013-02-27 | Ильдар Айдарович Султангузин | Method of producing 2,3,3,3-tetrafluoropropylene and 1,3,3,3-tetrafluoropropylene |
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| JP6107467B2 (en) * | 2012-06-29 | 2017-04-05 | セントラル硝子株式会社 | Process for producing 1-chloro-3,3,3-trifluoropropene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168494A (en) * | 2007-11-27 | 2008-04-30 | 常熟三爱富中昊化工新材料有限公司 | Preparation method for chlorotrifluoropropylene |
| WO2012145188A2 (en) * | 2011-04-20 | 2012-10-26 | Honeywell International Inc. | PROCESS FOR PRODUCING TRANS-1233zd |
| RU2476417C1 (en) * | 2011-10-20 | 2013-02-27 | Ильдар Айдарович Султангузин | Method of producing 2,3,3,3-tetrafluoropropylene and 1,3,3,3-tetrafluoropropylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304449A (en) * | 2017-01-23 | 2022-11-08 | 墨西哥氟石股份公司 | Process for removing haloalkyne impurities from (hydro) halohydrocarbon compositions |
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| WO2014175403A1 (en) | 2014-10-30 |
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| JPWO2014175403A1 (en) | 2017-02-23 |
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