CA1220216A - Process for the production of hexafluoropropylene oxide - Google Patents
Process for the production of hexafluoropropylene oxideInfo
- Publication number
- CA1220216A CA1220216A CA000402298A CA402298A CA1220216A CA 1220216 A CA1220216 A CA 1220216A CA 000402298 A CA000402298 A CA 000402298A CA 402298 A CA402298 A CA 402298A CA 1220216 A CA1220216 A CA 1220216A
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- CA
- Canada
- Prior art keywords
- hexafluoropropylene
- reaction
- hypochlorite
- aqueous phase
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
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- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for producing hexafluoropropylene oxide from hexafluoropropylene is described. The process comprises epoxidizing hexafluoropropylene in a two-phase system of an aqueous phase and an organic phase by the use of a hypochlo-rite as an oxidizing agent, the hypochlorite being dissolved or dispersed in the aqueous phase, in the presence of at least one catalyst selected from the group consisting of (a) quaternary ammonium salts, (b) quaternary phosphonium salts, (c) quaternary arsonium salts, and (d) lipophilic complexing agents for cations contained in the hypochlorite, and also, in the presence or absence of an inorganic base.
A process for producing hexafluoropropylene oxide from hexafluoropropylene is described. The process comprises epoxidizing hexafluoropropylene in a two-phase system of an aqueous phase and an organic phase by the use of a hypochlo-rite as an oxidizing agent, the hypochlorite being dissolved or dispersed in the aqueous phase, in the presence of at least one catalyst selected from the group consisting of (a) quaternary ammonium salts, (b) quaternary phosphonium salts, (c) quaternary arsonium salts, and (d) lipophilic complexing agents for cations contained in the hypochlorite, and also, in the presence or absence of an inorganic base.
Description
PROCESS FOR THE PROnUCTION OF HEXAFLUOROPROPYLENE OXIDE
FIELD OF THE INVENTION
The present invention relates to a process for the production of hexafluoropropylene oxide, and more particularly, to a process for producing hexafluoropropylene oxide (herein-after some-times referred to as "IllPO") from hexafluoropropylene ~hereinafter sometimes referred to as "HFP7') by the use of a hypochlorite as an oxidizing agent.
BAC~GROUND OF THE INVENTION
-}exafluoropropylene oxide is an intermediate which is used to prepare useful fluorine-containing compounds such as hexafluoroacetone and perfluorovinyl ether, as described in U.S. Patent 4,165,340. Furthermore, polymers of llFPO have a wide variety of uses, e.g., a heat transfer medium and lubri-cant oil, as described in U.S. Patents 3,660,315 and 3,775,439.
Hexafluoropropylene oxide can be prepared by epoxi-dization of hexafluoropropylene. It is, however, difficult to epoxidize hexafluoropropylene by the same method used in the epoxidization of propylene or allyl chloride since hexa-fluoropropylene has chemical properties which are verydifferent from those of hydrocarbon olefins such as propylene or chlorinated hydrocarbon olefins such as allyl chloride.
For example, both propylene and allyl chloride can be epoxidized by the chlorohydrin process. In the process ~L2~Z~;
propylene or allyl chloride is first converted into chloro-hydrin and, thereafter 9 ring closure is achieved by the use of alkalis. On the other hand, when the chlorohydrin process is used to epoxidize hexafluoropropylene, decomposition of the resulting chlorohydrin into carbonyl compounds occurs because of its instability, and it is therefore impossible -to prepare the desired hexafluoropropylene oxide from the chlorohydrin.
- Various methods for epoxldization~of hexafluoro-propylene have heretofore been proposed, which are dlfferent from those for hydrocarbon olefins and chlorinated hydrocarbon olefins. However, none of these methods can~be used advan-- tageously~for the production of hexafluoropropylene oxlde on a commercial scale.
Typical known methods of production of hexafluoro-propylene oxide include the method described in U.S. Patent 3,358,003 wherein hexafluoropropylene is oxidized into hexa-fluoropropylene oxide in a medium of alkaline hydrogen per-oxide and the method described in U.S. Patent 3,536,733 wherein hexafluoropropylene is oxidized into hexafluoropro-pylene oxide in the presence of an inert solvent. In accor-dance with these methods, however, it is not possible to obtain hexafluoropropylene oxide in good yields since the reaction is difficult to control, decomposition of hexafluoro-propylene oxide formed is difficult to prevent, or large amounts of by-products are formed. Furthermore, when the ~, ~' ~z~
HFP conversion is increased, the HFPO selectivity is lowered.
Therefore, in order to efficiently use hexafluoropropylene, it is necessary to stop the reaction at low IIFP conversions and to separate and recover unreacted hexafluoropropylene from hexafluoropropylene oxide for reuse. However, since the boiling point of hexafluoropropylene (-29.4C) is very near that of hexafluoropropylene oxide ~-27.4C), it is difficult to separate them by distillation. Therefore, it is necessary to employ a specific separation technique. For `
this purpose, there has been proposed a method in which ~.
hexafluoropropylene is reacted wlth bromine in order to convert it into a high-boillng dibromo compound. This compound is then separated from hexafluoropropylene oxide as the dibromo compound. Another proposed method is an extrac-tive distillation separation method as described in U.S.
Patents 3,326,780 and 4,134,796. These methods, however, are complicated and seriously increase the production cost of hexafluoropropylene oxide It is known, as described in IZ~. AKAD. NAUK. SSSR.
20 SER. KHIM., 79, (11) 2509, that hexafluoropropylene oxide is formed from hexafluoropropylene in a system comprising an - aqueous hypochlorite solution with a polar solvent, e.g., acetonitrile and diglyme added thereto. Investigations of the oxidation method using such hypochlorites have revealed that the HFPO selectivity is about 10~. Thus it has been
FIELD OF THE INVENTION
The present invention relates to a process for the production of hexafluoropropylene oxide, and more particularly, to a process for producing hexafluoropropylene oxide (herein-after some-times referred to as "IllPO") from hexafluoropropylene ~hereinafter sometimes referred to as "HFP7') by the use of a hypochlorite as an oxidizing agent.
BAC~GROUND OF THE INVENTION
-}exafluoropropylene oxide is an intermediate which is used to prepare useful fluorine-containing compounds such as hexafluoroacetone and perfluorovinyl ether, as described in U.S. Patent 4,165,340. Furthermore, polymers of llFPO have a wide variety of uses, e.g., a heat transfer medium and lubri-cant oil, as described in U.S. Patents 3,660,315 and 3,775,439.
Hexafluoropropylene oxide can be prepared by epoxi-dization of hexafluoropropylene. It is, however, difficult to epoxidize hexafluoropropylene by the same method used in the epoxidization of propylene or allyl chloride since hexa-fluoropropylene has chemical properties which are verydifferent from those of hydrocarbon olefins such as propylene or chlorinated hydrocarbon olefins such as allyl chloride.
For example, both propylene and allyl chloride can be epoxidized by the chlorohydrin process. In the process ~L2~Z~;
propylene or allyl chloride is first converted into chloro-hydrin and, thereafter 9 ring closure is achieved by the use of alkalis. On the other hand, when the chlorohydrin process is used to epoxidize hexafluoropropylene, decomposition of the resulting chlorohydrin into carbonyl compounds occurs because of its instability, and it is therefore impossible -to prepare the desired hexafluoropropylene oxide from the chlorohydrin.
- Various methods for epoxldization~of hexafluoro-propylene have heretofore been proposed, which are dlfferent from those for hydrocarbon olefins and chlorinated hydrocarbon olefins. However, none of these methods can~be used advan-- tageously~for the production of hexafluoropropylene oxlde on a commercial scale.
Typical known methods of production of hexafluoro-propylene oxide include the method described in U.S. Patent 3,358,003 wherein hexafluoropropylene is oxidized into hexa-fluoropropylene oxide in a medium of alkaline hydrogen per-oxide and the method described in U.S. Patent 3,536,733 wherein hexafluoropropylene is oxidized into hexafluoropro-pylene oxide in the presence of an inert solvent. In accor-dance with these methods, however, it is not possible to obtain hexafluoropropylene oxide in good yields since the reaction is difficult to control, decomposition of hexafluoro-propylene oxide formed is difficult to prevent, or large amounts of by-products are formed. Furthermore, when the ~, ~' ~z~
HFP conversion is increased, the HFPO selectivity is lowered.
Therefore, in order to efficiently use hexafluoropropylene, it is necessary to stop the reaction at low IIFP conversions and to separate and recover unreacted hexafluoropropylene from hexafluoropropylene oxide for reuse. However, since the boiling point of hexafluoropropylene (-29.4C) is very near that of hexafluoropropylene oxide ~-27.4C), it is difficult to separate them by distillation. Therefore, it is necessary to employ a specific separation technique. For `
this purpose, there has been proposed a method in which ~.
hexafluoropropylene is reacted wlth bromine in order to convert it into a high-boillng dibromo compound. This compound is then separated from hexafluoropropylene oxide as the dibromo compound. Another proposed method is an extrac-tive distillation separation method as described in U.S.
Patents 3,326,780 and 4,134,796. These methods, however, are complicated and seriously increase the production cost of hexafluoropropylene oxide It is known, as described in IZ~. AKAD. NAUK. SSSR.
20 SER. KHIM., 79, (11) 2509, that hexafluoropropylene oxide is formed from hexafluoropropylene in a system comprising an - aqueous hypochlorite solution with a polar solvent, e.g., acetonitrile and diglyme added thereto. Investigations of the oxidation method using such hypochlorites have revealed that the HFPO selectivity is about 10~. Thus it has been
2~6 found that it is not possible to prepare hexafluoropropylene oxide in good yields. The reason for this is believed to be that since the reaction system is a homogeneous mixture of the polar solvent and the aqueous hypochlorite solution, the hexaEluoropropylene oxide formed readily reacts with water under alkaline conditions, resulting in the decomposition thereof. Furthermore, this method .requires an additional-step to recover the polar solvent from the~reaction system after-the reaction. In view~of the above described defècts~
the method is not suitable for practical use~in the production~
of hexafluoropropylene~oxide.
- SUMMARY OF THE INVENTION
As a result of extensive investigati.ons to develop a method of producing hexafluoropropylene oxide from hexa-fluoropropylene by a simplified procedure and in high yields,it has been found that hexafluoropropylene oxide can be prepared from hexafluoropropylene in high yields in a two-phase system~ The two phases are an aqueous phase and an organic phase wherein a hypochlorite is used as an oxidizing agent. The agent is dissolved or dispersed in the aqueous phase, and at least one compound selected from the group - consisting of ~a) quaternary ammonium salts, ~b) quaternary phosphonium salts, ~c) quaternary arsonium salts, and~(d) lipophilic complexing agents for cations contained in hypo-~
2, chlorites is used as a catalys-.
. ~ .... .
~ 2~ 6 The present invention, thcrefore, provides a process for prodllcing hexafluoropropylene oxide from hexafluoropro-pylene ~hich comprises epoxidizing hexafluoropropylene in a two-phase system of an aqueous phase and an organic phase using a hypochlorite as an oxidizing agent, said hypochlorite being dissolved or dispersed in the aqueous phase, in the presence of at least one catalyst selected from the group consisting of (a) quaternary ammonium salts, (b) quaternary phosphonium salts, (c) quaternary arsonium salts, and (d) ~10 lipophilic complexing agen-ts for cations contained in the -~ hypochlorite, and in the presence or absence of an inorganic base.
BRIEF DESCRIPTION OF THE DRAIVINGS
The Figure is one example of a flow diagram illustrating a process for continuous production of hexafluoropropylene oxide from hexafluoropropylene accordin~ to the invention.
DETAILED DESCRIPTION OF THE INVENTION
In the two-phase reaction of the invention~ almost all of hexafluoropropylene and foTmed hexafluoropropylene oxide are present in the organic phase. The process of the invention offers the advantage that hexafluoropropylene oxide can be obtained at high selectivity even if the HFP conver-sion is increased. The reason for this is believed to be that since the formed hexafluoropropylene oxide is present in a phase different from the alkaline aqueous solution, the z~
decomposition of hexafluoropropylene oxide resulting from contact with the alkaline aqueous solution is prevented from occurring. In accordance with the process of the invention, therefore, it is possible to omit a tedious step of separa-ting hexafluoropropylene oxide from hexafluoropropylene and ~ ;a step of recycling hexafluoropropylene by increasing the HFP conversion.
After the reaction, the organic phase and the aqueous phase are separated, and from the organic phase, 0 hexafluoropropylene oxide can be eàsily isolated by separa-:-tion techniques, e.g., distillation. Since the residual organic phase from which hexafluoropropylene oxide has~been removed contains the catalyst and, therefore, can be recycled and reused as such, recovery of the solvent or catalyst is 5 greatly simplified.
Thus, in the process of the invention, hexafluoro-propylene oxide can be produced in high yields and the pro-cess of production is greatly simplified. This will reduce the initial cost or construction cost of the reaction equip-ment and the operation cost. Therefore, the present inven-tion is an economical production of hexafluoropropylene oxide.
The invention will hereinafter be explained in greater detail.
Hypochlorites which can be used in the invention ~ Z~ ~ 6 include alkali metal salts, e.g., lithium hypochlorite, sodiumhypochlorite, potassium hypochlorite, rubidium hypochlorite, and cesium hypochlorite, and alkaline earth metal ~excluding beryllium) salts, e.g., magnesium hypochlorite, calcium hypochlorite, strontium hypochlorite, and barium hypochlorite.
Of these compounds, sodium hypochlorite and calcium hypochlo-rite are particularly suitable -for use in the invention because - they are produced on a commercial scale for bleaching agents, sterilizers, etc.,~and are available inexpensively. Commer-cially available hypochlorites may be used as such, orhypochlorites prepared~from inorganic bases and chlorine gas - or hypochlorites prepared by electrolysls of inorganic chlo-rides in undivided cell may be used.
The hypochlorite as used herein is dissolved mainly in the aqueous phase, and the concentration of the hypochlo-rite in the aqueous phase is not subject to any special limitations. In general a preferred available chlorine content is within the range of from 1% to 25%, with the range of from 3% to 20% being particularly preferred. When the available chlorine content is too low, it is necessary to process a large amount of aqueous phase, which is dis-advantageous from an economic standpoint. On the other hand, when the available chlorine content is too high, the hypoch-lorite becomes instable, causing handling difficulties.
The ratio of hypochloTite to hexafluoropropylene .
~L2~C~2~;
is not critical and can be determined optionally. Usually satisfactory results are obtained when the hypochlorite is added in an amount, as calculated as hypochlorite ion, of from 0.5 to 30 gram equivalent per mole of the hexafluGro-propylene, with the range of from 0.8 to 10 gram equivalentbeing preferred and the range of from 1 to S gram equivalent being particularly preferred.
The process of the invention can be carried out either in the presence of inorganic bases or in the absence of inorganic bases. The practlce of the reaction in the presence of inorganic bases offers the following advantages.
One of the advantages is that the HFPO selectivity can be held at high levels even if the HFP conversion is increased.
Therefore, without any serious reduction in the HFPO selec-tivity, the HFP conversion can be increased in order todecrease the amount of the residual HFP. This permits pro-duction of hexafluoropropylene oxide of high purity in high yields without a step of separating hexafluoropropylene oxide from hexafluoropropylene. Another advantage is that good results can be obtained even if the ratio of the hypochlorite to the hexafluoropropylene is lowered. When the reaction is carried out in the absence of the inorganic base or in the presence of a very small amount of inorganic base, if the ratio of the hypochlorite to the hexafluoropropylene is lowered, the HFPO selectivity is reduced, and the residual ; - 8 -- . .
~L22C12~
available chlorine content is reduced in the course o~ the reaction. This leads to no further increase in the HFP
conversion. In this case, therefore, it is necessary to carry out the reaction in the presence of an excessive amount of hypochlorite in order to obtain good results. On the other hand, if the process of the inventiOn is performed in the presence of a specific amount o-f inorganic ~ase, the amount - of the hypochlorite being used can be reduced. This permits reduction in t~e produc~ion cost ass~ciated with the reduction in the amount o~ hypochlorite being used, redu~tion in the .
size of the reaction equipment,~and reduct~on in the cost of disposal processing.
Inorganic bases which can be used in the process of the invention include alkali metal hydroxides, e.-g.~ lithium hydroxide, sodium hydroxide, potassium hydroxide, rubisium hydroxide, and cesium hydroxide, and alkaline earth metal hydroxides, e.g., calcium hydroxide,strontium hydroxide, and barium hydroxide. These inorganic bases may be completely dissolved in the aqueous phase, or may not be completely dissolved and be partially present as a solid phase. Of the above described inorganic bases, sodium hydroxide is parti-cularly suitable for use in the invention ln view of cost, solubility in water, ease of handling, and so forth.
The amount of the inorganic base used in the process 2~i of the invention is not critical and can be determined appro-priately. In order to yield the above described advantages, the inorganic base is added in an amount of at least 0.1 gram equivalent per mole of hexafluoropropylene. The total amount of the inorganic base may be introduced into the reaction system from the beginning of the reaction, or in some cases, it may be added in appropriate portions in the course of the reaction.
At least one compound selected from the group consisting of (a) quaternary ammonium salts,~b) quaternary `
phosphonlum salts, (c) quaternary arsonium salts, and (d) lipophilic complexing agents for cations contained in hypo-chlorites is used as a catalyst in the process of the inven-tion. Preferably, the catalyst has an affinity with the : 15 organic phase.
Quaternary ammonium salts which can be used in the invention include those represented by the general formula (I):
[ l2 wherein Rl, R2, R3 and R4 may be either the same or different, and each represents a hydrocarbon group which is unsubstituted or substituted by a -functional group which is inert under the reaction conditions. The type and length of the hydro-.-.
~22~
carbon group are selected appropriately depending on the type of the solvent used, the rate of reaction required, and so forth. Examples of such hydrocarbon groups include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and an alkenylaryl group. Of these groups, an alkyl group, an aryl group, and an aralkyl group are particularly preferred. With regard to the length of the hydrocarbon group, the total number o-f carbon atoms contained in Rl, R2, R3 and R4 lS usually from 6 to 100 7 preferably from 8 to 70, and particularly preferably from 10 to 50, per quaternary ammonium ion. Inert functional groups which can be used as substituents for the hydrocarbon group are limited depending on the reaction conditions.
Usually a halogen atom, an acyl group~ a carboxy group, an ester group, a nitrile group, an alkoxyl group, etc. are used.
Rl and R2, or Rl, R2 and R3 may combine together to form a nitrogen-containing heterocyclic ring, or Rl, R2, R3 or R4 may constitute a part of a polymeric compound.
Quaternary ammonium ions which can be used include a tetraethylammonium ion, a tetra-n-propylammonium ion, a tetra-n-butylammonium ion, a tri-n-octylmethylammonium ion, - a cetyltrimethylammonium ion, a benzyltrimethylammonium ion, a benzyltriethylammonium ion, a cetylbenzyldimethylammonium - ion, a cetylpyridinium ion, a n-dodecylpyridinium ion, a phenyltrimethylammonium ion, a phenyltriethylammonium ion, ~ 6 a N-benzylpicolinium ion, a pentame-thonium ion a and a hexa-methonium ion. Of these, quaternary ammonium ions having a long-chain alkyl group such as a tri-n-octylmethylammonium ion and a tetra-n-butylammonium ion are preferably used.
Anions, ~X, in the general formula (I) are not subject to any special limitation, and various kinds of anions can be used. Usually, halogen ions, mineral acid ions excluding the halogen ions, organic acid ions, hydroxyl ion and so forth are used.
~ Examples of such anions, include a chloride ion, a bromide ion, an iodide ion, a fluoride ion, a hydrogen-- sulfate ion, a sulfate ion, a nitrate ion, a phosphate ion, a peTchlorate ion, a hydroxide ion, an acetate ion, a benzoate ion, a benzenesulfonate ion, and a p-toluenesulfo-nate ion. Of these ions, a chloride ion, a hydrogensulfa~e ion, and a hydroxide ion are particularly preferred.
Quaternary phosphonium salts which can be used in the invention include those represented by the general formula ~
[R5-~9-R7 ~ Y tll) ' R8 wherein R5, R6, R7 and R8 may be the same or different, and each represents a hydrocarbon group which is unsubstituted or substituted by a functional group which is inert under ~22~2~i the reaction conditions. The type and length of the hydro-carbon group are determined appropriately depending on the type of the solvent used, the rate of reaction required9 and so forth. Examples of such hydrocarbon groups include an alkyl group, an alkenyl group, a cycloalkyl group, a cyclo-alkenyl group, an aryl group, an aralkyl group, and an alkenylaryl group. Of these groups an alkyl group, an aryl ' group, and an aralkyl group are partlcularly preferred. With regard to the length of the hydrocarbon group, the total number of carbon atoms contained in R5, R6, R7 and R8 is -usually from 6 to~100~ preferably from 8 to 70, and partl-cularly preferably from 10 to 50, per quaternary phosphonium ion. Inert functional groups which can be used as substi-tuents for the hydrocarbon group are llmited by the reaction conditions Usually, a halogen atom, an acyl group, a carboxyl group, an ester group, a nitrile group, and an alkoxyl group are used. R5 and R6, or R5, R6 and R7 may combine together to form a heterocyclic ringj or R5, R6, R7 and R8 may form a part of the polymeric compound.
Examples of quaternary phosphonium ions include a tetraethylphosphonium ion, a tetra-n-butylphosphonium ion, a tri-n-octylethylphosphonium ion, a cetyltriethylphosphonium ion, a cetyltri-n-butylphosphonium ion, a n-butyltriphenyl-phosphonium ion, a n-amyltriphenylphosphonium ion, a n-- 25 hexyltriphenylphosphonium ion, a n-heptyltriphenylphosphonium .
:
2~L6 ion, a methyltliphenylphosphonium ion, a benzyltriphcnyl-phosphonium ion, and a tetraphenylphosphonium ion. Of these, quaternary phosphonium ions having a long-chain alkyl group such as a tri-n-octylethylphosphonium ion and a tetra-n-butylphosphonium ion are perferably used.
Anions, ~Y, in the general formula (II) are not subject to any special limitations, and various kinds of anions can be used. Usually, halogen ions, mineral acid ions excluding the halogen ions, organic acid ions, and so forth are used.
Examples of such anions include a chloride ion, a bromide ion, an iodide ion, a fluoride lon, a hydrogensulfate ion, a sulfate ion, a nitrate ion, a phosphate ion, a perchlo-rate ion, and a p-toluenesulfonate ion. Particularly prefer-red are a chloride ion and a bromide ion.
Quaternary arsonium salts as used herein are suffi-cient to have an affinity to the organic phase and -to be capable of providing quaternary arsonium iolls which are stably present under the reaction conditions of the invention.
Examples include tetraarylarsonium salts such as tetraphenyl-` arsonium chloride and tetraphenylarsonium bromide, triaryl-alkylarsonium salts such as triphenylmethylarsonium chlorideg and their polymeric derivatives.
Lipophilic complexing agents for cations contained in hypochlorites are required to have both an ability with 2~2~6 respect to complexing the cations and an affinity to the organic phase, and naturally, to be stable under the reaction conditions of the invention. Any complexing agents meeting the above requirements can be used in the invention, and thus a wide variety of compounds are useful.
Typical examples of the lipophilic complexing agents which can be used in the invention are shown below although the invention is not limited there,to.
~1) Large Ring Compounds Large ring compounds are commonly called "crown ethers" ~as described in, for example, Pedersen, J. Amer.
Chem Soc., 89, 2495, 7017 ~1967)), and are known to have a high coordination ability to alkali metal ions and alkaline earth metal ions. Almost all of such crown ethers are represented by the general formula ~III), including their substituted derivatives.
wherein n is an integer of from 4 to 20, m is an integer of ' 1~ Q2~ --- and Qn which may be the same or different, each is an integer of from 2 to 4.
Examples of such crown ethers ~named according to the Pedersen's nomenclature) include 18-crown-6, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5, dibenzo-15-crown-5, dibenzo-21-crown-7, dibenzo-24-crown-8-, dibenzo-30-~2Z~2~6 crown-10, and dicyclohexyl-24-crown-8 (2) Large Ring Aminoethers Examples of large ring aminoethers are bicyclic aminoethers and monocyclic aminoethers.
Bicyclic aminoethers are commonly called "cryptands"
~as described in, for example~ Lehn, Tetrahedron Lett., 2885, 2889 ~1969)), and areknown to have a very high coordination ability to alkali metal ions and alkaline earth metal ions.
Almost all of cryptands are represented by the general formula ~IV), including their substituted derivatives.
, CH2~ ~ CH2 CH2~ ~ CH2~ CH
N \ CH2 ~ CH ~ ~ 2 ~ CH2 ~ CH2 (IV) CH2 ~0 /~
CH2 ~ CH2 - CH2 ~ CH2 ~ 2 ~o=O, 1, 2 ; p=O, 1, 2 ; q=O, 1,2) Preferred examples of such cryptands are shown below:
1/~ j~oAo~
N ~ ~ N N ~ O N
,j o~ o~ oJ
~IV-a) ~IV-b) - .
;22 o~b-~ ~`o/ \o-~
/~0/ \0/~ ~\~o/\, o~N
~o~oJ ~o~oJ
(IV-c) (IV-d) ~ . 'l, .
~o)~/~o~ ~ ~`~~
N ~ ~o~N N \,0 N
- ~ o~/oJ ~<o ~ n IV-e) (IV-f) ~0~\0~1 ~0~0 N /\,o ~ o/\~N N ~ O~\,O~\~N
~- C H ~- C 14 H Z g (IV-g) (IV-h) - . . .. .
2~6 Examples of monocyclic aminoethers include those compounds represented by the general formula ~V) and their substituted derivatives.
/ CH2 CH2~ O/ 2 \CH ~ 2 Rg- N r N-Rlo (V) CH2- CH2~ \ CH2 / 2 ~ o- CH -CH
S wherein r=O, 1 or 2; s=O, 1 or 2; and Rg and Rlo, each represents H or a substituted or unsubstituted hydrocarbon group containing from 1 to 80 carbon atoms.
Preferred examples are shown below:
~o~b/\~ ~--~'~1 HN NH HN NH
~O~ o~o~J
~ ~V-a) ~V-b) ~`~~ o~o~\o~
n-ClOH21 N N-n-cl0~l2l HN ~H
~o~oJ ~o~ o ,, .. ..
:~ (V-c) . (V-d) '. ' ~ - 18 -~L~2~6
the method is not suitable for practical use~in the production~
of hexafluoropropylene~oxide.
- SUMMARY OF THE INVENTION
As a result of extensive investigati.ons to develop a method of producing hexafluoropropylene oxide from hexa-fluoropropylene by a simplified procedure and in high yields,it has been found that hexafluoropropylene oxide can be prepared from hexafluoropropylene in high yields in a two-phase system~ The two phases are an aqueous phase and an organic phase wherein a hypochlorite is used as an oxidizing agent. The agent is dissolved or dispersed in the aqueous phase, and at least one compound selected from the group - consisting of ~a) quaternary ammonium salts, ~b) quaternary phosphonium salts, ~c) quaternary arsonium salts, and~(d) lipophilic complexing agents for cations contained in hypo-~
2, chlorites is used as a catalys-.
. ~ .... .
~ 2~ 6 The present invention, thcrefore, provides a process for prodllcing hexafluoropropylene oxide from hexafluoropro-pylene ~hich comprises epoxidizing hexafluoropropylene in a two-phase system of an aqueous phase and an organic phase using a hypochlorite as an oxidizing agent, said hypochlorite being dissolved or dispersed in the aqueous phase, in the presence of at least one catalyst selected from the group consisting of (a) quaternary ammonium salts, (b) quaternary phosphonium salts, (c) quaternary arsonium salts, and (d) ~10 lipophilic complexing agen-ts for cations contained in the -~ hypochlorite, and in the presence or absence of an inorganic base.
BRIEF DESCRIPTION OF THE DRAIVINGS
The Figure is one example of a flow diagram illustrating a process for continuous production of hexafluoropropylene oxide from hexafluoropropylene accordin~ to the invention.
DETAILED DESCRIPTION OF THE INVENTION
In the two-phase reaction of the invention~ almost all of hexafluoropropylene and foTmed hexafluoropropylene oxide are present in the organic phase. The process of the invention offers the advantage that hexafluoropropylene oxide can be obtained at high selectivity even if the HFP conver-sion is increased. The reason for this is believed to be that since the formed hexafluoropropylene oxide is present in a phase different from the alkaline aqueous solution, the z~
decomposition of hexafluoropropylene oxide resulting from contact with the alkaline aqueous solution is prevented from occurring. In accordance with the process of the invention, therefore, it is possible to omit a tedious step of separa-ting hexafluoropropylene oxide from hexafluoropropylene and ~ ;a step of recycling hexafluoropropylene by increasing the HFP conversion.
After the reaction, the organic phase and the aqueous phase are separated, and from the organic phase, 0 hexafluoropropylene oxide can be eàsily isolated by separa-:-tion techniques, e.g., distillation. Since the residual organic phase from which hexafluoropropylene oxide has~been removed contains the catalyst and, therefore, can be recycled and reused as such, recovery of the solvent or catalyst is 5 greatly simplified.
Thus, in the process of the invention, hexafluoro-propylene oxide can be produced in high yields and the pro-cess of production is greatly simplified. This will reduce the initial cost or construction cost of the reaction equip-ment and the operation cost. Therefore, the present inven-tion is an economical production of hexafluoropropylene oxide.
The invention will hereinafter be explained in greater detail.
Hypochlorites which can be used in the invention ~ Z~ ~ 6 include alkali metal salts, e.g., lithium hypochlorite, sodiumhypochlorite, potassium hypochlorite, rubidium hypochlorite, and cesium hypochlorite, and alkaline earth metal ~excluding beryllium) salts, e.g., magnesium hypochlorite, calcium hypochlorite, strontium hypochlorite, and barium hypochlorite.
Of these compounds, sodium hypochlorite and calcium hypochlo-rite are particularly suitable -for use in the invention because - they are produced on a commercial scale for bleaching agents, sterilizers, etc.,~and are available inexpensively. Commer-cially available hypochlorites may be used as such, orhypochlorites prepared~from inorganic bases and chlorine gas - or hypochlorites prepared by electrolysls of inorganic chlo-rides in undivided cell may be used.
The hypochlorite as used herein is dissolved mainly in the aqueous phase, and the concentration of the hypochlo-rite in the aqueous phase is not subject to any special limitations. In general a preferred available chlorine content is within the range of from 1% to 25%, with the range of from 3% to 20% being particularly preferred. When the available chlorine content is too low, it is necessary to process a large amount of aqueous phase, which is dis-advantageous from an economic standpoint. On the other hand, when the available chlorine content is too high, the hypoch-lorite becomes instable, causing handling difficulties.
The ratio of hypochloTite to hexafluoropropylene .
~L2~C~2~;
is not critical and can be determined optionally. Usually satisfactory results are obtained when the hypochlorite is added in an amount, as calculated as hypochlorite ion, of from 0.5 to 30 gram equivalent per mole of the hexafluGro-propylene, with the range of from 0.8 to 10 gram equivalentbeing preferred and the range of from 1 to S gram equivalent being particularly preferred.
The process of the invention can be carried out either in the presence of inorganic bases or in the absence of inorganic bases. The practlce of the reaction in the presence of inorganic bases offers the following advantages.
One of the advantages is that the HFPO selectivity can be held at high levels even if the HFP conversion is increased.
Therefore, without any serious reduction in the HFPO selec-tivity, the HFP conversion can be increased in order todecrease the amount of the residual HFP. This permits pro-duction of hexafluoropropylene oxide of high purity in high yields without a step of separating hexafluoropropylene oxide from hexafluoropropylene. Another advantage is that good results can be obtained even if the ratio of the hypochlorite to the hexafluoropropylene is lowered. When the reaction is carried out in the absence of the inorganic base or in the presence of a very small amount of inorganic base, if the ratio of the hypochlorite to the hexafluoropropylene is lowered, the HFPO selectivity is reduced, and the residual ; - 8 -- . .
~L22C12~
available chlorine content is reduced in the course o~ the reaction. This leads to no further increase in the HFP
conversion. In this case, therefore, it is necessary to carry out the reaction in the presence of an excessive amount of hypochlorite in order to obtain good results. On the other hand, if the process of the inventiOn is performed in the presence of a specific amount o-f inorganic ~ase, the amount - of the hypochlorite being used can be reduced. This permits reduction in t~e produc~ion cost ass~ciated with the reduction in the amount o~ hypochlorite being used, redu~tion in the .
size of the reaction equipment,~and reduct~on in the cost of disposal processing.
Inorganic bases which can be used in the process of the invention include alkali metal hydroxides, e.-g.~ lithium hydroxide, sodium hydroxide, potassium hydroxide, rubisium hydroxide, and cesium hydroxide, and alkaline earth metal hydroxides, e.g., calcium hydroxide,strontium hydroxide, and barium hydroxide. These inorganic bases may be completely dissolved in the aqueous phase, or may not be completely dissolved and be partially present as a solid phase. Of the above described inorganic bases, sodium hydroxide is parti-cularly suitable for use in the invention ln view of cost, solubility in water, ease of handling, and so forth.
The amount of the inorganic base used in the process 2~i of the invention is not critical and can be determined appro-priately. In order to yield the above described advantages, the inorganic base is added in an amount of at least 0.1 gram equivalent per mole of hexafluoropropylene. The total amount of the inorganic base may be introduced into the reaction system from the beginning of the reaction, or in some cases, it may be added in appropriate portions in the course of the reaction.
At least one compound selected from the group consisting of (a) quaternary ammonium salts,~b) quaternary `
phosphonlum salts, (c) quaternary arsonium salts, and (d) lipophilic complexing agents for cations contained in hypo-chlorites is used as a catalyst in the process of the inven-tion. Preferably, the catalyst has an affinity with the : 15 organic phase.
Quaternary ammonium salts which can be used in the invention include those represented by the general formula (I):
[ l2 wherein Rl, R2, R3 and R4 may be either the same or different, and each represents a hydrocarbon group which is unsubstituted or substituted by a -functional group which is inert under the reaction conditions. The type and length of the hydro-.-.
~22~
carbon group are selected appropriately depending on the type of the solvent used, the rate of reaction required, and so forth. Examples of such hydrocarbon groups include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and an alkenylaryl group. Of these groups, an alkyl group, an aryl group, and an aralkyl group are particularly preferred. With regard to the length of the hydrocarbon group, the total number o-f carbon atoms contained in Rl, R2, R3 and R4 lS usually from 6 to 100 7 preferably from 8 to 70, and particularly preferably from 10 to 50, per quaternary ammonium ion. Inert functional groups which can be used as substituents for the hydrocarbon group are limited depending on the reaction conditions.
Usually a halogen atom, an acyl group~ a carboxy group, an ester group, a nitrile group, an alkoxyl group, etc. are used.
Rl and R2, or Rl, R2 and R3 may combine together to form a nitrogen-containing heterocyclic ring, or Rl, R2, R3 or R4 may constitute a part of a polymeric compound.
Quaternary ammonium ions which can be used include a tetraethylammonium ion, a tetra-n-propylammonium ion, a tetra-n-butylammonium ion, a tri-n-octylmethylammonium ion, - a cetyltrimethylammonium ion, a benzyltrimethylammonium ion, a benzyltriethylammonium ion, a cetylbenzyldimethylammonium - ion, a cetylpyridinium ion, a n-dodecylpyridinium ion, a phenyltrimethylammonium ion, a phenyltriethylammonium ion, ~ 6 a N-benzylpicolinium ion, a pentame-thonium ion a and a hexa-methonium ion. Of these, quaternary ammonium ions having a long-chain alkyl group such as a tri-n-octylmethylammonium ion and a tetra-n-butylammonium ion are preferably used.
Anions, ~X, in the general formula (I) are not subject to any special limitation, and various kinds of anions can be used. Usually, halogen ions, mineral acid ions excluding the halogen ions, organic acid ions, hydroxyl ion and so forth are used.
~ Examples of such anions, include a chloride ion, a bromide ion, an iodide ion, a fluoride ion, a hydrogen-- sulfate ion, a sulfate ion, a nitrate ion, a phosphate ion, a peTchlorate ion, a hydroxide ion, an acetate ion, a benzoate ion, a benzenesulfonate ion, and a p-toluenesulfo-nate ion. Of these ions, a chloride ion, a hydrogensulfa~e ion, and a hydroxide ion are particularly preferred.
Quaternary phosphonium salts which can be used in the invention include those represented by the general formula ~
[R5-~9-R7 ~ Y tll) ' R8 wherein R5, R6, R7 and R8 may be the same or different, and each represents a hydrocarbon group which is unsubstituted or substituted by a functional group which is inert under ~22~2~i the reaction conditions. The type and length of the hydro-carbon group are determined appropriately depending on the type of the solvent used, the rate of reaction required9 and so forth. Examples of such hydrocarbon groups include an alkyl group, an alkenyl group, a cycloalkyl group, a cyclo-alkenyl group, an aryl group, an aralkyl group, and an alkenylaryl group. Of these groups an alkyl group, an aryl ' group, and an aralkyl group are partlcularly preferred. With regard to the length of the hydrocarbon group, the total number of carbon atoms contained in R5, R6, R7 and R8 is -usually from 6 to~100~ preferably from 8 to 70, and partl-cularly preferably from 10 to 50, per quaternary phosphonium ion. Inert functional groups which can be used as substi-tuents for the hydrocarbon group are llmited by the reaction conditions Usually, a halogen atom, an acyl group, a carboxyl group, an ester group, a nitrile group, and an alkoxyl group are used. R5 and R6, or R5, R6 and R7 may combine together to form a heterocyclic ringj or R5, R6, R7 and R8 may form a part of the polymeric compound.
Examples of quaternary phosphonium ions include a tetraethylphosphonium ion, a tetra-n-butylphosphonium ion, a tri-n-octylethylphosphonium ion, a cetyltriethylphosphonium ion, a cetyltri-n-butylphosphonium ion, a n-butyltriphenyl-phosphonium ion, a n-amyltriphenylphosphonium ion, a n-- 25 hexyltriphenylphosphonium ion, a n-heptyltriphenylphosphonium .
:
2~L6 ion, a methyltliphenylphosphonium ion, a benzyltriphcnyl-phosphonium ion, and a tetraphenylphosphonium ion. Of these, quaternary phosphonium ions having a long-chain alkyl group such as a tri-n-octylethylphosphonium ion and a tetra-n-butylphosphonium ion are perferably used.
Anions, ~Y, in the general formula (II) are not subject to any special limitations, and various kinds of anions can be used. Usually, halogen ions, mineral acid ions excluding the halogen ions, organic acid ions, and so forth are used.
Examples of such anions include a chloride ion, a bromide ion, an iodide ion, a fluoride lon, a hydrogensulfate ion, a sulfate ion, a nitrate ion, a phosphate ion, a perchlo-rate ion, and a p-toluenesulfonate ion. Particularly prefer-red are a chloride ion and a bromide ion.
Quaternary arsonium salts as used herein are suffi-cient to have an affinity to the organic phase and -to be capable of providing quaternary arsonium iolls which are stably present under the reaction conditions of the invention.
Examples include tetraarylarsonium salts such as tetraphenyl-` arsonium chloride and tetraphenylarsonium bromide, triaryl-alkylarsonium salts such as triphenylmethylarsonium chlorideg and their polymeric derivatives.
Lipophilic complexing agents for cations contained in hypochlorites are required to have both an ability with 2~2~6 respect to complexing the cations and an affinity to the organic phase, and naturally, to be stable under the reaction conditions of the invention. Any complexing agents meeting the above requirements can be used in the invention, and thus a wide variety of compounds are useful.
Typical examples of the lipophilic complexing agents which can be used in the invention are shown below although the invention is not limited there,to.
~1) Large Ring Compounds Large ring compounds are commonly called "crown ethers" ~as described in, for example, Pedersen, J. Amer.
Chem Soc., 89, 2495, 7017 ~1967)), and are known to have a high coordination ability to alkali metal ions and alkaline earth metal ions. Almost all of such crown ethers are represented by the general formula ~III), including their substituted derivatives.
wherein n is an integer of from 4 to 20, m is an integer of ' 1~ Q2~ --- and Qn which may be the same or different, each is an integer of from 2 to 4.
Examples of such crown ethers ~named according to the Pedersen's nomenclature) include 18-crown-6, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5, dibenzo-15-crown-5, dibenzo-21-crown-7, dibenzo-24-crown-8-, dibenzo-30-~2Z~2~6 crown-10, and dicyclohexyl-24-crown-8 (2) Large Ring Aminoethers Examples of large ring aminoethers are bicyclic aminoethers and monocyclic aminoethers.
Bicyclic aminoethers are commonly called "cryptands"
~as described in, for example~ Lehn, Tetrahedron Lett., 2885, 2889 ~1969)), and areknown to have a very high coordination ability to alkali metal ions and alkaline earth metal ions.
Almost all of cryptands are represented by the general formula ~IV), including their substituted derivatives.
, CH2~ ~ CH2 CH2~ ~ CH2~ CH
N \ CH2 ~ CH ~ ~ 2 ~ CH2 ~ CH2 (IV) CH2 ~0 /~
CH2 ~ CH2 - CH2 ~ CH2 ~ 2 ~o=O, 1, 2 ; p=O, 1, 2 ; q=O, 1,2) Preferred examples of such cryptands are shown below:
1/~ j~oAo~
N ~ ~ N N ~ O N
,j o~ o~ oJ
~IV-a) ~IV-b) - .
;22 o~b-~ ~`o/ \o-~
/~0/ \0/~ ~\~o/\, o~N
~o~oJ ~o~oJ
(IV-c) (IV-d) ~ . 'l, .
~o)~/~o~ ~ ~`~~
N ~ ~o~N N \,0 N
- ~ o~/oJ ~<o ~ n IV-e) (IV-f) ~0~\0~1 ~0~0 N /\,o ~ o/\~N N ~ O~\,O~\~N
~- C H ~- C 14 H Z g (IV-g) (IV-h) - . . .. .
2~6 Examples of monocyclic aminoethers include those compounds represented by the general formula ~V) and their substituted derivatives.
/ CH2 CH2~ O/ 2 \CH ~ 2 Rg- N r N-Rlo (V) CH2- CH2~ \ CH2 / 2 ~ o- CH -CH
S wherein r=O, 1 or 2; s=O, 1 or 2; and Rg and Rlo, each represents H or a substituted or unsubstituted hydrocarbon group containing from 1 to 80 carbon atoms.
Preferred examples are shown below:
~o~b/\~ ~--~'~1 HN NH HN NH
~O~ o~o~J
~ ~V-a) ~V-b) ~`~~ o~o~\o~
n-ClOH21 N N-n-cl0~l2l HN ~H
~o~oJ ~o~ o ,, .. ..
:~ (V-c) . (V-d) '. ' ~ - 18 -~L~2~6
(3) Polyethylene Glycol and Its Derivatives Various kinds of polyethylene glycols can be used.
Those having a degree of polymerization of at least 10 are preferred.
Polyethylene glycol derivatives include the compounds represented by the general formula (VI) or ~VII) and their substituted derivatives, copolymers of ethylene oxide and other monomers, and surface active agents containing the polyethylene glycol structure.
Rllo~cH2-cH2-o ~ H (VI) -~wherein t=5 or more; and Rll repTesents a substituted or unsubstituted hydrocarbon group containlng from 1 to 80 carbon atoms) R12O~H2-CH2-O ~ R13 ~VII) ~wherein u=3 OT moTe; and R12 and R13, each represents a substituted or unsubstituted hydrocarbon group).
Pre-Eerred examples of the polyethylene glycol deri-vatives represented by the general formula ~VI) or (VII) are shown below:
n-C16H33~CH2~cH2 ~ (VI-a) ... n-C8H17 ~ CH2-CH2-O ~ H (VI-b) --C9Hl9 ~ o~CH2-CH2-O ~ H (VI-c) CH3O~CH2-cH2-O ~ CH3 (VII-a) n-C4HgO~cH2-cH2-o ~ n~C4H9 (VII-b) ~2~2~6 ~ ~C~13 ~ ~
O~ /0 0~
(VII-c) (VII-d) An example of a copolymer of ethylene oxlde and other monomers is an ethylene oxide-propylene oxide block copolymer.
Examples of surface active agents containing the polyethylene glycol structure include polyoxyethylene alkyl-thio ether, polyoxyethylene alkylamine, polyoxyethylene alkyl ether sulfuric acid ester salts, polyoxyethylene alkyl phenyl . ether sulfuric acid ester salts, polyoxyethylene carboxylate, . 10 polyoxyethylene-type alkylolamide, and polyoxyethylene alkyl ether.
Those having a degree of polymerization of at least 10 are preferred.
Polyethylene glycol derivatives include the compounds represented by the general formula (VI) or ~VII) and their substituted derivatives, copolymers of ethylene oxide and other monomers, and surface active agents containing the polyethylene glycol structure.
Rllo~cH2-cH2-o ~ H (VI) -~wherein t=5 or more; and Rll repTesents a substituted or unsubstituted hydrocarbon group containlng from 1 to 80 carbon atoms) R12O~H2-CH2-O ~ R13 ~VII) ~wherein u=3 OT moTe; and R12 and R13, each represents a substituted or unsubstituted hydrocarbon group).
Pre-Eerred examples of the polyethylene glycol deri-vatives represented by the general formula ~VI) or (VII) are shown below:
n-C16H33~CH2~cH2 ~ (VI-a) ... n-C8H17 ~ CH2-CH2-O ~ H (VI-b) --C9Hl9 ~ o~CH2-CH2-O ~ H (VI-c) CH3O~CH2-cH2-O ~ CH3 (VII-a) n-C4HgO~cH2-cH2-o ~ n~C4H9 (VII-b) ~2~2~6 ~ ~C~13 ~ ~
O~ /0 0~
(VII-c) (VII-d) An example of a copolymer of ethylene oxlde and other monomers is an ethylene oxide-propylene oxide block copolymer.
Examples of surface active agents containing the polyethylene glycol structure include polyoxyethylene alkyl-thio ether, polyoxyethylene alkylamine, polyoxyethylene alkyl ether sulfuric acid ester salts, polyoxyethylene alkyl phenyl . ether sulfuric acid ester salts, polyoxyethylene carboxylate, . 10 polyoxyethylene-type alkylolamide, and polyoxyethylene alkyl ether.
(4) Polyvinyl Pyrrolidone and Its Derivatives -. Polyvinyl pyrrolidone derivatives include copoly-mers o-f ~inyl pyrrolidone and other monomers.
(5) Amineoxides represented by the general formula (VIII) and their substituted derivatives 14R15R1N ~VIII) .. . .. . . .
~ Z ~ 6 wherein R14, Rl5 and R16, each is a hydrocarbon group, the total number of carbon atoms contained in R14, R15 and R16 is at least 10, and R14 and Rl~, or R14, 15 16 combine together to form a nitrogen-containing heterocyclic ring.
Examples include tri-n-octylamineoxide and 4-(5-nonyl)pyridine-N-oxide.
~6) Compounds resulting from substitution of one or more or - all oxygen atoms in large ring polyethers, large ring amino-lQ ethers, polyethylene glycol, polyethylene glycol der vatives, and their substituted derivatives by nitrogen atom (R17-N- ), sulfur atom, phosphorus atom (R18-P_ j, amineoxide group O , O
(Rlg-N ), sulfinyl group, sulfonyl group or the group Rlg-P=
(wherein R17, R18 and Rlg, each is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group).
Examples of these compounds are shown below-' ~0~ ~0 0 o o ~,oJ
(IX-a) (IX-b) . .
- . . . . . . .
~L2~ 6 ~S~S~ ~`~
N ~ O ~ O ~ N ~ S ~
l o oJ
o (IX-c) tIX-d ~ N
O o ':
N
(IX-e) In addition to the above described lipophilic complexing agents, various compounds containing functiondl groups, such as a carbonyl group, a sulfinyl group,a sulfonyl group, phosphoryl group~an ether group, an amino group, an imidazole ring, a furan ring, and a pyridine ring, having a coordi-` nation ability to metal cations can be used in the process - of the invention. These lipophilic complexing agents may be supported on polymeric compounds or various insoluble carriers - by various supporting techniques.
~ .
.. . . .
~L2~ 6 The amount of the catalyst used in the process of the invention is selected appropriately depending on the structure of the catalyst~ the type of the solvent, the reaction temperature, the requisite rate of reaction, and so forth. Usually the catalyst is used in an amount of from 0 0001 to 10 moles per gram equivalent of hypochlorite ion, with the range of from 0.001 to 1 mole being particularly preferred. When the amount of the catalyst is too small, the rate of reaction is unsuitably low, whereas when the catalyst is used in an excess amount, the rate of reaction is so high that it is difficult to control the reaction,and the cost of the catalyst increases, which is disadvantageous from an economic standpoint.
The reaction of the invention is carried out in a two-phase system of an aqueous phase and an organic phase.
In this case, the organic phase is su-fficient to form a phase which contains hexafluoropropylene and is dif-ferent from the aqueous phase. It is not necessary for the organic phase to meet any further requirements. ~or example, the organic phase may be either a phase composed mainly of hexafluoro-propylene per se, or a phase composed of a water sparingly soluble catalyst and hexafluoropropylene, or a phase composed of an inert solvent and hexafluoropropylene, said inert solvent being substantially immiscible or sparingly miscible in the aqueous phase.
.
~ 6 In the practice of the invention, it is only nece-ssary that there be an organic phase containing substantially all hexafluoropropylene and an aqueous phase containing the hypochlorite. Thus, there may be present one or more different phases in the system in addition to the two phases. For example, either in a system wherein the organic phase consists of two phases composed of different media having low mutual solubilities with each other, or in a system wherein the catalyst is supported on a water-insoluble carrier, forming a third phase, the process of the invention can be carried out.
Organic solvents which are used to form the organic phase are inert solvents which are substantially immiscible or sparingly miscible in the aqueous phase. Examples of such inert solvents include aliphatic hydrocarbons, e.gO, n-hexane, n-octane, and n-decané; alicyc]ic hydrocarbons, e.g., cyclo-hexane, methylcyclohexane, and decalin; aromatic hydrocarbons, e.g., benzene, toluene, and xylene; ethers, e.g., diisopropyl ether and di-n-butyl ether; chlorinated hydrocarbons, e.g., Z0 methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene; chlorofluorocarbons, e.g., 1,2-dichloro-1,1,2,2-tetrafluoroethane, fluorotrichloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, and 1,1,2,Z-tetrachloro-1,2-difluoroethane; perfluorocarbons, e.g., perfluorocyclobutane, perfluorodimethylcyclobutane, perfluorohexane, perfluorooctane, ' .
~Z~6 perfluorodecane, and hexafluorobenzene; and mixtures thereof.
The organic solvent is selected appropriately taking into account the solubility in hexafluoropropylene or hexafluoro-propylene oxide, the solubility in the catalyst used in the reaction, the separation capability from the aqueous phase, the reaction conditions, e.g., reaction pressure and reaction temperature, and so forth. Of the above described solvents, fluorine-containing solvents such as chlorofluorocarbons, perfluoro compounds, and partially fluorinated hydrocarbons are suitable for use in the process of the invention because of their high solubilities in hexafluoropropylene or hexa-fluoropropylene oxide, and also, chlorinated hydrocarbons are suitable for use in the process of the invention because they generally have high solubilities in the catalysts.
The volume ratio of the organic phase to the aqueous phase is not critical and can be determined appro-priately depending on the reaction method, the reaction condi-tions, and so forth. Usually the organic phase is from 0.05 to 20 times as much as the aqueous phase, with the range of from 0.2 to 5 times being particularly preferred.
In the practice of the process of the invention, the reaction temperature is determined according to the amount of the catalyst, the composition of the reaction liquid, the requisite rate of reactlon7 and so forth. The reaction temperature is usually within the range of from -25C to 60C, ~L;22~2~!L6 preferably within the range of from -20C to 40C, and parti-cularly preferably ~ithin the range of from -18~C to 20C.
When the reaction temperature is too low, the reaction does not proceed at practically acceptable rates, and in extreme cases, the aqueous phase freezes and the reaction does not proceed at all. On the other hand, when the reaction tempera-ture is too high, the decomposition of hexafluoropropylene oxide becomes significant, resulting in a reduction in the HFPO selectivity.
With regard to the reaction pressure, as long as the pressure is high enough to keep the organic phase con-taining hexafluoropropylene or hexafluoropropylene oxlde in a liquid phase, it is not necessary to meet any further requisites. However, the reaction pressure varies depending on the type and composition of the organic phase, and it is usually within the range of from l to 20 atmospheric pressures.
The process of the invention can be carried out by a number of methods including a batch method, a semi-flow method, and a flow method. In commercial production, it is preferable to use the flow method.
The process of the invention can be carried out continuously and commercially advantageously, for example, by a method in which hexafluoropropylene oxide is first synthesized from hexafl~uoropropylene by the two-phase reac-tion method of the invention. Thereafter, the organic phase , .
G
and the aqueous phase are separated -Erom each other, the hexafluoropropylene oxide is isolated from the organic phase, and hexafluoropropylene is added to the residual organic phase containing the catalyst which is then re-used in the two-phase reaction.
In carrying out the two-phase reaction by the flow method, there can be employed a counterflow process and a parallelflow process in which the organic phase containing hexafluoropropylene and the catalyst, and the aqueous phase containing the hypochlorite and the inorganic base are brought into contact with each other. In the practice of the two-phase reaction, it is necessary to fully mix the two phases in the reactor. For that purpose, conventional techniques using, for example, a stirring blade or a stationary mixing device can be employed. In the case of the counterflow process, the two-phase reaction and the phase-separation can be carried out simultaneously. On the other hand, as the parallelflow reaction, there can be mentioned a tube-type reaction and a vessel-type flow reaction. In the case of the tube type reaction~ it is necessary for the two phases to pass through a tube-type reactor in the state that they are finely dispersed. It is necessary, therefore, to install a two phase-mixer before the tube type reactor, or to design the tube type reactor so that it includes the two phase-mixer. In the parallelflow reaction, since the organic ~ Z~ ~6 phase and the aqueous phase are withdrawn from the two-phase reactor while they are mixed together, it is necessary to separate the organic phase and the aqueous phase in a decantor. The aqueous phase after the two-phase reaction contains unreacted hypochlorite, chlorides resulting from the reaction of the hypochlorite, the inorganic base, a part of the catalyst 9 and various by-products. The aqueous phase is disposed as such, or when the aqueous phase contains large amounts of the unreacted hypochlorite and catalyst, it is possible to recover the hypochlorite and catalyst from the aqueous phase for re-use thereof. The organic phase after the two-phase rèaction contains hexafluoropropylene oxide formed, unreacted hexafluoropropylene, catalyst, and so forth. From the organic phase, hexafluoropropylene oxide and hexafluoropropylene can be easily separated by separa-tion techniques, e.g., distillation. The organic phase -from which hexafluoropropylene oxide and hexafluoropropylene have been removed still contains the catalyst. Therefore, after addition of hexafluoropropylene, the organic phase can be returned to the two-phase reaction zone and re-used therein.
In the case of several catalysts, part of the catalyst trans-fers into the aqueous phase during the two-phase reaction, causing a reduction in the catalyst content of the organic phase. In such cases, it is necessary to appropriately supplement the catalyst to the organic phase.
- 2~ -.. .
%~6 The following Examples and Comparative Examples are given to illustrate the invention in greater detail although the invention is not limited thereto.
The aqueous sodium hypochlorite solutions used in the examples are shown in Table 1.
Table 1 Aqueous Sodium Hypochlorite Available Chlorine Sodium Hydroxide Solution Content (%) Concentration ~N) *l A 12 0.15 B-0 2 12 0.025 *~
B-l ~ 12 0.10 B-2 3 12 1.53 *312 0.40 -B-4 4 6 0.40 C 10.2 0.95 D 3.8 0.40 The aqueous sodium hypochlorite solutions of Table 1 were prepared as follows:
*l Chlorine gas was blown into an aqueous solution of sodium hydroxide maintained at -10C to prepare the solution.
*2 Comrnercially available solution.
- *3 Sodium hydroxide was added to Solution B-0 to prepare the solutions.
*4 Sodium hydroxide and water were added to Solution B-0 to prepare the solution.
EXA~IPLE 1 A 50-mQ pressure bottole in which a stirrer had been placed was charged with the Eollowing ingredients:
1,1,2-Trichloro-1,2,2-trifluoro-ethane ~hereinfafter referred to as "F-113") 18 mQ
Aqueous sodium hypochlorite solution A 20 mQ
Hexafluoropropylene ` 1.8 g ~12 milimoles) Trioctylmethylammonium chloride ~hereinafter referred to as "TO~IAC") 0.16 g ~0.4 milimoles) These ingredients were colled down to 0C and, thereafter, by rotating the stirrer in the reactor with a - 15 magnetic stirrer, they were mixed to start the reaction.
During the reaction9 the temperature was maintained as 0C.
One hour after the start of the reaction, the rotation of the stirrer was stopped. The reaction solution was allowed to stand to separate into an aqueous phase and a F-113 phase.
Quantitative analysis of the hexafluoropropylene and~
hexafluoropropylene oxide contained in the F-113 phase by gas chromatography showed that the HFP conversion was 96%
and the HFPO selectivity was 84%.
%~
COMPA~\TIVE EXAMPLE 1 The procedure of Example 1 was repeated with the exception that TOMAC (catalyst) was not used.
There was obtained only a trace amount of hexaflu-oropropylene oxide, and almost all hexafluoropropylene was recovered.
EXAMPLE 2 to 15 The procedure of Example 1 was repeated with the exception that 0.16 g of each of the quaternary ammonium salts shown in Table 2 was used in place of TOMAC as a catalyst.
The results are shown in Table 2 below.
Table 2 Exam- Reaction HFP Con- HFPO Selec-~ e_ Catalyst _ime(hrs) _rsion(%) tivity (%) 15 2 (n-Bu)4NCQ 2 65 71 3 (n-Bu)~NBr 3 52 68 4 (n-Bu)4NI 4 53 66 ~n-Bu)4NOH 2 57 75
~ Z ~ 6 wherein R14, Rl5 and R16, each is a hydrocarbon group, the total number of carbon atoms contained in R14, R15 and R16 is at least 10, and R14 and Rl~, or R14, 15 16 combine together to form a nitrogen-containing heterocyclic ring.
Examples include tri-n-octylamineoxide and 4-(5-nonyl)pyridine-N-oxide.
~6) Compounds resulting from substitution of one or more or - all oxygen atoms in large ring polyethers, large ring amino-lQ ethers, polyethylene glycol, polyethylene glycol der vatives, and their substituted derivatives by nitrogen atom (R17-N- ), sulfur atom, phosphorus atom (R18-P_ j, amineoxide group O , O
(Rlg-N ), sulfinyl group, sulfonyl group or the group Rlg-P=
(wherein R17, R18 and Rlg, each is a hydrogen atom, or a substituted or unsubstituted hydrocarbon group).
Examples of these compounds are shown below-' ~0~ ~0 0 o o ~,oJ
(IX-a) (IX-b) . .
- . . . . . . .
~L2~ 6 ~S~S~ ~`~
N ~ O ~ O ~ N ~ S ~
l o oJ
o (IX-c) tIX-d ~ N
O o ':
N
(IX-e) In addition to the above described lipophilic complexing agents, various compounds containing functiondl groups, such as a carbonyl group, a sulfinyl group,a sulfonyl group, phosphoryl group~an ether group, an amino group, an imidazole ring, a furan ring, and a pyridine ring, having a coordi-` nation ability to metal cations can be used in the process - of the invention. These lipophilic complexing agents may be supported on polymeric compounds or various insoluble carriers - by various supporting techniques.
~ .
.. . . .
~L2~ 6 The amount of the catalyst used in the process of the invention is selected appropriately depending on the structure of the catalyst~ the type of the solvent, the reaction temperature, the requisite rate of reaction, and so forth. Usually the catalyst is used in an amount of from 0 0001 to 10 moles per gram equivalent of hypochlorite ion, with the range of from 0.001 to 1 mole being particularly preferred. When the amount of the catalyst is too small, the rate of reaction is unsuitably low, whereas when the catalyst is used in an excess amount, the rate of reaction is so high that it is difficult to control the reaction,and the cost of the catalyst increases, which is disadvantageous from an economic standpoint.
The reaction of the invention is carried out in a two-phase system of an aqueous phase and an organic phase.
In this case, the organic phase is su-fficient to form a phase which contains hexafluoropropylene and is dif-ferent from the aqueous phase. It is not necessary for the organic phase to meet any further requirements. ~or example, the organic phase may be either a phase composed mainly of hexafluoro-propylene per se, or a phase composed of a water sparingly soluble catalyst and hexafluoropropylene, or a phase composed of an inert solvent and hexafluoropropylene, said inert solvent being substantially immiscible or sparingly miscible in the aqueous phase.
.
~ 6 In the practice of the invention, it is only nece-ssary that there be an organic phase containing substantially all hexafluoropropylene and an aqueous phase containing the hypochlorite. Thus, there may be present one or more different phases in the system in addition to the two phases. For example, either in a system wherein the organic phase consists of two phases composed of different media having low mutual solubilities with each other, or in a system wherein the catalyst is supported on a water-insoluble carrier, forming a third phase, the process of the invention can be carried out.
Organic solvents which are used to form the organic phase are inert solvents which are substantially immiscible or sparingly miscible in the aqueous phase. Examples of such inert solvents include aliphatic hydrocarbons, e.gO, n-hexane, n-octane, and n-decané; alicyc]ic hydrocarbons, e.g., cyclo-hexane, methylcyclohexane, and decalin; aromatic hydrocarbons, e.g., benzene, toluene, and xylene; ethers, e.g., diisopropyl ether and di-n-butyl ether; chlorinated hydrocarbons, e.g., Z0 methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene; chlorofluorocarbons, e.g., 1,2-dichloro-1,1,2,2-tetrafluoroethane, fluorotrichloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, and 1,1,2,Z-tetrachloro-1,2-difluoroethane; perfluorocarbons, e.g., perfluorocyclobutane, perfluorodimethylcyclobutane, perfluorohexane, perfluorooctane, ' .
~Z~6 perfluorodecane, and hexafluorobenzene; and mixtures thereof.
The organic solvent is selected appropriately taking into account the solubility in hexafluoropropylene or hexafluoro-propylene oxide, the solubility in the catalyst used in the reaction, the separation capability from the aqueous phase, the reaction conditions, e.g., reaction pressure and reaction temperature, and so forth. Of the above described solvents, fluorine-containing solvents such as chlorofluorocarbons, perfluoro compounds, and partially fluorinated hydrocarbons are suitable for use in the process of the invention because of their high solubilities in hexafluoropropylene or hexa-fluoropropylene oxide, and also, chlorinated hydrocarbons are suitable for use in the process of the invention because they generally have high solubilities in the catalysts.
The volume ratio of the organic phase to the aqueous phase is not critical and can be determined appro-priately depending on the reaction method, the reaction condi-tions, and so forth. Usually the organic phase is from 0.05 to 20 times as much as the aqueous phase, with the range of from 0.2 to 5 times being particularly preferred.
In the practice of the process of the invention, the reaction temperature is determined according to the amount of the catalyst, the composition of the reaction liquid, the requisite rate of reactlon7 and so forth. The reaction temperature is usually within the range of from -25C to 60C, ~L;22~2~!L6 preferably within the range of from -20C to 40C, and parti-cularly preferably ~ithin the range of from -18~C to 20C.
When the reaction temperature is too low, the reaction does not proceed at practically acceptable rates, and in extreme cases, the aqueous phase freezes and the reaction does not proceed at all. On the other hand, when the reaction tempera-ture is too high, the decomposition of hexafluoropropylene oxide becomes significant, resulting in a reduction in the HFPO selectivity.
With regard to the reaction pressure, as long as the pressure is high enough to keep the organic phase con-taining hexafluoropropylene or hexafluoropropylene oxlde in a liquid phase, it is not necessary to meet any further requisites. However, the reaction pressure varies depending on the type and composition of the organic phase, and it is usually within the range of from l to 20 atmospheric pressures.
The process of the invention can be carried out by a number of methods including a batch method, a semi-flow method, and a flow method. In commercial production, it is preferable to use the flow method.
The process of the invention can be carried out continuously and commercially advantageously, for example, by a method in which hexafluoropropylene oxide is first synthesized from hexafl~uoropropylene by the two-phase reac-tion method of the invention. Thereafter, the organic phase , .
G
and the aqueous phase are separated -Erom each other, the hexafluoropropylene oxide is isolated from the organic phase, and hexafluoropropylene is added to the residual organic phase containing the catalyst which is then re-used in the two-phase reaction.
In carrying out the two-phase reaction by the flow method, there can be employed a counterflow process and a parallelflow process in which the organic phase containing hexafluoropropylene and the catalyst, and the aqueous phase containing the hypochlorite and the inorganic base are brought into contact with each other. In the practice of the two-phase reaction, it is necessary to fully mix the two phases in the reactor. For that purpose, conventional techniques using, for example, a stirring blade or a stationary mixing device can be employed. In the case of the counterflow process, the two-phase reaction and the phase-separation can be carried out simultaneously. On the other hand, as the parallelflow reaction, there can be mentioned a tube-type reaction and a vessel-type flow reaction. In the case of the tube type reaction~ it is necessary for the two phases to pass through a tube-type reactor in the state that they are finely dispersed. It is necessary, therefore, to install a two phase-mixer before the tube type reactor, or to design the tube type reactor so that it includes the two phase-mixer. In the parallelflow reaction, since the organic ~ Z~ ~6 phase and the aqueous phase are withdrawn from the two-phase reactor while they are mixed together, it is necessary to separate the organic phase and the aqueous phase in a decantor. The aqueous phase after the two-phase reaction contains unreacted hypochlorite, chlorides resulting from the reaction of the hypochlorite, the inorganic base, a part of the catalyst 9 and various by-products. The aqueous phase is disposed as such, or when the aqueous phase contains large amounts of the unreacted hypochlorite and catalyst, it is possible to recover the hypochlorite and catalyst from the aqueous phase for re-use thereof. The organic phase after the two-phase rèaction contains hexafluoropropylene oxide formed, unreacted hexafluoropropylene, catalyst, and so forth. From the organic phase, hexafluoropropylene oxide and hexafluoropropylene can be easily separated by separa-tion techniques, e.g., distillation. The organic phase -from which hexafluoropropylene oxide and hexafluoropropylene have been removed still contains the catalyst. Therefore, after addition of hexafluoropropylene, the organic phase can be returned to the two-phase reaction zone and re-used therein.
In the case of several catalysts, part of the catalyst trans-fers into the aqueous phase during the two-phase reaction, causing a reduction in the catalyst content of the organic phase. In such cases, it is necessary to appropriately supplement the catalyst to the organic phase.
- 2~ -.. .
%~6 The following Examples and Comparative Examples are given to illustrate the invention in greater detail although the invention is not limited thereto.
The aqueous sodium hypochlorite solutions used in the examples are shown in Table 1.
Table 1 Aqueous Sodium Hypochlorite Available Chlorine Sodium Hydroxide Solution Content (%) Concentration ~N) *l A 12 0.15 B-0 2 12 0.025 *~
B-l ~ 12 0.10 B-2 3 12 1.53 *312 0.40 -B-4 4 6 0.40 C 10.2 0.95 D 3.8 0.40 The aqueous sodium hypochlorite solutions of Table 1 were prepared as follows:
*l Chlorine gas was blown into an aqueous solution of sodium hydroxide maintained at -10C to prepare the solution.
*2 Comrnercially available solution.
- *3 Sodium hydroxide was added to Solution B-0 to prepare the solutions.
*4 Sodium hydroxide and water were added to Solution B-0 to prepare the solution.
EXA~IPLE 1 A 50-mQ pressure bottole in which a stirrer had been placed was charged with the Eollowing ingredients:
1,1,2-Trichloro-1,2,2-trifluoro-ethane ~hereinfafter referred to as "F-113") 18 mQ
Aqueous sodium hypochlorite solution A 20 mQ
Hexafluoropropylene ` 1.8 g ~12 milimoles) Trioctylmethylammonium chloride ~hereinafter referred to as "TO~IAC") 0.16 g ~0.4 milimoles) These ingredients were colled down to 0C and, thereafter, by rotating the stirrer in the reactor with a - 15 magnetic stirrer, they were mixed to start the reaction.
During the reaction9 the temperature was maintained as 0C.
One hour after the start of the reaction, the rotation of the stirrer was stopped. The reaction solution was allowed to stand to separate into an aqueous phase and a F-113 phase.
Quantitative analysis of the hexafluoropropylene and~
hexafluoropropylene oxide contained in the F-113 phase by gas chromatography showed that the HFP conversion was 96%
and the HFPO selectivity was 84%.
%~
COMPA~\TIVE EXAMPLE 1 The procedure of Example 1 was repeated with the exception that TOMAC (catalyst) was not used.
There was obtained only a trace amount of hexaflu-oropropylene oxide, and almost all hexafluoropropylene was recovered.
EXAMPLE 2 to 15 The procedure of Example 1 was repeated with the exception that 0.16 g of each of the quaternary ammonium salts shown in Table 2 was used in place of TOMAC as a catalyst.
The results are shown in Table 2 below.
Table 2 Exam- Reaction HFP Con- HFPO Selec-~ e_ Catalyst _ime(hrs) _rsion(%) tivity (%) 15 2 (n-Bu)4NCQ 2 65 71 3 (n-Bu)~NBr 3 52 68 4 (n-Bu)4NI 4 53 66 ~n-Bu)4NOH 2 57 75
6 (n-Bu)4NHSO4 1 66 83 20 7 (n-Bu)4NCQO4 3 23 74 . 8 Et4NCQ 3 11 40 9 (n C12~l25)Me3NC 56 57 (n-C14 H29)Me2(PhCH2)NCQ 3 65 71 .. . . . ...
11 (phcH2)~e3NcQ 1 75 52 12 ~ N-~n-C H 3)CQ- 4 33 58 13 ~ N-CH2PhCQ 2 22 35 14 Polybrene ~ *1 4 33 51 n-C12H25~I CH2 C2 2 81 62 *l Trade mark ~Aldrich Chemical Co.) ~ I - (CH2)6-N~ (CH2) ~ 2Br 1,5-dimethyl-1,5-diazaundecamethyl.ene polymethobromide EX,~IPLES 16 to 22 The procedure of Example 1 ~as repeated with the e~ception that 0.60 g ~4 milimoles) of hexafluoropropylene was used, and the type of the solvent and the amount of the catalyst, (n-Bu)4N~SO4, were changed as shown in Table 3.
The results are shown in Table 3 belo~.
Table 3 HFP Con- HFPO
Exam- ~n-Bu) NSO H Reaction version Selectivity ple Solvent ~g)4 4 _ime~hrs) _ ~%) ~%) ! 16 F-113 1 0.16 1.0 81 77 , 17 PFDMCB 2 0.16 3.0 . g7 76 .
~ - 32 -q Q~
18 CCQ4 0.16 0.5 71 76 l9 CHCQ3 0.03 0.5 81 56 CH2CQ2 0.03 0.5 90 40 21 CQCH2CH2CQ 0.03 0 5 93 39 22 n-hexane 0.16 1.0 77 74 *l 1,1,2-trichloro-1,2,2-trifluoroethane *2 perfluorodimethylcyclobutane EXAMPLE 23 ~
The procedure of Example 1 was repeated wherein 20mQ of an aqueous solution containing 4.6 g of bleaching powder (composed mainly of calcium hypochlorite) with an available chlorine content of 65 %was used in place of 20 mQ
of the aqueous sodium hypochlorite solution A with an avail-able chlorine content of 12 %, 1.5 g o-f hexafluoropropylene and 0.12 g of TOMAC were used, and the reaction was carried out at a temperature of 20C for a period of 15 minutes.
The HFP conversion was 9~ %~ and the HFPO selectivity was 39 %.
The procedure of Example 1 was repeated wherein 30 mQ
of an aqueous potassium hypochlorite solution with an available chlorine content of 7 % was used in place of 20 mQ of the aqueous sodium hypochlorite solution A with an available chlorine content of 12 %, and 1.5 g of hexafluoropropylene and 0.12 g of TO~C were used.
..... . .
The HFP conversion was 41 %, and the HFPO selectivity was 53 %.
. EXAMPLE 25 The procedure of Example 1 was repeated wherein 0.12 g ~0.35 milimole) of tetra-n-butylphosphonium bromide was used as a catalyst.
Thirty minutes after the start of the reaction, the HFP conversion was 84 %, and the HFPO selectivity was 67 %.
The procedure of Bxample 25 was repeated wherein the amount of the catalyst, tetra-n-butylphosphonium bromide, was changed from 0.12 g to 0.04 g, and the reaction was carried out at a -temperature of 20C.
The HFP conversion was-71 %, and the HFPO selectivity was 62 %.
The procedure of Example 26 was repeated wherein the reaction was carried out at a temperature of 40C.
The HFP conversion was 83 %, and the HFPO selectivity w.as 54 %.
The procedure of Example 1 was repeated wherein .
0.20 g of tetra-n-butylphosphonium bromide was used as a catalyst, and the reaction was carried out at a temperature of -10C.
"
. .
The ~IFP conversion was 77 %, and the HFP0 selectivity was 69 %.
EXA~IPLE 29 The procedure of Example 1 was repeated wherein 0.12 g ~0.29 milimole) of amyltriphenylphosphonium bromide was used as a catalyst, and the reaction was carried out for a period of 4 hours.
The HFP conversion was 70 %, and the HFP0 selec-tivity was 66 %.
The procedure of Example 1 was repeated wherein chloroform was used in place of F-113, 0.04 g (0.12 milimole) of tetra-n-butylphosphonium bromide was used as a catalyst, and hexafluoropropylene was used in the amount of 0.6 g : 15 ~4 milimoles).
The HFP conversion was 89 %, and the HFP0 selec-tivity was 61 %.
The procedure of Example 30 was repeated wherein 0.02 g ~0.04 milimole) of hydrochloric acid tetraphenylarso-nium chloride ~Ph4ArCQ-HCQ) was used as a catalyst.
. The HFP conversion was 78 %, and the HFP0 selec-tivity was 74 %.
EXAMPLES 32 to 38 The procedure of Example 1 was repeated wherein chloroform was used in place of F-113, hexafluoropropylene . .
~2~ L6 was used in the amo~mt of 0.5 g, and as a catalyst, each of the large ring polyethers and large ring aminoethers shown in Table 4 was used.
The results are shown in Table 4 below.
Table 4 Amount of HFP Con- HFPO Selec-Exam- Catalyst Reaction version tivity ple Catalyst _ (g)Time~}Irs) (%) (~) 32 18-crown-6 1 0.36 0.5 74 82 33 dibenzo-18- 0.36 2.0 84 80 CTOWn 2 1034 benzo-15-crown-5 3 0.36 2.0 78 81 ~ryptofix~222B 4 0.04 8 1.0 85 74 36 ~ryptofix#-221 5 0.12 0.5 92 63 37 ~ryptofix#-22 6 0.12 2.0 86 80 38 ~ryptofix#-22DD 7 0.12 l.0 7~ 8 5 15 The chemical structures of the compounds used are shown below:
# trade mark . ;. . .
, [D2~L~
*1 *2 /~ /--\
~ o ~ ~o O 0~
O ~ ' O ~ ~ O
l o ~ -*3 *4 *5 ~, u ~ n - *6 ~*7 - fo~o^~ ~o~o ~
.- HN NH CloH2l-N ~ ClOH21 0~_~!0~ ~O ~
.... .
: ' .
~2~2~ ~
*1 to *3: Named according to the Pederson's nomenculature (J. I~m. Chem Soc., 89, 7071 (1967)).
*4 to *7: Trade mar~s (produced by ~Ierck ~ Co.) *8 : 50 % Toluene solution XA~IPLE 39 The procedure of Example 1 was repeated ~herein 0.24 g of Cryptofix 222B (trade mark, produced by ~Ierck ~ Co.) was used as a catalyst.
Four hours after the start of the reaction, the HFP
convcrsion was 53 %~ and the HFPO selectivity was 74 %.
The procedure of Example 1 was repeated wherein 0.36 g of a polyether having the foTmula shown below was used as a catalyst.
\~
O O O O P ' \ J \ r /
Four hours after the start of the reaction, the HFP conversion was 61 ~, and the HFPO selectivity was 74 %.
EXA~IPLE 41 The procedure of Example 1 was repeated wherein 0.12 g of a nonionic surface active agent, polyoxyethylene oleyl ether ~produced by Nippon Oils ~ Fats Co., Ltd.:
H.L.B., 16.6), was used as a catalyst.
~22C~fi Three hours after the s~art of the reaction, the HFP conversion was 75 %, and the HFPO selectivity was 76 ~.
EX~IPLE 42 The procedure of Example 1 was repeated wherein 0.12 g of tri-n-octylamine-N-oxide was used as a catalyst.
Two hours a-fter the start of the reaction, the HFP
conversion was 26 %, and the HFPO selectivity was 45 %.
EXAMPLE 43~
. The procedure of Example 1 was repeated wherein 0.12 g of 4-(5-nonyl)pyridine-N-oxide was used as a catalyst.
Three hours after the start of the reaction, the HFP conversion was 51 %, and the HFPO selectivity was 36 %.
: EXAMPLE 44 The procedure of Example 32 was Tepeated wherein 15 0.36 g of polyvinyl pyrrolidone (average molecular weight, 40,000) was used as a ca~alyst.
Two hours after the start o-f the reaction, the HFP conversion was 76 %, and the HFPO selectivity was 82 %.
EX~MPLE 45 20 The procedure of Example 1 was repeated wherein . 1.2 g (8 milimoles) of hexafluoropropylene was used, and -: 20 mQ of an aqueous sodium hypochlorite solution B-O ~con-taining 40 milimoles of sodium hypochlorite and 0.5 milimole : of sodium hydroxide? was used in place of the aqueous sodium hypochlorite solution A. The molar ratio of sodium hydroxide ~ 6 to hexafluoropropylene was 0.06/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 5.0/1.
One hour after the start of the reaction, the HFP
conversion was 87 %, and the HFPO selectivity was 57 %. In this case, even though the reaction was further continued, no increase in the HFP conversion was observed.
The procedure of Exarnple 45 was repeated wherein 20 mQ of an aqueous sodium hypochlorite solution B-l (con-taining 40 milimoles of sodium hypochlorite and 2 milimolesof sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.25/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 5.0/1.
One hour after the start of the reaction, the HFP
conversion was 91 %, and the HFPO selectivity was 72 %.
The procedure of Examp]e 45 was repeated wherein Z0 mQ of an aqueous sodium hypochlorite solution B-2 (con-taining 40 milimoles of sodium hypochlorite and 31 milimolesof sodium hydroxide) was used. The moIar ratio of sodium hydroxide to hexafluoropropylene was 3.8/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 5.0/1.
One hour after the start of the reaction, the HFP
conversion was 99 %, and the HFPO selectivity was 77 %.
EXA~IPLE 48 The procedure of Example 1 was repeated wherein 20 mQ of an aqueous sodium hypochlorite solution C (con-taining 34 milimoles of sodium hypochlorite and 19 milimoles of sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 1.9/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 3.4/1.
Fifteen minutes after the start of the reaction, the HFP conversion was 9S %, and ~he HFPO selectivity was 78 %.
Thirty minutes after the start of the reaction, the HFP con-version was 99 %, and the HFPO selectivity was 76 %.
E~A~IPLE 49 A 300-mQ autoclave of glass was charged with 150 mQ
of an aqueous sodium hypochlorite solution B-3 ~containing 300 milimoles of sodium hypochlorite and 60 milimoles of sodium hydroxide), 100 mQ of F-113, 11 g (73 milimoles) o~
hexafluoropropylene, and 0.65 g ~1.6 milimoles) of TO~IAC.
The reaction was carried out at a temperature of from -10C :
to -5C and a rate of stirring of 1,000 r.p.m. for a period of 25 minutes. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.82/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 4.1/1.
Gas chromatographic analysis of the products indicated that the EIFP conversion was 96 %, and the HFPO selectivity was 76 %.
- ~1 -z~
The procedure of Example 49 was repeated wherein lO0 mQ of diisopropyl ether was used in place of F-113 as an organic solvent, and the reaction was carried out for a period o-f 20 minutes.
The HFP conversion was 90 %, and the HFPO selecti-vity was 70 %.
EXAMPLE 51 ~
The proceduTe of Example 49 was repeated wherein 100 mQ of a mixed solvent of benzene and n-hexane (volume ratio, 1/9) was used in place of F-113 as an organic solvent, TO~C was used in the amount of 0.33 g (0.8 milimole) in place of 0.65 g,. and the reaction was carried out for a period of 30 minutes.
The HFP conversion was 80 %, and the HFPO selecti-~- vity was 78 %.
The procedure of Example 45 was repeated wherein 5.7 mQ of an aqueous sodium hypochlorite solution C (con-.20 taining 9.6 milimoles of sodium hypochlorite and 5.4 milimoles : of sodium hydroxide) was used. The molar ratio of sodium .. ~ hydroxide to hexafluoropropylene was 0.68/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 1.2/1.
. Fifteen minutes after the start of the reaction, the HFP conversion was 50 %,..and.the HFPO selectivity was 73 %.
.- , ' .
.. - 4~ -, .
2~i EXA~IPLE 53 The procedure of Example 45 was repeated wherein 15.2 mQ of an aqueous sodium hypochlorite solution D (con-taining 9.6 milimoles of sodium hypochlorite and 6.1 milimoles of sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.76/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 1.2/1. .
Fifteen minutes after the start of the reaction, the HFP conversion was 77 %, and the HFPO selectivity was 74 %.
EXA~IPLE 54 The procedure of Example 1 was repeated wherein 20 mQ of an aqueous sodium hypochlorite solution B-4 ~con-taining 20 milimoles of sodium hypochlorite and 8 milimoles of sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.80/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 2.0/1.
One hour after the start of the reaction, the HFP
conversion was 91 %, and the HFPO selectivity was 80 %.
EXA~IPLE 55 In this example 7 hexafluoropropylene oxide was prepared from hexafluoropropylene by the use of continuous reaction equipment as illustrated in the Figure, comprising a stationary mixer l (length: 150 mm: including a twisted ' .
blade type mixing element), a 160-mQ tubular reactor 2, a decanter 3, a HFPO distillation column 4, and a 1,000-mQ
organic phase tank 5.
The stationary mixer 1, tubular reactor 2~ and decanter 3 were cooled down to -10C, and the pressure was maintained at 3 kg/cm2'(gauge pressure) with nitrogen gas.
A F-113 solution containing 0.045 mole/Q of TOMAC was circu-lated in the reaction equipment at a flow rate of 33 mQ/min.
Then, an aqueous sodium hypochlorite solution B-4 ~containing 1.0 mole/Q of sodium hypochlorite and 0.40 mole/Q o-f sodiwn hydroxide~ was introduced into the stationary mixer 1 at a flow rate of 27 mQ/min, and was withdrawn simultaneously from the decanter 3. Hexafluoropropylene was introduced into an organic phase line before the stationary mixer 1 at a flow rate of 2.10 g/
min ~14.0 milimoles/min) to start the reaction. In the tubular reactor 2 the molar ratio of sodium hydroxide to hexafluoropropylene was 0.77/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 1.9/1. The organic phase and aqueous phase were finely dispersed in the stationary mixer 1, and pa~sed through the tubular reactor 2 in the dispersed state during-which the reaction proceeded between the two phases.
The reaction solution leaving the tubular reactor 2 was introduced into the decanter 3 where it was separated into the organic phase and aqueous phase. The aqueous phase was discharge out of the reaction equipment. The organic phase : ' :
.
~2~32~
containing the formed hexafluoropropylene oxide was sent to the HFPO distillation column 4 where the formed hexafluorpro-pylene oxide and the unreacted hexafluoropropylene were separated from the organic phase. During the period from 1 to 2 hours after the start of the reaction, the average distillation rate of hexafluoropropylene oxide was 1.80 g/min (10.8 milimoles/min), and the average distillation rate of hexafluoropropylene was 0.02 g/min ~0.13 milimoles/min).
The organic phase from which the hexafluoropropylene oxide and hexafluoropropylene had been distilled away in the HFPO
distillation column 4 was sent to the organic phase tank 5 and, thereafter, was returned to the stationary mixer 1.
While the invention has been described in detail and with reference to specific embodiment thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein withou~ departing from the spirit and scope thereof.
11 (phcH2)~e3NcQ 1 75 52 12 ~ N-~n-C H 3)CQ- 4 33 58 13 ~ N-CH2PhCQ 2 22 35 14 Polybrene ~ *1 4 33 51 n-C12H25~I CH2 C2 2 81 62 *l Trade mark ~Aldrich Chemical Co.) ~ I - (CH2)6-N~ (CH2) ~ 2Br 1,5-dimethyl-1,5-diazaundecamethyl.ene polymethobromide EX,~IPLES 16 to 22 The procedure of Example 1 ~as repeated with the e~ception that 0.60 g ~4 milimoles) of hexafluoropropylene was used, and the type of the solvent and the amount of the catalyst, (n-Bu)4N~SO4, were changed as shown in Table 3.
The results are shown in Table 3 belo~.
Table 3 HFP Con- HFPO
Exam- ~n-Bu) NSO H Reaction version Selectivity ple Solvent ~g)4 4 _ime~hrs) _ ~%) ~%) ! 16 F-113 1 0.16 1.0 81 77 , 17 PFDMCB 2 0.16 3.0 . g7 76 .
~ - 32 -q Q~
18 CCQ4 0.16 0.5 71 76 l9 CHCQ3 0.03 0.5 81 56 CH2CQ2 0.03 0.5 90 40 21 CQCH2CH2CQ 0.03 0 5 93 39 22 n-hexane 0.16 1.0 77 74 *l 1,1,2-trichloro-1,2,2-trifluoroethane *2 perfluorodimethylcyclobutane EXAMPLE 23 ~
The procedure of Example 1 was repeated wherein 20mQ of an aqueous solution containing 4.6 g of bleaching powder (composed mainly of calcium hypochlorite) with an available chlorine content of 65 %was used in place of 20 mQ
of the aqueous sodium hypochlorite solution A with an avail-able chlorine content of 12 %, 1.5 g o-f hexafluoropropylene and 0.12 g of TOMAC were used, and the reaction was carried out at a temperature of 20C for a period of 15 minutes.
The HFP conversion was 9~ %~ and the HFPO selectivity was 39 %.
The procedure of Example 1 was repeated wherein 30 mQ
of an aqueous potassium hypochlorite solution with an available chlorine content of 7 % was used in place of 20 mQ of the aqueous sodium hypochlorite solution A with an available chlorine content of 12 %, and 1.5 g of hexafluoropropylene and 0.12 g of TO~C were used.
..... . .
The HFP conversion was 41 %, and the HFPO selectivity was 53 %.
. EXAMPLE 25 The procedure of Example 1 was repeated wherein 0.12 g ~0.35 milimole) of tetra-n-butylphosphonium bromide was used as a catalyst.
Thirty minutes after the start of the reaction, the HFP conversion was 84 %, and the HFPO selectivity was 67 %.
The procedure of Bxample 25 was repeated wherein the amount of the catalyst, tetra-n-butylphosphonium bromide, was changed from 0.12 g to 0.04 g, and the reaction was carried out at a -temperature of 20C.
The HFP conversion was-71 %, and the HFPO selectivity was 62 %.
The procedure of Example 26 was repeated wherein the reaction was carried out at a temperature of 40C.
The HFP conversion was 83 %, and the HFPO selectivity w.as 54 %.
The procedure of Example 1 was repeated wherein .
0.20 g of tetra-n-butylphosphonium bromide was used as a catalyst, and the reaction was carried out at a temperature of -10C.
"
. .
The ~IFP conversion was 77 %, and the HFP0 selectivity was 69 %.
EXA~IPLE 29 The procedure of Example 1 was repeated wherein 0.12 g ~0.29 milimole) of amyltriphenylphosphonium bromide was used as a catalyst, and the reaction was carried out for a period of 4 hours.
The HFP conversion was 70 %, and the HFP0 selec-tivity was 66 %.
The procedure of Example 1 was repeated wherein chloroform was used in place of F-113, 0.04 g (0.12 milimole) of tetra-n-butylphosphonium bromide was used as a catalyst, and hexafluoropropylene was used in the amount of 0.6 g : 15 ~4 milimoles).
The HFP conversion was 89 %, and the HFP0 selec-tivity was 61 %.
The procedure of Example 30 was repeated wherein 0.02 g ~0.04 milimole) of hydrochloric acid tetraphenylarso-nium chloride ~Ph4ArCQ-HCQ) was used as a catalyst.
. The HFP conversion was 78 %, and the HFP0 selec-tivity was 74 %.
EXAMPLES 32 to 38 The procedure of Example 1 was repeated wherein chloroform was used in place of F-113, hexafluoropropylene . .
~2~ L6 was used in the amo~mt of 0.5 g, and as a catalyst, each of the large ring polyethers and large ring aminoethers shown in Table 4 was used.
The results are shown in Table 4 below.
Table 4 Amount of HFP Con- HFPO Selec-Exam- Catalyst Reaction version tivity ple Catalyst _ (g)Time~}Irs) (%) (~) 32 18-crown-6 1 0.36 0.5 74 82 33 dibenzo-18- 0.36 2.0 84 80 CTOWn 2 1034 benzo-15-crown-5 3 0.36 2.0 78 81 ~ryptofix~222B 4 0.04 8 1.0 85 74 36 ~ryptofix#-221 5 0.12 0.5 92 63 37 ~ryptofix#-22 6 0.12 2.0 86 80 38 ~ryptofix#-22DD 7 0.12 l.0 7~ 8 5 15 The chemical structures of the compounds used are shown below:
# trade mark . ;. . .
, [D2~L~
*1 *2 /~ /--\
~ o ~ ~o O 0~
O ~ ' O ~ ~ O
l o ~ -*3 *4 *5 ~, u ~ n - *6 ~*7 - fo~o^~ ~o~o ~
.- HN NH CloH2l-N ~ ClOH21 0~_~!0~ ~O ~
.... .
: ' .
~2~2~ ~
*1 to *3: Named according to the Pederson's nomenculature (J. I~m. Chem Soc., 89, 7071 (1967)).
*4 to *7: Trade mar~s (produced by ~Ierck ~ Co.) *8 : 50 % Toluene solution XA~IPLE 39 The procedure of Example 1 was repeated ~herein 0.24 g of Cryptofix 222B (trade mark, produced by ~Ierck ~ Co.) was used as a catalyst.
Four hours after the start of the reaction, the HFP
convcrsion was 53 %~ and the HFPO selectivity was 74 %.
The procedure of Example 1 was repeated wherein 0.36 g of a polyether having the foTmula shown below was used as a catalyst.
\~
O O O O P ' \ J \ r /
Four hours after the start of the reaction, the HFP conversion was 61 ~, and the HFPO selectivity was 74 %.
EXA~IPLE 41 The procedure of Example 1 was repeated wherein 0.12 g of a nonionic surface active agent, polyoxyethylene oleyl ether ~produced by Nippon Oils ~ Fats Co., Ltd.:
H.L.B., 16.6), was used as a catalyst.
~22C~fi Three hours after the s~art of the reaction, the HFP conversion was 75 %, and the HFPO selectivity was 76 ~.
EX~IPLE 42 The procedure of Example 1 was repeated wherein 0.12 g of tri-n-octylamine-N-oxide was used as a catalyst.
Two hours a-fter the start of the reaction, the HFP
conversion was 26 %, and the HFPO selectivity was 45 %.
EXAMPLE 43~
. The procedure of Example 1 was repeated wherein 0.12 g of 4-(5-nonyl)pyridine-N-oxide was used as a catalyst.
Three hours after the start of the reaction, the HFP conversion was 51 %, and the HFPO selectivity was 36 %.
: EXAMPLE 44 The procedure of Example 32 was Tepeated wherein 15 0.36 g of polyvinyl pyrrolidone (average molecular weight, 40,000) was used as a ca~alyst.
Two hours after the start o-f the reaction, the HFP conversion was 76 %, and the HFPO selectivity was 82 %.
EX~MPLE 45 20 The procedure of Example 1 was repeated wherein . 1.2 g (8 milimoles) of hexafluoropropylene was used, and -: 20 mQ of an aqueous sodium hypochlorite solution B-O ~con-taining 40 milimoles of sodium hypochlorite and 0.5 milimole : of sodium hydroxide? was used in place of the aqueous sodium hypochlorite solution A. The molar ratio of sodium hydroxide ~ 6 to hexafluoropropylene was 0.06/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 5.0/1.
One hour after the start of the reaction, the HFP
conversion was 87 %, and the HFPO selectivity was 57 %. In this case, even though the reaction was further continued, no increase in the HFP conversion was observed.
The procedure of Exarnple 45 was repeated wherein 20 mQ of an aqueous sodium hypochlorite solution B-l (con-taining 40 milimoles of sodium hypochlorite and 2 milimolesof sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.25/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 5.0/1.
One hour after the start of the reaction, the HFP
conversion was 91 %, and the HFPO selectivity was 72 %.
The procedure of Examp]e 45 was repeated wherein Z0 mQ of an aqueous sodium hypochlorite solution B-2 (con-taining 40 milimoles of sodium hypochlorite and 31 milimolesof sodium hydroxide) was used. The moIar ratio of sodium hydroxide to hexafluoropropylene was 3.8/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 5.0/1.
One hour after the start of the reaction, the HFP
conversion was 99 %, and the HFPO selectivity was 77 %.
EXA~IPLE 48 The procedure of Example 1 was repeated wherein 20 mQ of an aqueous sodium hypochlorite solution C (con-taining 34 milimoles of sodium hypochlorite and 19 milimoles of sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 1.9/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 3.4/1.
Fifteen minutes after the start of the reaction, the HFP conversion was 9S %, and ~he HFPO selectivity was 78 %.
Thirty minutes after the start of the reaction, the HFP con-version was 99 %, and the HFPO selectivity was 76 %.
E~A~IPLE 49 A 300-mQ autoclave of glass was charged with 150 mQ
of an aqueous sodium hypochlorite solution B-3 ~containing 300 milimoles of sodium hypochlorite and 60 milimoles of sodium hydroxide), 100 mQ of F-113, 11 g (73 milimoles) o~
hexafluoropropylene, and 0.65 g ~1.6 milimoles) of TO~IAC.
The reaction was carried out at a temperature of from -10C :
to -5C and a rate of stirring of 1,000 r.p.m. for a period of 25 minutes. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.82/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 4.1/1.
Gas chromatographic analysis of the products indicated that the EIFP conversion was 96 %, and the HFPO selectivity was 76 %.
- ~1 -z~
The procedure of Example 49 was repeated wherein lO0 mQ of diisopropyl ether was used in place of F-113 as an organic solvent, and the reaction was carried out for a period o-f 20 minutes.
The HFP conversion was 90 %, and the HFPO selecti-vity was 70 %.
EXAMPLE 51 ~
The proceduTe of Example 49 was repeated wherein 100 mQ of a mixed solvent of benzene and n-hexane (volume ratio, 1/9) was used in place of F-113 as an organic solvent, TO~C was used in the amount of 0.33 g (0.8 milimole) in place of 0.65 g,. and the reaction was carried out for a period of 30 minutes.
The HFP conversion was 80 %, and the HFPO selecti-~- vity was 78 %.
The procedure of Example 45 was repeated wherein 5.7 mQ of an aqueous sodium hypochlorite solution C (con-.20 taining 9.6 milimoles of sodium hypochlorite and 5.4 milimoles : of sodium hydroxide) was used. The molar ratio of sodium .. ~ hydroxide to hexafluoropropylene was 0.68/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 1.2/1.
. Fifteen minutes after the start of the reaction, the HFP conversion was 50 %,..and.the HFPO selectivity was 73 %.
.- , ' .
.. - 4~ -, .
2~i EXA~IPLE 53 The procedure of Example 45 was repeated wherein 15.2 mQ of an aqueous sodium hypochlorite solution D (con-taining 9.6 milimoles of sodium hypochlorite and 6.1 milimoles of sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.76/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 1.2/1. .
Fifteen minutes after the start of the reaction, the HFP conversion was 77 %, and the HFPO selectivity was 74 %.
EXA~IPLE 54 The procedure of Example 1 was repeated wherein 20 mQ of an aqueous sodium hypochlorite solution B-4 ~con-taining 20 milimoles of sodium hypochlorite and 8 milimoles of sodium hydroxide) was used. The molar ratio of sodium hydroxide to hexafluoropropylene was 0.80/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 2.0/1.
One hour after the start of the reaction, the HFP
conversion was 91 %, and the HFPO selectivity was 80 %.
EXA~IPLE 55 In this example 7 hexafluoropropylene oxide was prepared from hexafluoropropylene by the use of continuous reaction equipment as illustrated in the Figure, comprising a stationary mixer l (length: 150 mm: including a twisted ' .
blade type mixing element), a 160-mQ tubular reactor 2, a decanter 3, a HFPO distillation column 4, and a 1,000-mQ
organic phase tank 5.
The stationary mixer 1, tubular reactor 2~ and decanter 3 were cooled down to -10C, and the pressure was maintained at 3 kg/cm2'(gauge pressure) with nitrogen gas.
A F-113 solution containing 0.045 mole/Q of TOMAC was circu-lated in the reaction equipment at a flow rate of 33 mQ/min.
Then, an aqueous sodium hypochlorite solution B-4 ~containing 1.0 mole/Q of sodium hypochlorite and 0.40 mole/Q o-f sodiwn hydroxide~ was introduced into the stationary mixer 1 at a flow rate of 27 mQ/min, and was withdrawn simultaneously from the decanter 3. Hexafluoropropylene was introduced into an organic phase line before the stationary mixer 1 at a flow rate of 2.10 g/
min ~14.0 milimoles/min) to start the reaction. In the tubular reactor 2 the molar ratio of sodium hydroxide to hexafluoropropylene was 0.77/1, and the molar ratio of sodium hypochlorite to hexafluoropropylene was 1.9/1. The organic phase and aqueous phase were finely dispersed in the stationary mixer 1, and pa~sed through the tubular reactor 2 in the dispersed state during-which the reaction proceeded between the two phases.
The reaction solution leaving the tubular reactor 2 was introduced into the decanter 3 where it was separated into the organic phase and aqueous phase. The aqueous phase was discharge out of the reaction equipment. The organic phase : ' :
.
~2~32~
containing the formed hexafluoropropylene oxide was sent to the HFPO distillation column 4 where the formed hexafluorpro-pylene oxide and the unreacted hexafluoropropylene were separated from the organic phase. During the period from 1 to 2 hours after the start of the reaction, the average distillation rate of hexafluoropropylene oxide was 1.80 g/min (10.8 milimoles/min), and the average distillation rate of hexafluoropropylene was 0.02 g/min ~0.13 milimoles/min).
The organic phase from which the hexafluoropropylene oxide and hexafluoropropylene had been distilled away in the HFPO
distillation column 4 was sent to the organic phase tank 5 and, thereafter, was returned to the stationary mixer 1.
While the invention has been described in detail and with reference to specific embodiment thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein withou~ departing from the spirit and scope thereof.
Claims (39)
1. A process for producing hexafluoropropylene oxide from hexafluoropropylene, which comprises epoxidizing hexa-fluoropropylene in a two-phase system of an aqueous phase and an organic phase using a hypochlorite as an oxidizing agent, said hypochlorite being dissolved or dispersed in the aqueous phase, in the presence of at least one catalyst selected from the group consisting of (a) quaternary ammonium salts, (b) quaternary phosphonium salts, (c) quaternary arsonium salts, and (d) lipophilic complexing agents for cations contained in the hypochlorite.
2. A process as claimed in Claim 1, wherein said aqueous phase is further comprised of an inorganic base.
3. A process as claimed in Claim 2, wherein the reac-tion is carried out in the presence of at least 0.1 gram equivalent of the inorganic base per mole of the hexafluoro-propylene.
4. A process as claimed in Claim 2 or 3, wherein the inorganic base is sodium hydroxide.
5. A process as claimed in Claim 1 or 2, wherein the hypochlorite is selected from the group consisting of sodium hypochlorite and potassium hypochlorite.
6. A process as claimed in Claim 1 , wherein the reaction is carried out at a temperature ranging between -25°C
and 60°C.
and 60°C.
7. A process as claimed in Claim 1 or 2, wherein the organic phase contains at least one solvent selected from the group consisting of chlorinated hydrocarbons and fluorine-containing solvents.
8. A process as claimed in Claim 1 or 2, wherein the quaternary ammonium salt has a total number of carbon atoms of from 6 to 100 per quaternary ammonium ion.
9. A process as claimed in Claim 1 or 2, wherein the quaternary phosphonium salt has a total number of carbon atoms of from 6 to 100 per quaternary phosphonium ion.
10. A process as claimed in Claim 1 or 2, wherein the quaternary arsonium salt is selected from the group consisting of tetraarylarsonium salt and triarylalkylarsonium salt.
11. A process as claimed in Claim 1 , wherein as the oxidizing agent, a hypochloric acid alkali metal salt and/or a hypochloric acid alkaline earth metal (excluding beryllium) salt is used, and as the catalyst, a lipophilic complexing agent for alkali metal ions and/or alkaline earth metal (exclud-ing beryllium) ions is used.
12. A process as claimed in Claim 11, wherein the lipophilic complexing agent is a large ring polyether.
13. A process as claimed in Claim 11, wherein the lipophilic complexing agent is a large ring aminoether.
14. A process as claimed in Claim 11, wherein the lipophilic complexing agent is polyethylene glycol or its derivative.
15. A process as claimed in Claim 11, wherein the lipophilic complexing agent is polyvinyl pyrrolidone or its derivative.
16. A process as claimed in Claim 11, wherein the lipophilic complexing agent is an amineoxide represented by the general formular (VIII) or its derivative R14R15R16N?O (VIII) wherein R14, R15 and R16, each is a hydrocarbon group, the total number of carbon atoms contained in R14, R15 and R16 is at least 10, and R14 and R15, or R14, R15 and R16 may combine together to form a nitrogen-containing ring.
17. A process as claimed in Claim 1 or 2, wherein after the synthesis of hexafluoropropylene oxide from hexafluoropropylene by the two-phase reaction, the organic phase and aqueous phase are separated from each other, the hexafluoropropylene oxide is isolated from the organic phase, and hexafluoropropylene is added to the residual organic phase containing the catalyst and the resulting mixture is re-used in the two-phase reaction.
18. A process as claimed 1, wherein the available chlorine content in the aqueous phase is from 1 % to 25 %.
19. A process as claimed in Claim 18, wherein the available chlorine content in the aqueous phase is from 3 %
to 20 %.
to 20 %.
20. A process as claimed in Claim 1, wherein the catalyst is contained in an amount of from 0.0001 to 10 moles per gram equivalent of hypochlorite ion.
21. A process as claimed in Claim 20, wherein the catalyst is contained in an amount of from 0.001 to 1 mole per gram equivalent of hypochlorite ion.
22. A process as claimed in Claim 1, wherein the organic phase is from 0.05 to 20 times as much as the aqueous phase.
23. A process as claimed in Claim 22, wherein the organic phase is from 0.2 to 5 times as much as the aqueous phase.
24. A process as claimed in Claim 6, wherein the reaction is carried out at a temperature ranging between -20°C to 40°C.
25. A process as claimed in Claim 24, wherein the reaction is carried at a temperature ranging between -18°C
to 20°C.
to 20°C.
26. A process as claimed in Claim 2, wherein the reaction is carried out at a temperature ranging between -25°C and 60°C.
27. A process as claimed in Claim 2, wherein as the oxidizing agent, a hypochloric acid alkali metal salt and/or a hypochloric acid alkaline earth metal (excluding beryllium) salt is used, and as the catalyst, a lipophilic complexing agent for alkali metal ions and/or alkaline earth metal (excluding beryllium) ions is used.
28. A process as claimed in Claim 2, wherein the available chlorine content in the aqueous phase is from 1 % to 25 %.
29. A process as claimed in Claim 2, wherein the catalyst is contained in an amount of from 0.0001 to 10 moles per gram equivalent of hypochlorite ion.
30. A process as claimed in Claim 2, wherein the organic phase is from 0.05 to 20 times as much as the aqueous phase.
31. A process as claimed in Claim 27, wherein the lipophilic complexing agent is a large ring polyether.
32. A process as claimed in Claim 27, wherein the lipophilic complexing agent is a large ring aminoether.
33. A process as claimed in Claim 27, wherein the lipophilic complexing agent is polyethylene glycol or its derivative.
34. A process as claimed in Claim 27, wherein the lipophilic complexing agent is polyvinyl pyrrolidone or its derivative.
35. A process as claimed in Claim 27, wherein the lipophilic complexing agent is an amineoxide represented by the general formular (VIII) or its derivative R14R15R16N?O (VIII) wherein R14, R15 and R16, each is a hydrocarbon group, the total number of carbon atoms contained in R14, R15 and R16 is at least 10, and R14 and R15, or R14, R15 and R16 may combine together to form a nitrogen-containing ring.
36. A process as claimed in Claim 28, wherein the available chlorine content in the aqueous phase is from 3 % to 20%.
37. A process as claimed in Claim 29, wherein the catalyst is contained in an amount of from 0.001 to 1 mole per gram equivalent of hypochlorite ion.
38. A process as claimed in Claim 30, wherein the organic phase is from 0.2 to 5 times as much as the aqueous phase.
39. A process as claimed in Claim 26, wherein the reaction is carried out at a temperature ranging from -20°C to 40°C.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56067834A JPS57183773A (en) | 1981-05-06 | 1981-05-06 | Preparation of hexafluoropropylene oxide |
| JP67834/81 | 1981-05-06 | ||
| JP56205581A JPS58105978A (en) | 1981-12-19 | 1981-12-19 | Preparation of hexafluoropropylene oxide |
| JP205581/81 | 1981-12-19 | ||
| JP210487/81 | 1981-12-26 | ||
| JP56210487A JPS58113187A (en) | 1981-12-26 | 1981-12-26 | Preparation of hexafluoropropylene oxide |
| JP57015539A JPS58134086A (en) | 1982-02-04 | 1982-02-04 | Synthetic method of hexafluoropropylene oxide |
| JP15539/82 | 1982-02-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1220216A true CA1220216A (en) | 1987-04-07 |
Family
ID=27456401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000402298A Expired CA1220216A (en) | 1981-05-06 | 1982-05-05 | Process for the production of hexafluoropropylene oxide |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US4902810A (en) |
| EP (1) | EP0064293B1 (en) |
| CA (1) | CA1220216A (en) |
| DE (1) | DE3274643D1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3369988D1 (en) * | 1982-07-26 | 1987-04-09 | Asahi Chemical Ind | Fluoroepoxides and a process for production thereof |
| IT1170254B (en) * | 1983-11-28 | 1987-06-03 | Montedison Spa | PROCESS FOR THE PREPARATION OF PERFLUOROPROPENE OXIDE |
| US5276189A (en) * | 1988-10-25 | 1994-01-04 | Asahi Kasei Kogyo K.K. | Process for the treatment of quaternary onium salts and its application to the preparation of hexafluoropropylene oxide |
| EP0387725B1 (en) * | 1989-03-13 | 1997-01-22 | Sumitomo Seika Chemicals Co., Ltd. | Production of thiophene-2,5-dicarboxylic acid diesters and tetrahydrothiophene-2,5-dicarboxylic acid diesters |
| JPH03148270A (en) * | 1989-08-25 | 1991-06-25 | E I Du Pont De Nemours & Co | Three liquid phase epoxidation of perfluoroolefin |
| JPH0383973A (en) * | 1989-08-28 | 1991-04-09 | Sumitomo Pharmaceut Co Ltd | Threo-selective production of epoxy modification |
| JPH04247078A (en) * | 1990-08-29 | 1992-09-03 | E I Du Pont De Nemours & Co | Process for epoxidizing hexafluoropropylene |
| JP3524120B2 (en) * | 1992-05-08 | 2004-05-10 | 生化学工業株式会社 | Pretreatment agent, pretreatment method, measurement method using pretreated sample, measurement kit, and sample determination method |
| CN1224620C (en) * | 1999-05-04 | 2005-10-26 | 纳幕尔杜邦公司 | Polyfluorinated epoxides and associated polymers and processes |
| KR100468526B1 (en) * | 2001-10-23 | 2005-01-27 | 한국과학기술연구원 | Production Method of Hexafluoropropylene oxide from Hexafluoropropylene and NaOCl |
| KR100816878B1 (en) * | 2006-10-16 | 2008-03-27 | 한국화학연구원 | Manufacturing method of hexafluoropropylene-oxide with high yield |
| CN1966498B (en) * | 2006-11-14 | 2010-05-12 | 上海三爱富新材料股份有限公司 | Hexafluoroepoxypropane preparation process |
| ZA200907387B (en) * | 2008-10-27 | 2010-07-28 | Univ Kwazulu Natal | Recovery of components making up a liquid mixture |
| EP2857390B1 (en) * | 2009-03-17 | 2017-12-06 | Daikin Industries, Limited | Method for producing hexafluoropropylene oxide |
| EP2409971B1 (en) * | 2009-03-18 | 2017-05-10 | Daikin Industries, Ltd. | Method for separating hexafluoropropylene oxide from hexafluoropropylene |
| KR101176788B1 (en) | 2009-09-24 | 2012-08-24 | 한국화학연구원 | Apparatus and method for semi-batch continuous manufacturing of hexafluoropropylene oxide |
| MX2012007352A (en) * | 2009-12-23 | 2013-05-20 | Liberty Diversified International Inc | System and method for structure design. |
| CN105524030A (en) * | 2015-12-29 | 2016-04-27 | 天津市长芦化工新材料有限公司 | Method for synthesis of hexafluoropropylene oxide by use of two-liquid-phase buffer solution method under atmospheric pressure |
| CN105461663B (en) * | 2015-12-31 | 2018-05-11 | 天津市长芦化工新材料有限公司 | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of temperate condition |
| CN105439981B (en) * | 2015-12-31 | 2019-03-15 | 天津市长芦化工新材料有限公司 | The device and method of hexafluoropropylene oxide is continuously prepared under a kind of condition of normal pressure |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2700686A (en) * | 1951-02-15 | 1955-01-25 | Eastman Kodak Co | Hydroxy substituted polyfluorinated compounds |
| US3358003A (en) * | 1959-07-17 | 1967-12-12 | Fluorocarbon epoxides | |
| US3313829A (en) * | 1962-06-05 | 1967-04-11 | David H Rosenblatt | Process for making epoxides from ethylenic compounds with electron-with drawing groups |
| US3536733A (en) * | 1967-08-10 | 1970-10-27 | Du Pont | Method for the preparation of halogenated epoxides |
| US3996259A (en) * | 1975-11-06 | 1976-12-07 | The Dow Chemical Company | Oxidation of organic compounds by aqueous hypohalites using phase transfer catalysis |
| US4006169A (en) * | 1976-02-26 | 1977-02-01 | Smithkline Corporation | Epoxidation of α,β-ethylenic ketones |
| US4098831A (en) * | 1977-08-03 | 1978-07-04 | E. I. Du Pont De Nemours And Company | Nitrobenzotrichloride or bromide process |
| US4356291A (en) * | 1981-04-03 | 1982-10-26 | E. I. Du Pont De Nemours And Company | Purification and polymerization of hexafluoropropylene oxide |
-
1982
- 1982-05-04 DE DE8282103810T patent/DE3274643D1/en not_active Expired
- 1982-05-04 EP EP82103810A patent/EP0064293B1/en not_active Expired
- 1982-05-05 CA CA000402298A patent/CA1220216A/en not_active Expired
-
1987
- 1987-07-06 US US07/072,189 patent/US4902810A/en not_active Expired - Lifetime
-
1989
- 1989-05-03 US US07/346,667 patent/US4925961A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0064293B1 (en) | 1986-12-10 |
| US4925961A (en) | 1990-05-15 |
| EP0064293A1 (en) | 1982-11-10 |
| DE3274643D1 (en) | 1987-01-22 |
| US4902810A (en) | 1990-02-20 |
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