CN105143155B - 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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- CN105143155B CN105143155B CN201480023284.4A CN201480023284A CN105143155B CN 105143155 B CN105143155 B CN 105143155B CN 201480023284 A CN201480023284 A CN 201480023284A CN 105143155 B CN105143155 B CN 105143155B
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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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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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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 the chloro- 3,3,3- trifluoro propenes of (E) -1- (hereinafter also referred to R-1233zd (E bodies)).
In addition, in this specification, cis-trans isomer is represented with Z-E, cis body is shown with Z body surfaces, trans body E body surfaces show,
The mixture of Z bodies and E bodies and do not differentiate between Z bodies and E bodies be referred to as EZ bodies.
Background technology
In this specification, sometimes for halogenated hydrocarbon by the abbreviation of its compound (cold-producing medium numbering etc.) note chemical combination name it
In parantheses afterwards, but in this manual, also referred to as replace chemical combination name using which sometimes as needed.
Greenhouse gases HFA 134a (hereinafter also referred to R-134a), 1,1,1,3,3- five fluorine as an alternative
Propane (hereinafter also referred to R-245fa) is used as cold-producing medium, foaming agent, abluent, solvent and aerosol and function
The starting monomer and synthesis intermediate of property material, in recent years R-1233zd (E bodies) expected.
Method as the R-1233zd (E bodies) is manufactured, for example, propose the presence in the pentachloropropane as catalyst
Under, it is fluorinated with fluohydric acid gas and is made after dichloro trifluoro propane, the dichloro trifluoro propane to obtaining in alkali alcosol enters
The method (for example, referring to patent documentation 1) of row dehydrochlorination.Further it is proposed that 1,1- bis- chloro- 3 is made, 3,3- trifluoro propane (with
It is also referred to as down R-243fa) method that contacts to carry out dehydrochlorination reaction with aqueous alkali (for example, referring to patent documentation 2).
In these techniques, disclose and R-1233zd (E bodies) can be manufactured by R-243fa.
R-1233zd (E bodies) is in terms of it can use as the starting monomer of functional material and synthesis intermediate
Consider, preferably obtained with high-purity.Additionally, in the use of cold-producing medium, foaming agent, abluent, solvent, aerosol etc., it is considered to
To various decrees, sign obligation, rule etc. are closed, preferably obtained with high-purity.
But, in technology set forth above, there is a problem of to obtain R-1233zd (E bodies) with high-purity.
Therefore, present situation is that requirement provides a kind of method for passing through simplicity, obtains highly purified R- with high selectivity
The manufacture method of the R-1233zd (E bodies) of 1233zd (E bodies), and pass through compositionss obtained by the manufacture method.
Furthermore it is known that industrially in the method for easy method manufacture dichloro trifluoro propane (for example, referring to patent documentation
3).But, in the method, it is known that together with R-243fa, 1,3- bis- chloro- 1,3,3- trifluoro propane (hereinafter referred to as R-243fb)
Produce as by-product.
Prior art literature
Patent documentation
Patent documentation 1：Chinese patent discloses No. 101168494 publications
Patent documentation 2：No. 2012/145188 text of International Publication No.
Patent documentation 3：Japanese Patent Laid-Open 8-73385 publication
The content of the invention
Invent technical problem to be solved
Patent documentation 1, and 2 method in, it is believed that with R-1233zd (E bodies) while generating (E) -3- as by-product
Chloro- 1,3,3- trifluoro propenes (hereinafter referred to as R-1233ze (E bodies)) and chloro- 1,3, the 3- trifluoro propenes of (Z) -3- are (hereinafter referred to as
R-1233ze (Z bodies)).The inventors discovered that, R-1233zd (E bodies) and R-1233ze (E bodies) and R-1233ze (Z bodies) is steamed
Fraction is from being difficult.That is, exist by patent documentation 1, and 2 method can not obtain highly purified R-1233zd's (E bodies)
Problem.
Additionally, the present inventor is had found when R-1233zd (E bodies) is manufactured by R-243fa, if as the isomery of R-243fa
The R-243fb of body is present in reaction system, then R-243fb is changed into R-1233ze (E bodies) and R-1233ze (Z bodies).
The problem of the present invention is to provide a kind of method by simplicity and obtains highly purified R-1233zd with high selectivity
The manufacture method of the R-1233zd (E bodies) of (E bodies).
Solve the technical scheme adopted by technical problem
The inventors discovered that, in the manufacture method of R-1233zd (E bodies), R-243fa and R- are contained by purification
The first chamber of 243fb, obtain total amount relative to R-243fa and R-243fb, the content of R-243fb be 5 moles of % with
Under second chamber after, carry out the dehydrochlorination reaction of the R-243fa in second chamber, obtain R-1233zd (E bodies), by
This can obtain highly purified R-1233zd (E bodies) by easy method, with high selectivity, so as to complete the present invention.
The manufacture method of (E) -1- chloro-3,3,3 ,-trifluoropropenes (R-1233zd (E bodies)) of the present invention is characterised by, incites somebody to action
Contain 1,1- bis- chloro- 3,3,3- trifluoro propane (R-243fa) and 1,3- bis- chloro- 1, the of 3,3- trifluoro propane (R-243fb)
One compositionss purification, makes relative to 1,1- bis- chloro- 3,3,3- trifluoro propane (R-243fa) and 1,3- bis- chloro- 1,3,3- tri-
The total amount of fluoro-propane (R-243fb), 1,3- bis- chloro- 1, the content of 3,3- trifluoro propane (R-243fb) are the of 5 moles of below %
Two compositionss, then, obtain 1, the 1- bis- chloro- 3 in second chamber, 3,3- trifluoro propane (R-243fa) dehydrochlorination reactions
To (E) -1- chloro-3,3,3 ,-trifluoropropenes (R-1233zd (E bodies)).
The effect of invention
If using the present invention, a kind of method by simplicity can be provided and obtains highly purified R- with high selectivity
The manufacture method of the R-1233zd (E bodies) of 1233zd (E bodies).
Description of the drawings
Fig. 1 is the figure of the behavior for representing the purification in embodiment 3.
Fig. 2 is the figure of the behavior for representing the purification in comparative example 3.
Specific embodiment
Hereinafter the operation of " by first chamber purification, obtaining second chamber " in the manufacture method of the present invention is referred to as
" purification procedures (1) ".Additionally, " dehydrochlorination reaction of the R-243fa in second chamber will be carried out, R-1233zd (E are obtained
Body) " operation be referred to as " manufacturing process (A) ".
Also, " operation of manufacture first chamber " is referred to as into " manufacturing process (B) ", will be to obtained by manufacturing process (A)
Reactant mixture carries out the operation of purification and is referred to as " purification procedures (2) ".
(manufacture method of R-1233zd (E bodies))
The manufacture method of the R-1233zd (E bodies) of the present invention includes purification procedures (1) and manufacturing process (A), preferably enters one
Step includes at least arbitrary operation of manufacturing process (B) and purification procedures (2).
In the case where the manufacture method of R-1233zd (E bodies) includes manufacturing process (B), the manufacture of R-1233zd (E bodies)
Method is generally carried out according to the order of manufacturing process (B), purification procedures (1), manufacturing process (A).
In the case where the manufacture method of R-1233zd (E bodies) includes purification procedures (2), the manufacture of R-1233zd (E bodies)
Method is generally carried out according to the order of purification procedures (1), manufacturing process (A), purification procedures (2).
In the case where the manufacture method of R-1233zd (E bodies) includes manufacturing process (B) and purification procedures (2), R-
The manufacture method of 1233zd (E bodies) is generally according to manufacturing process (B), purification procedures (1), manufacturing process (A) and purification procedures
(2) order is carried out.
<Purification procedures (1)>
Purification procedures (1) are the first chambers that purification contains R-243fa and R-243fb, are obtained relative to R-243fa
And the total amount of R-243fb, the operation of the second chamber that the content of R-243fb is 5 moles of below %.As purification procedures
(1) purification process in is not particularly limited, and can suitably be selected according to purpose, for example, can enumerate distillation, absorption etc..
Wherein, from from the aspect of easily can carry out, preferably distill.
[distillation]
Distillation can be carried out at ambient pressure, also also can be carried out under reduced pressure under elevated pressure.Wherein, preferably enter at ambient pressure
OK.
In the case where being distilled, using the appropriate fraction in distillation as second chamber.
First chamber at least contain R-243fa and R-243fb, further as needed, can containing beyond these into
Divide (hereinafter referred to as other compositions).
As the other compositions, for example, can enumerate compound chloroform (chloroform), the tetrachloro being close to R-243fa boiling points
Methane (carbon tetrachloride), 1,2- dichloroethanes, 1,1- dichloroethanes, 1,1,2- tri- chloro- 3,3- Difluoroethanes (R-122), 1,1,
Chloro- 1,3,3, the 3- tetrafluoropropane (R-244fa) of 2- trichloro ethylenes, 1-, bis- chloro- 3,3- difluoropropenes (R-1232zd of (EZ) -1,3-
(EZ bodies)), chloro- 1,3, the 3- trifluoro propenes of (EZ) -3- (R-1233ze (EZ bodies)), (Z) -1- chloro-3,3,3 ,-trifluoropropenes (below
Referred to as R-1233zd (Z bodies)), 3,3- bis- chloro- 1,1,3- trifluoro propene (R-1233zc), other dichlorodifluoromethanes are (hereinafter referred to as
R-22), dichlorofluoromethane (hereinafter referred to as R-21), fluoroform (hereinafter referred to as R-23) etc..
R-243fb and other compositions are generated as by-product in the operation of the manufacture R-243fa such as manufacturing process (B),
It is included in first chamber.
Preferably 50 moles more than % of the content ratio of the R-243fa in first chamber.
Preferably 10 moles below % of the content ratio of the R-243fb in first chamber.
In the case where first chamber contains other compositions, the content ratio of the other compositions in first chamber is preferred
30 moles of below %.
In second chamber, rub for 5 relative to the content ratio of the R-243fb of the total amount of R-243fa and R-243fb
You are below %, preferably 3 moles below %, more preferably 1 mole below %.If the content of R-243fb is in preferred scope,
Readily aspect is favourable for impurity then in dehydrochlorination reaction product is reduced, purification.
As the content ratio of the R-243fb in second chamber, preferably 5 moles below %, further preferred 1 mole of %
Hereinafter, particularly preferred 0.5 mole of below %.
Generally by the purification of first chamber, other compositions are also removed as R-243fb, thereby, the second combination
The content of the other compositions in thing also tails off.In the case of there are other compositions in second chamber, in second chamber
Preferably 1 mole below % of the ratio of other compositions, more preferably 0.1 mole below %.
In terms of the reactivity of the dehydrochlorination reaction after raising, and the impurity after dehydrochlorination reaction reduce,
From the aspect of purification is easy, in particularly preferred second chamber, the total content ratio of R-243fa and R-243fb is 100
Mole %.
<Manufacturing process (A)>
The dehydrochlorination reaction of manufacturing process (A) preferably by second chamber is contacted with metal hydroxide solutions come
Carry out.As metal hydroxide solutions, the alcoholic solution of metal hydroxidess aqueous solution and metal hydroxidess can be enumerated.
Here, as metal hydroxidess, alkaline-earth metal hydroxide, alkali metal hydroxide etc. can be enumerated.
Dehydrochlorination reaction from response time, reaction yield and R-1233zd (E bodies) it is selective from the aspect of,
It is preferred that so that the method that second chamber is contacted with alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst is carried out.
As alkaline-earth metal hydroxide, for example, can enumerate magnesium hydroxide, calcium hydroxide, Strontium hydrate., barium hydroxide.As alkali gold
Category hydroxide, for example, can enumerate Lithium hydrate, sodium hydroxide, potassium hydroxide.
As metal hydroxidess aqueous solution, for example, can enumerate sodium hydrate aqueous solution, potassium hydroxide aqueous solution.As gold
Category hydroxide alcohol solution, can enumerate the ethanol solution of sodium hydroxide.Wherein, from R-1233zd (E bodies) it is selective in terms of
Consider, preferably metal hydroxidess aqueous solution, more preferably sodium hydrate aqueous solution, potassium hydroxide aqueous solution.
The concentration of metal hydroxide solutions, from from the aspect of response speed, as solute (metal hydroxidess)
Quality %, preferably 0.5～40 mass %, more preferably 5～30 mass %.It is metal hydroxidess water in metal hydroxide solutions
In the case of solution, if concentration within the above range if easily can carry out 2 layers separation.
As the usage amount of the metal hydroxide solutions in dehydrochlorination reaction, relative to R-243fa, metal hydroxide
The alkali number of thing preferably 0.5～2.0 molar equivalent, the more preferably alkali number of 1.0～1.5 molar equivalents.
Used in dehydrochlorination reaction in the case of metal hydroxidess aqueous solution, in order that reaction is efficiently carried out,
Preferably use phase transfer catalyst.
As phase transfer catalyst, for example, can enumerate quaternary ammonium salt, quaternary salt, quaternary salt, sulfonium salt, crown ether etc..It is wherein preferred
Quaternary ammonium salt.
[quaternary ammonium salt]
As quaternary ammonium salt, for example, can enumerate compound that following formulas (i) represent (hereinafter sometimes referred to " compound
(i)”)。
[changing 1]
In formula (i), R11～R14Alkyl, Y are represented separately-Represent anion.
As R11～R14In alkyl, can for example enumerate alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl etc..Its
In, preferably alkyl, aryl.
As R11～R14Carbon number, with every 1 molecule R11R12R13R14N+Total carbon number meter, preferably 4～100.
R11～R14Can be identical group, or different groups respectively.
R11～R14Can be replaced by inert functional groups at reaction conditions.As inert functional groups, according to reaction condition
Difference, for example, can enumerate halogen atom, ester group, itrile group, acyl group, carboxyl, alkoxyl etc..
As Y-, can for example enumerate chloride ion, fluorion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphoric acid from
Son, high chloro acid ion, hydrogen sulfate ion, hydroxide ion, acetato-, benzoate, benzenesulfonic acid ion, to toluene sulphur
Acid ion etc..Wherein, preferably chloride ion, bromide ion, iodide ion, hydrogen sulfate ion, hydroxide ion.
It is as compound (i), from from the aspect of the versatility and reactivity of compound (i), preferably following
R11R12R13R14N+With following Y-Combination.
R11R12R13R14N+：Tetramethyl ammonium, tetraethyl ammonium ion, four n-pro-pyl ammonium ions, tetra-n-butyl ammonium ion,
Three n-octyl ammonium ions.
Y-：Fluorion, chloride ion, bromide ion, iodide ion, hydroxide ion.
As the quaternary ammonium ion in quaternary ammonium salt, for example, can enumerate tetramethyl ammonium, tetraethyl ammonium ion, four n-pro-pyl ammoniums
Ion, tetra-n-butyl ammonium ion, three n-octyl ammonium ions, cetyltrimethylammonium ammonium ion, benzyl trimethyl ammonium ion, benzyl
Base triethyl ammonium ion, cetyl benzyl dimethyl ammonium ion, cetyl pyridinium ion, dodecyl pyridinium ion,
Phenyl trimethicone ammonium ion, phenyl triethylammonium ammonium ion, N- benzyl methyl pyridinium ions, five first ammonium ion (Japaneses：ペンタ
メ ト ニ ウ system イ オ Application), pregnancy ammonium ion (Japanese：ヘ キ サ メ ト ニ ウ system イ オ Application) etc..
As quaternary ammonium salt, particularly preferred tetrabutylammonium chloride.
[quaternary salt]
As quaternary salt, the compound that following formulas (ii) are represented can be enumerated.
[changing 2]
In formula (ii), R21～R24Alkyl, Y are represented separately-Represent anion.
As R21～R24In alkyl, can for example enumerate alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl etc..Its
In, preferably alkyl, aryl.
As the quaternary ion (R in formula (ii)21R22R23R24P+), can for example enumerate tetraethyl ion, tetra-n-butyl
Ion, three n-octyl ethyl ions, cetyl triethyl group ion, three normal-butyl ion of cetyl, normal-butyl triphen
Base ion, n-pentyl triphenyl ion, methyl triphenyl ion, benzyltriphenyl phosphonium ion, tetraphenylphosphonium ion etc..
As Y-, can for example enumerate chloride ion, fluorion, bromide ion, iodide ion, sulfate ion, nitrate ion, phosphoric acid from
Son, high chloro acid ion, hydrogen sulfate ion, hydroxide ion, acetato-, benzoate, benzenesulfonic acid ion, to toluene sulphur
Acid ion etc..Wherein, preferably fluorion, chloride ion, bromide ion.
[quaternary salt]
As quaternary salt, the compound that following formulas (i i i) are represented can be enumerated.
[changing 3]
In formula (iii), R31～R34Alkyl, Y are represented separately-Represent anion.
As R31～R34In alkyl, can for example enumerate alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl etc..Its
In, preferably alkyl, aryl.
As Y-, preferably halide ion, more preferably fluorion, chloride ion, bromide ion.
As quaternary salt, for example, can enumerate fluorination trityl group salt, fluorination tetraphenyl salt, triphenylmethylphosphonium chloride
Salt, tetraphenylarsonium chloride base salt, tetraphenylphosphonibromide bromide salt, their polymeric derivative etc..
As quaternary salt, particularly preferred triphenylmethylphosphonium chloride salt.
[sulfonium salt]
As sulfonium salt, the compound that following formulas (iv) are represented can be enumerated.
[changing 4]
In formula (iv), R41～R43Alkyl, Y are represented separately-Represent anion.
As R41～R43In alkyl, can for example enumerate alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl etc..Its
In, preferably alkyl, aryl.
As Y-, preferably halide ion, more preferably fluorion, chloride ion, bromide ion.
As sulfonium salt, for example, can enumerate di-n-butyl methyl sulfonium iodine salt, three normal-butyl sulfonium tetrafluoroborates, dihexyl methyl
Sulfonium iodine salt, dicyclohexylmethyl sulfonium iodine salt, chlorination dodecyl methyl ethyl sulfonium salt, three (diethylamino) sulfonium difluoro trimethyl
Silicate etc..
As sulfonium salt, particularly preferred chlorination dodecyl methyl ethyl sulfonium salt.
[crown ether]
As crown ether, for example, can enumerate 18- crown-s 6, dibenzo-18 crown-6 etc..
As the usage amount 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 for example can by using the second chamber as raw material and alkali metal hydroxide aqueous solution,
Reactor is imported with the appropriate ratio for selecting with phase transfer catalyst so as to be fully contacted, using conventional method be stirred come
Implement.
As the reaction temperature in dehydrochlorination reaction, from reactivity and the selective side of R-1233zd (E bodies)
Face consideration, preferably 0～80 DEG C.In addition, reaction temperature can be suitably adjusted according to the pressure state of reaction vessel during reaction.
For example, in the case of carrying out dehydrochlorination reaction at ambient pressure, preferably 0～60 DEG C, more preferably 20～60 DEG C of reaction temperature.If
Reaction temperature in preferred scope, then to R-243fa is with more efficient response speed and carries out dechlorination with high selectivity
It is favourable in terms of changing hydrogen.
In addition it is also possible to carry out dehydrochlorination reaction in compressive reaction container, as optimum condition in this case, it is
98000～200000Pa and 20～60 DEG C.
Dehydrochlorination reaction can batch-type carry out, also can continuous stream formula carry out.
As for dehydrochlorination reaction reactor material, can enumerate for example glass, ferrum, nickel or using them as master
Want alloy of composition etc..
Wherein, the preferred alloy containing ferrum such as rustless steel.
<Manufacturing process (B)>
As manufacturing process (B), preferably make vinylidene fluoride (vinylidene) and R-21 reactions and obtain the first combination
The operation of thing.Hereinafter, the manufacturing process (B) is referred to as into manufacturing process (B-1).
By using manufacturing process (B-1), the purification being obtained in purification procedures (1) is easy, R-243fa and R-
The poor first chamber of the other compositions beyond 243fb.
Reaction in above-mentioned manufacturing process (B-1) can be represented with following reaction equations (1).In addition, in following reaction equations
C3H3Cl2F3Dichloro trifluoro propane (R-243) is represented, R-243 is the dichloro trifluoro propane isomers such as R-243fa, R-243fb
General name.The R-243 obtained with the reaction is typically the isomer mixture containing R-243fa and R-243fb.
[changing 5]
CF2=CH2+CHCl2F→C3H3Cl2F3 (1)
In addition, also containing chloroform, R-23,1,1,1- HFC-143a in addition to R-243 in the product of reaction equation (1)
(hereinafter referred to as R-143a) etc..
The content ratio of the R-243fb in the compositionss that above-mentioned manufacturing process (B-1) is obtained according to reaction condition (especially
The species of reaction temperature and the catalyst for being used) and it is different, but R-243fa is commonly angled relative to for 1 mole of more than %.
Reaction in above-mentioned manufacturing process (B-1) preferably uses catalyst and carries out.As catalyst, for example, can enumerate chlorination
The modified chlorinated zirconium of the process such as aluminum, Jing Arcton 11s, lewis acid catalyst etc..As lewis acid catalyst, for example may be used
Enumerate halogenide of at least any of element containing Al, Sb, Nb, Ta, W, Re, B, Sn, Ga, In, Zr, Hf and Ti etc..
In the case that used in above-mentioned manufacturing process (B-1), aluminum chloride is as catalyst, by obtained by reaction equation (1)
Compositionss containing R-243 are the compositionss for mainly containing R-243fa and R-243fb as product, in addition, are also made
Contain chloroform, R-23, R-143a etc. for product.Said composition can be used as first chamber.
(for example, referring to Japanese special in the case that used in above-mentioned manufacturing process (B-1), modified chlorinated zirconium is as catalyst
Sharp Unexamined Patent 4-253928 publication), it is to mainly contain R-243fa and R-243fb to make by compositionss obtained by reaction equation (1)
For the compositionss of product, in addition, also contain the compositions such as a small amount of chloroform, R-23, R-143a as product.Should
Compositionss can be used as first chamber.
In the case that used in above-mentioned manufacturing process (B-1), lewis acid catalyst is as catalyst, by reaction equation
(1) compositionss obtained by are the compositionss for mainly containing R-243fa and R-243fb as product, in addition, also conduct
Product contains the compositions such as a small amount of chloroform, R-23, R-143a.Said composition can be used as first chamber.
Method as first chamber is obtained, it is also possible to operation (the hereinafter referred to as manufacturing process using following methods
(B-2)) replacing aforesaid manufacturing process (B-1).
<Manufacturing process (B-2)>
Manufacturing process (B-2) as long as make five halogenopropanes and hydrogen fluoride reaction and obtain the operation of first chamber i.e.
Can, it is not particularly limited, can be suitably selected according to purpose.
Reaction in manufacturing process (B-2) can be represented with following reaction equations (2).In addition, in following reaction equations
C3H3Cl2F3Represent R-243.
[changing 6]
CClmF(3-m)CH2CHCl2+mHF→C3H3Cl2F3 (2)
In reaction equation (2), m is 1～3 integer.
The content ratio of the R-243fb in the compositionss that above-mentioned manufacturing process (B-2) is obtained according to reaction condition (especially
The species of reaction temperature and the catalyst for being used) and it is different, but R-243fa is commonly angled relative to for 1 mole of more than %.
<Purification procedures (2)>
Can be further purified as needed by compositionss obtained by the dehydrochlorination reaction in the present invention.As purification,
Distillation, absorption, cleaning etc. can be enumerated.As cleaning, can enumerate using acidic aqueous solution, neutral aqueous solution or alkaline aqueous solution
Cleaning.As purification, particularly preferably distill.
Used in dehydrochlorination reaction in the case of metal hydroxidess aqueous solution, reacted compositionss contain water.
Therefore, when purification is carried out, compositionss are separated into into organic layer and water layer first, afterwards, organic layer are distilled.
In the present invention, first chamber (material combination in the purification procedures (1) before dehydrochlorination reaction is carried out by reducing
Thing) in R-243fb, reduce with R-1233zd (E bodies) be difficult to separate (for example, separated), as R-1233zd (E
Body) isomer R-1233ze (E bodies) and R-1233ze (Z bodies) content, thereby can be carried out by conventional distillation
Isolate and purify, obtain highly purified R-1233zd (E bodies).
<The purposes of R-1233zd (E)>
By R-1233zd (E) alternative greenhouse gases R-134a, R-245fa obtained by the manufacture method of the present invention
And it is used as starting monomer and the synthesis of cold-producing medium, foaming agent, abluent, solvent and aerosol and functional material
Use intermediate.
In the case where R-1233zd (E) to be used as the starting monomer and synthesis intermediate of functional material, especially
Preferably high-purity (such as 99.0 moles more than %).
Embodiment
Hereinafter, embodiments of the invention are illustrated, but the invention is not restricted to following embodiments.
[analysis condition]
Composition analysis use gas chromatography.Chromatographic column using DB-1301 (1 μm of 250 μ m thickness of length 60m × internal diameter,
Agilent Technologies (ア ジ レ Application ト テ Network ノ ロ ジ Co., Ltd.) make).Further, since R-1233ze (E bodies) and
R-1233ze (Z bodies) not by the structures shape between EZ constitutional isomers, therefore in the present embodiment, for convenience, by above-mentioned gas
In GC headspace analysis condition, the short EZ constitutional isomers of retention time are labeled as " R-1233ze (E or Z bodies)：Isomer A ", will
The EZ constitutional isomers of retention time length are labeled as " R-1233ze (E or Z bodies)：Isomer B ".
(catalyst preparation example 1)
<The preparation of modified chlorinated Zr catalyst>
Four are put in the cooler that top is connected with height 15cm, four mouthfuls of 1L glass system flasks for being put into magnetic stick
Zirconium chloride 256.9g.Then it is while the cooler and flask dry ice that are connected to top are cooled to -78 DEG C, slow to put into
The R-21 of 636g.While being stirred with magnetic-type stirrer, make to be connected to the cooler on top and the temperature of flask is slow
0 DEG C is risen to, continues stirring 2.5 hours after interior temperature reaches 0 DEG C.Afterwards, stopping is connected to the cooler and flask on top
Cool down, at room temperature 1 night of drying under reduced pressure.After drying terminates, 236.1g catalyst is reclaimed.
(Production Example 1)
<Synthesis containing R-243fa compositionss>
The group containing R-243fa as initial stage solvent is put in hastelloy 10L autoclaves
(R-243fa is 40 moles of % to compound, and R-243fb is 8 moles of %, and chloroform is 29 moles of %, and R-22 is 2 moles of %, and R-21 is 7
Mole %, other compositions are 13 moles of %) after the 1000g and catalyst 78g prepared by catalyst preparation example 1, it is cooled to -10
Till～-5 DEG C.Cooled down while stirred, so that interior temperature keeps below the R-21 that 0 DEG C of speed slowly puts into 7202g.
Then, cool down and stir, with 8 hours input vinylidene fluoride (inclined fluorine second while interior temperature keeps below 0 DEG C
Alkene) 4480g.Feed intake after end, stir 30 minutes, with nitrogen displacement gas phase portion, terminate reaction.After reaction terminates, stirring one
While from the bottom extraction stock solution of 10L autoclaves.The amount of the reaction stock solution of extraction is 12822g.Afterwards, with being provided with the filter of 5 μm of footpaths
The pressure filter of paper filters reaction stock solution, obtains the uniform organic layer of 12470g.Recovery section organic layer, by gas chromatogram
Method (GC) to composition be analyzed result, organic layer ratio of components it is as follows.
R-243fa：56 moles of %
R-243fb：9 moles of %
Chloroform：5 moles of %
R-143a：1 mole of %
R-21：9 moles of %
Other compositions：20 moles of %
(Production Example 2)
<Distillation purifying containing R-243fa compositionss>
Possess can be heated with mantle heater 10L glass system stoves, magnetic-type reflux, reflux timer,
And in the glass distillation column of the footpath 3cm height 97cm of Di Muluo coolers, fill Heli Pack No.1 (golden net strain formulas in bamboo
Commercial firm (Zhu Zhongjin Co., Ltd.) makes) (43 layers of number of plates measured value), distilled using which.Obtained by Production Example 1
Return time/distillate the ratio of time is adjusted to by the 11000g input distilling apparatus in organic layer by reflux timer
50/1～300/1, distilled at ambient pressure.
As a result, it is the compositionss of 99.5 moles of more than %, R-243fb less than 0.5 mole of % to obtain R-243fa
946g。
Additionally, obtaining compositionss 5646g that R-243fa is that 94.0 moles of %, R-243fb are 6.0 moles of %.
(Production Example 3)
Repeatedly implement Production Example 1, Production Example 2 respectively, following 4157g is prepared containing R- by the compositionss being mixed to get
243fa compositionss 1,13225g compositionss containing R-243fa 2,1570g compositionss containing R-243fa 3.
Compositionss containing R-243fa 1：R-243fa is 99.9 moles of %, and R-243fb is 0.1 mole of %
Compositionss containing R-243fa 2：R-243fa is 94.0 moles of %, and R-243fb is 5.9 moles of %, and other compositions are 0.1
Mole %
Compositionss containing R-243fa 3：R-243fa is 84.7 moles of %, and R-243fb is 15.3 moles of %
Compositionss containing R-243fa 1 used in below example 1,2.Compositionss containing R-243fa 2 used in comparative example 1.
Compositionss containing R-243fa 3 used in comparative example 2.
(embodiment 1)
<The synthesis of R-1233zd (E bodies)：Compositionss containing R-243fa (R-243fb is 0.1 mole of %) are existed with aqueous alkali
Dehydrochlorination reaction in phase transfer catalyst>
In hastelloy 10L autoclaves, addition tetrabutylammonium chloride (TBAC) 19.3g,
Compositionss containing R-243fa obtained by Production Example 31 (R-243fa is 99.9 moles of %, and R-243fb is 0.1 mole of %)
After 3861.9g (23.1 moles), 5～10 DEG C will be kept internal temperature at while 20 mass % sodium hydrate aqueous solutions of input
6907.7g (34.7 moles of NaOH).After with nitrogen displacement gas phase portion, make interior temperature rise to 25 DEG C, stir 2 hours, then make in interior temperature
40 DEG C are risen to, is stirred 6 hours.2 hours are stood after making interior temperature be cooled to 5 DEG C, from reactor lower part according to organic layer, water layer order
Reclaimed.Organic layer yield is 2913.1g, and water layer yield is 7832.4g.By gas chromatography (GC) to organic layer
The result that is analyzed of composition and other reaction results be shown in table 1.
(embodiment 2)
<The synthesis of R-1233zd (E bodies)：Compositionss containing R-243fa (R-243fb is 0.1 mole of %) are in alkali alcoholic solution
Dehydrochlorination reaction>
In glass system 1L autoclave, sodium hydroxide 116.8g (2.9 moles), ethanol (Junsei Chemical Co., Ltd. is added
(positive chemistry) Lot.2012K2003) (R-243fa is for compositionss containing R-243fa 1 obtained by 270.5g and Production Example 3
99.9 moles of %, R-243fb are 0.1 mole of %) 349.5g (2.1 moles).Make interior temperature rise to 45 DEG C, after stirring 9 hours, beat
Gas phase portion valve is driven, volatile ingredient 534.8g is reclaimed in the SUS316 inflators cooled down with dry ice.Volatile ingredient is reclaimed after terminating,
Interior temperature is cooled to into room temperature, distilled water 525.0g is put into, is stirred 24 hours.Stirring open reactor after terminating, reclaims water layer
690.3g.Organic layer is not isolated in confirmation from water phase.The composition of volatile ingredient is carried out point by gas chromatography (GC)
The result of analysis and other reaction results are shown in table 1.
(comparative example 1)
<The synthesis of R-1233zd (E bodies)：Compositionss containing R-243fa (R-243fb is 5.9 moles of %) are existed with aqueous alkali
Dehydrochlorination reaction in phase transfer catalyst>
In hastelloy 10L autoclaves, tetrabutylammonium chloride (TBAC) 19.3g, system is added
(R-243fa is 94.0 moles of %, and R-243fb is 5.9 moles of %, other compositions to make compositionss containing R-243fa 2 obtained by example 3
0.1 mole of %) after 3861.9g (23.1 moles), 5～10 DEG C will be kept internal temperature at while 20 mass % sodium hydroxide of input
Aqueous solution 6907.7g (34.7 moles of NaOH).After with nitrogen displacement gas phase portion, make interior temperature rise to 25 DEG C, stir 2 hours, then make
Interior temperature rises to 40 DEG C, stirs 8 hours.2 hours are stood after making interior temperature be cooled to 5 DEG C, from reactor lower part according to organic layer, water
Layer order is reclaimed.Organic layer yield is 2835.4g, and water layer yield is 7723.7g.It is right by gas chromatography (GC)
The result and other reaction results that the composition of organic layer is analyzed is shown in table 1.
(comparative example 2)
<The synthesis of R-1233zd (E bodies)：Compositionss containing R-243fa (R-243fb is 15.3 moles of %) are in alkali alcoholic solution
Dehydrochlorination reaction>
In the SUS316 autoclaves of 200mL, sodium hydroxide 16.7g (0.42 mole), ethanol (pure chemical strain is added
Formula commercial firm Lot.2012K2003) (R-243fa rubs for 84.7 for compositionss containing R-243fa 3 obtained by 38.8g and Production Example 3
You are %, and R-243fb is 15.3 moles of %) 50.0g (0.30 mole).Make interior temperature rise to 45 DEG C, after stirring 6 hours, open gas
Phase portion valve, reclaims volatile ingredient 77.0g in the SUS316 inflators cooled down with dry ice.Volatile ingredient is reclaimed after terminating, will be interior
Temperature is cooled to room temperature, puts into distilled water 75.3g, stirs 1 hour.Stirring open reactor after terminating, reclaims yellow aqueous solution
97.0g.Organic layer is not isolated in confirmation from water phase.The composition of volatile ingredient is analyzed by gas chromatography (GC)
Result and other reaction results be shown in table 1.
Table 1
In table 1, " R-243fa conversion ratios (%) ", " R-1233zd (E bodies) selection rate (%) ", and " R-1233zd (E
Body) in R-1233ze (E or Z)：Isomer A containing ratios (%) " is obtained by following formula.
In addition, table 1 and it is following in " Et " expression " ethyl ".
(R-243fa conversion ratios (%) are (X))
X=100 × (Xa-Xb)/Xa
Xa：R-243fa amounts (mole %) in raw material
Xb：Reacted R-243fa measures (mole %)
(R-1233zd (E bodies) selection rate (%) is (Y))
Y=100 × Ya/ (Ya+Yb+Yc+Yd+Ye)
Ya：Reacted R-1233zd (E bodies) content ratio (mole %)
Yb：Reacted R-1233zd (Z bodies) content ratio (mole %)
Yc：Reacted 3,3,3- trifluoropropyne content ratios (mole %)
Yd：CF3CH=CHOEt (E) content ratio (mole %)
Ye：CF3CH=CHOEt (Z) content ratio (mole %)
(the R-1233ze (E or Z) in R-1233zd (E bodies)：Isomer A containing ratios (%) is (Z))
Z=100 × Za/ (Za+Zb)
Za：Reacted R-1233ze (E or Z)：Isomer A content ratios (mole %)
Zb：Reacted R-1233zd (E bodies) content ratio (mole %)
(Production Example 4)
Implement 2 comparative examples 1, combining containing R-1233zd (E bodies) for below 5564g is prepared by the compositionss being mixed to get
Thing 1.
Containing R-1233zd (E bodies) compositionss 1：R-1233zd (E bodies) is 86.0 moles of %, and R-1233zd (Z bodies) rubs for 6.4
You are %, and 3,3,3- trifluoropropynes are 1.0 moles of %, and R-243fa is 3.8 moles of %, R-1233ze (E or Z bodies)：Isomer A is
2.2 moles of %, R-1233ze (E or Z bodies)：Isomer B is 0.4 mole of %, and R-1233zc is 0.3 mole of %
(embodiment 3)
<The distillation purifying of the organic layer containing the R-1233zd (E bodies) synthesized by embodiment 1>
Possess can heat 5LSUS stoves, reflux pipe, reflux timer, multitube cooling capacitor, nitrogen tube
The low-boiling point material of road, back pressure pump and dry ice cooling reclaims footpath 2.7cm × height 300cm (charges height of catcher
Heli Pack No.3 (golden net Co. Ltd. system in bamboo) (number of plates measured value 30 is filled in SUS distillation column 250cm)
Layer), distilled using which.By the organic layer obtained by embodiment 1, (R-1233zd (E bodies) is 90.0 moles of %, R-1233zd
(Z bodies) is 6.4 moles of %, and 3,3,3- trifluoropropynes are 1.6 moles of %, and R-243fa is 1.9 moles of %, and other compositions rub for 0.1
Your %) in 2900g input distilling apparatus in, the ratio of return time/set apart is adjusted to into 150/1 by reflux timer
～300/1, adjust back pressure pump and 0.2MPa is pressurised into nitrogen, distilled.As a result the R-1233zd of 2364g has been obtained
(E bodies) is more than the compositionss of 99.0 moles of %.Additionally, as stove residual component, reclaiming 218g compositionss.The distillation of the present embodiment
Behavior is shown in Fig. 1, and the composition of stove residual component is shown in table 2.
(comparative example 3)
<The distillation purifying of the organic layer containing the R-1233zd (E bodies) synthesized by comparative example 1>
Distilled using distilling apparatus same as Example 3.
Obtained by by 5564g Production Examples 4 containing R-1233zd (E bodies) compositionss 1, (R-1233zd (E bodies) rubs for 86.0
You are %, and R-1233zd (Z bodies) is 6.4 moles of %, and 3,3,3- trifluoropropynes are 1.0 moles of %, and R-243fa is 3.8 moles of %, R-
1233ze (E or Z bodies)：Isomer A is 2.2 moles of %, R-1233ze (E or Z bodies)：Isomer B is 0.4 mole of %, R-
1233zc is 0.3 mole of %) input distilling apparatus, the ratio of return time/set apart is adjusted to by reflux timer
300/1～600/1, adjust back pressure pump and 0.2MPa is pressurised into nitrogen, distilled.As a result R-1233zd (E are not obtained
Body) more than the compositionss of 99.0 moles of %, but obtained R-1233zd (E bodies) and R-1233ze (E or Z bodies)：Isomer A's
Blend compositions.Blend compositions (R-1233zd (E bodies)+R-1233ze (E or Z bodies)：Isomer A is more than 99.0 moles of %)
Receipts amount is 3630g, consisting of 98.3 moles of % of R-1233zd (E bodies), R-1233ze (E or Z bodies)：Isomer A1.7 rubs
You are %.Additionally, as stove residual component, reclaiming 559g compositionss.The distillation behavior of this comparative example is shown in Fig. 2, stove residual component
Composition be shown in table 2.
Table 2
The probability utilized in industry
The manufacture method of the R-1233zd (E bodies) of the present invention is due to obtaining height by easy method, with high selectivity
The R-1233zd (E bodies) of purity, therefore suitable for the manufacture of highly purified R-1233zd (E bodies).
In addition, quoting the explanation of the Japanese patent application 2013-092488 that on April 25th, 2013 files an application here
Announcement of all the elements of book, claims, accompanying drawing and summary as description of the invention.
Claims (14)
1. a kind of manufacture method of (E) -1- chloro-3,3,3 ,-trifluoropropenes, it is characterised in that
To contain 1,1- bis- chloro- 3,3,3- trifluoro propane and 1,3- bis- chloro- 1, the first chamber purification of 3,3- trifluoro propane,
Make relative to 1,1- bis- chloro- 3,3,3- trifluoro propane and 1,3- bis- chloro- 1, the total amount of 3,3- trifluoro propane, 1,3- bis- is chloro-
Second chamber of the content of 1,3,3- trifluoro propane in 5 moles of below %,
Then, 1, the 1- bis- chloro- 3 in second chamber is made, 3,3- trifluoro propane carry out dehydrochlorination reaction, obtain (E) -1-
Chloro- 3,3,3- trifluoro propenes.
2. manufacture method as claimed in claim 1, it is characterised in that in second chamber relative to 1,1- bis- chloro- 3,3,
The content of the bis- chloro- 1,3,3- trifluoros propane of 1,3- of the total amount of bis- chloro- 1,3,3- trifluoros propane of 3- trifluoros propane and 1,3- is 1
Mole below %.
3. manufacture method as claimed in claim 1 or 2, it is characterised in that the distillation that is purified by of first chamber is carried out.
4. manufacture method as claimed in claim 1, it is characterised in that dehydrochlorination reaction is by making second chamber and metal
Hydroxide solution contacts to carry out.
5. manufacture method as claimed in claim 4, it is characterised in that metal hydroxide solutions are that metal hydroxidess are water-soluble
Liquid.
6. the manufacture method as described in claim 4 or 5, it is characterised in that metal hydroxidess are alkali metal hydroxide.
7. the manufacture method as described in claim 4, it is characterised in that presence of the dehydrochlorination reaction in phase transfer catalyst
Under carry out.
8. manufacture method as claimed in claim 7, it is characterised in that phase transfer catalyst is quaternary ammonium salt.
9. manufacture method as claimed in claim 1, it is characterised in that make vinylidene fluoride and dichlorofluoromethane carry out instead
Should, obtain first chamber.
10. manufacture method as claimed in claim 9, it is characterised in that make 1,1- difluoros in the presence of aluminum chloride catalyst
Ethylene and dichlorofluoromethane are reacted.
11. manufacture methods as claimed in claim 9, it is characterised in that make 1,1- in the presence of modified chlorinated Zr catalyst
Difluoroethylene and dichlorofluoromethane are reacted.
12. manufacture methods as claimed in claim 9, it is characterised in that make 1,1- bis- in the presence of a lewis acid catalyst
Fluorothene and dichlorofluoromethane are reacted.
13. manufacture methods as claimed in claim 1, it is characterised in that reacted five halogenopropanes and fluohydric acid gas, obtained
First chamber.
14. manufacture methods as claimed in claim 1, it is characterised in that the compositionss to being obtained by dehydrochlorination reaction are entered
Row purification.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-092488 | 2013-04-25 | ||
| JP2013092488 | 2013-04-25 | ||
| PCT/JP2014/061631 WO2014175403A1 (en) | 2013-04-25 | 2014-04-24 | Process for producing (e)-1-chloro-3,3,3-trifluoropropene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105143155A CN105143155A (en) | 2015-12-09 |
| CN105143155B true CN105143155B (en) | 2017-03-22 |
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| CN201480023284.4A Expired - Fee Related CN105143155B (en) | 2013-04-25 | 2014-04-24 | Process for producing (e)-1-chloro-3,3,3-trifluoropropene |
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| Country | Link |
|---|---|
| JP (1) | JP6245259B2 (en) |
| CN (1) | CN105143155B (en) |
| WO (1) | WO2014175403A1 (en) |
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| CN106458800A (en) * | 2014-06-06 | 2017-02-22 | 旭硝子株式会社 | Method 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 |
| US20160332935A1 (en) * | 2015-05-12 | 2016-11-17 | Honeywell International Inc. | Integrated Process for Making HCFO-1233zd and HFC-245fa |
| US9764998B2 (en) | 2015-05-12 | 2017-09-19 | Honeywell International Inc. | Process for making HCFO-1233zd |
| CN112239704B (en) | 2015-09-04 | 2022-04-01 | Ａｇｃ株式会社 | Solvent composition, cleaning method, and method for forming coating film |
| EP3347334A4 (en) * | 2015-09-11 | 2019-05-01 | The Chemours Company FC, LLC | Dehydrohalogenation of hydrochlorofluorocarbons |
| MX2019006410A (en) * | 2016-12-02 | 2019-09-04 | Honeywell Int Inc | Process for drying hcfo-1233zd. |
| GB201701099D0 (en) * | 2017-01-23 | 2017-03-08 | Mexichem Fluor Sa De Cv | Process |
Citations (3)
| 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 |
Family Cites Families (1)
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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 |
-
2014
- 2014-04-24 CN CN201480023284.4A patent/CN105143155B/en not_active Expired - Fee Related
- 2014-04-24 JP JP2015513841A patent/JP6245259B2/en not_active Expired - Fee Related
- 2014-04-24 WO PCT/JP2014/061631 patent/WO2014175403A1/en active Application Filing
Patent Citations (3)
| 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 |
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| JPWO2014175403A1 (en) | 2017-02-23 |
| WO2014175403A1 (en) | 2014-10-30 |
| CN105143155A (en) | 2015-12-09 |
| JP6245259B2 (en) | 2017-12-13 |
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