New Industrial Process for Manufacturing of Perfluoro (Methyl Vinyl Ether)(PFMVE) and of 1,1,2,2-Tetrafluoro-1-(Trifluoromethoxy)ethane (TFTFME)

Abstract

The invention relates to a new industrial process for manufacturing of perfluoro(methylvinylether) (PFMVE), and of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), involving reactions in liquid phase and performing reactions, for example, in a (closed) column reactor or in a microreactor, respectively. The invention also relates to a new industrial process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) by HF-elimination from the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227). The invention also relates to a new industrial process for manufacturing of the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) by selective fluorination of the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane), i.e., perfluorination of only the CH.sub.3O-group (i.e., methoxy-group) of the compound HFE-254 is selectively fluorinated to a CF.sub.3O-group (i.e., trifluoromethoxy-group).

Claims

1. A process for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), ##STR00030## wherein the process comprises the steps of a direct fluorination reaction (A) and HF-elimination reaction (B), in a reactor or reactor system, resistant to elemental fluorine (F2) and hydrogen fluoride (HF): (A) in a first reaction step a direct fluorination by reacting the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III), ##STR00031## with an about stoichiometric quantity of elemental fluorine (F2) comprised in a fluorination gas to selectively substitute in the compound of formula (III) the three hydrogen atoms of the 1-(methoxy) group of the compound HFE-254 of formula (III) for fluorine, and wherein the reaction is carried out at temperature in the range of from about 0° C. to about +60° C. and at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute to yield the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), ##STR00032## and with or without isolating and/or purifying the (intermediate) fluorination product (TFTFME), (E 227); preferably without isolating and/or purifying the (intermediate) fluorination product (TFTFME), (E 227), (B) in a second reaction step an elimination reaction, wherein HF (hydrogen fluoride) is eliminated from the (intermediate) fluorination product (TFTFME), (E 227), of formula (II), obtained in step (A), and the elimination reaction is performed (i) as a(n) (exothermic) elimination reaction in the presence of one or more nitrogen-containing organic bases, and/or in the presence of one or more inorganic bases, wherein the temperature of the (exothermic) elimination reaction is controlled to not exceed a temperature of about 60° C., and wherein the (exothermic) elimination reaction is carried out at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute or (ii) as a, non-catalytic or preferably catalytic, more preferably Ni (nickel) catalytic, thermal elimination reaction at a temperature in the range of about 60° C. to about 120° C., to yield the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I), and (C) withdrawing and collecting the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I) obtained in step (B) from the reactor or reactor system, and (D) optionally isolating and/or purifying the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I).

2. A process for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), ##STR00033## wherein the process comprises, in a reactor or reactor system, resistant to elemental fluorine (F.sub.2) and hydrogen fluoride (HF), performing an HF-elimination reaction step (B), wherein in the elimination reaction, HF (hydrogen fluoride) is eliminated from the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), ##STR00034## and the elimination reaction step (B) is performed (i) as a(n) (exothermic) elimination reaction in the presence of one or more nitrogen-containing organic bases, and/or in the presence of one or more inorganic bases, wherein the temperature of the (exothermic) elimination reaction is controlled to not exceed a temperature of about 60° C., and wherein the (exothermic) elimination reaction is carried out at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute, or (ii) as a, non-catalytic or preferably catalytic, more preferably Ni (nickel) catalytic, thermal elimination reaction at a temperature in the range of about 60° C. to about 120° C., to yield the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I), and (C) withdrawing and collecting the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I) obtained in step (B) from the reactor or reactor system, and (D) optionally isolating and/or purifying the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I).

3. A process for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), ##STR00035## wherein the process comprises, in a reactor or reactor system, resistant to elemental fluorine (F.sub.2) and hydrogen fluoride (HF), performing a direct fluorination reaction step (A), wherein in the direct fluorination reaction the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III), ##STR00036## is fluorinated with an about stoichiometric quantity of elemental fluorine (F.sub.2) comprised in a fluorination gas to selectively substitute in the compound of formula (III) the three hydrogen atoms of the 1-(methoxy) group of the compound HFE-254 of formula (III) for fluorine, and wherein the reaction is carried out at temperature in the range of from about 0° C. to about +60° C., and at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute, to yield the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), ##STR00037## and (C) withdrawing and collecting the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II) obtained in step (A) from the reactor or reactor system, and (D) optionally isolating and/or purifying the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II).

4. The process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the fluorination (A) reaction is performed in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), and wherein the fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is in a range of from about 1% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume; preferably wherein (i) the fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is in a range of from about 1% by volume of elemental fluorine (F.sub.2) up to about 30% by volume of elemental fluorine (F.sub.2), more preferably of from about 5% by volume of elemental fluorine (F.sub.2) up to about 25% by volume of elemental fluorine (F.sub.2), even more preferably of from about 5% by volume of elemental fluorine (F.sub.2) up to about 20% by volume of elemental fluorine (F.sub.2), each range based on the total F.sub.2-fluorination gas composition as 100% by volume; or (ii) the fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is in a range of from about 85% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), more preferably of from about 90% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume.

5. The process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the fluorination (A) reaction is performed in a tube reactor system, in a continuous flow reactor system, in a coil reactor system, or in a microreactor system, preferably in a microreactor system, and wherein the fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is in a range of from about 85% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), more preferably of from about 90% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume.

6. A process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in a (closed) column reactor.

7. A process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the liquid reaction medium of the direct fluorination reaction (A) is circulated in a loop in a (closed) column reactor to perform the fluorination reaction (A), while the fluorination gas comprising elemental fluorine (F2) is fed into the (closed) column reactor and is passed through the liquid reaction medium to react with the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III); preferably wherein the loop is operated with a circulation velocity in the range of from about 1,000 l/h to about 2,000 l/h, more preferably in the range of from about 1,250 l/h to about 1,750 l/h; still more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+200 l/h; even more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+100 l/h; and most preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+50 l/h.

8. The process according to claim 7, wherein for the direct fluorination reaction (A) the closed column reactor is equipped with at least one of the following: (i) at least one heat exchanger (system), at least one liquid reservoir, with inlet and outlet for, and containing the liquid reaction medium; (ii) a pump for pumping and circulating the liquid reaction medium; (iii) one or more nozzle jets, preferably wherein the one or more nozzle jets are placed at the top of the column reactor, for spraying the circulating reaction medium into the closed column reactor; (iv) one or more feeding inlets for introducing the fluorination gas comprising or consisting of elemental fluorine (F2) into the (closed) column reactor; (v) optionally one or more sieves, preferably two sieves, preferably the one or more sieves placed at the bottom of the (closed) column reactor; (vi) and at least one gas outlet equipped with a pressure valve, and at least one outlet for withdrawing the fluorinated compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II) from the (closed) column reactor.

9. A process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the liquid reaction medium of the HF-elimination reaction (B) is circulated in a loop in a (closed) column reactor to perform the HF-elimination reaction (B), and wherein the loop is operated with a circulation velocity in the range of from about 1,000 l/h to about 2,000 l/h, preferably in the range of from about 1,250 l/h to about 1,750 l/h; more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+200 l/h; even more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h±100 l/h; and most preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+50 l/h.

10. The process according to claim 9, wherein for the HF-elimination reaction (B) the closed column reactor is equipped with at least one of the following: (i) at least one heat exchanger system, at least one liquid reservoir, with inlet and outlet for, and containing the liquid reaction medium; (ii) a pump for pumping and circulating the liquid reaction medium; (iii) one or more nozzle jets, preferably wherein the one or more nozzle jets are placed at the top of the column reactor, for spraying the circulating reaction medium into the closed column reactor; (iv) optionally, in case of (i) preferably performing the HF-elimination reaction as a(n) (exothermic) elimination reaction in the presence of one or more nitrogen-containing organic bases, one or more feeding inlets for introducing the one or more nitrogen-containing organic bases into the closed column reactor; (v) optionally one or more sieves, preferably two sieves, preferably the one or more sieves placed at the bottom of the closed column reactor; (vi) and at least one gas outlet equipped with a pressure valve, and at least one outlet for withdrawing the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I) from the closed column reactor.

11. The process according to claim 6 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein column reactor is a packed bed tower reactor, preferably a packed bed tower reactor is packed with fillers resistant to the reactants and especially resistant to elemental fluorine (F.sub.2) and to hydrogen fluoride (HF) such as, e.g., with Raschig fillers, E-TFE fillers, and/or HF-resistant metal fillers, e.g., Hastelloy metal fillers, and/or (preferably) HDPTFE-fillers, more preferably wherein the packed bed tower reactor is a gas scrubber system (tower) which is packed with any of the before mentioned HF-resistant Hastelloy metal fillers and/or HDPTFE-fillers, and preferably with HDPTFE-fillers.

12. The process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in at least one step in a continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm, more preferably in at least one step in a microreactor; still more preferably wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in at least in one step as a continuous processes, wherein the continuous process is performed in at least one continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm; even more preferably wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in at least in one step as a continuous processes, wherein the continuous process is performed in at least one microreactor.

13. A process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), characterized in that prior to starting any of the process steps (A) and (B) one or more of the reactors used, preferably each and any of the reactors used, are purged with an inert gas or a mixture of inert gases, preferably with He (helium) and/or N.sub.2 (nitrogen) as the inert gas, more preferably with N.sub.2 (nitrogen) as the inert gas.

14. A process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), characterized in that in the fluorination reaction step (A) the reaction is performed in a SiC-reactor; preferably in that in the fluorination reaction step (A) the reaction is performed in a SiC-microreactor.

15. A process according to claim 1, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), characterized in that in the HF-elimination step (B) the reaction is performed in a nickel-reactor (Ni-reactor) or in a reactor with an inner surface with high nickel-content (Ni-content); preferably in that in the HF-elimination step (B) the reaction is performed in a nickel-microreactor (Ni-microreactor) or in a microreactor with an inner surface with high nickel-content (Ni-content).

16. A process according to claim 1 for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), characterized in that, independently, the product yielding from fluorination reaction step (A) and/or the product yielding from HF-elimination step (B) are subjected to distillation.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0159] FIG. 1 shows the manufacture of PFVME out of HFE 254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) and F2 fluorination gas, over E 227 (TFTFME) as an intermediate compound, and using a counter current reactor system.

[0160] FIG. 2 shows the manufacture of PFMVE by reaction of HFE 254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) with F2 fluorination gas, over E 227 (TFTFME) as an intermediate compound in a sequence of two microreactors.

DETAILED DESCRIPTION OF THE INVENTION

[0161] As briefly described in the Summary of the Invention, and defined in the claims and further detailed by the following description and examples herein, the invention relates to a new industrial process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE), and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), which is a suitable intermediate in the manufacture of perfluoro(methyl vinyl ether) (PFMVE), involving reactions in liquid phase and performing reactions in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), as well as in a tube reactor system, a continuous flow reactor system, in a coil reactor system or in a microreactor system, preferably performing reactions in a counter-current reactor system or in a microreactor, respectively, as each described here under and in the claims.

[0162] In one aspect, the invention pertains to a process for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I),

##STR00022##

[0163] wherein the process comprises the steps of a direct fluorination reaction (A) and HF-elimination reaction (B), in a reactor or reactor system, resistant to elemental fluorine (F.sub.2) and hydrogen fluoride (HF):

[0164] (A) in a first reaction step a direct fluorination by reacting the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III),

##STR00023##

[0165] with an about stoichiometric quantity of elemental fluorine (F2) comprised in a fluorination gas to selectively substitute in the compound of formula (III) the three hydrogen atoms of the 1-(methoxy) group of the compound HFE-254 of formula (III) for fluorine, and wherein the reaction is carried out at temperature in the range of from about 0° C. to about +60° C.,

[0166] preferably at temperature in the range of from about 0° C. to about +60° C., more preferably of at temperature in the range from about 10° C. to about +50° C., even more preferably at temperature in the range of from about 20° C. to about +40° C.,

[0167] and at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute,

[0168] preferably at a pressure in the range of from about 5 bar absolute bar to about 20 bar absolute, more preferably at a pressure in the range of from about 5 bar absolute bar to about 15 bar absolute, even more preferably at a pressure in the range of from about 5 bar absolute bar to about 12 bar absolute, and most preferably at a pressure in the range of from about 6 bar absolute bar to about 11 bar absolute,

[0169] to yield the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II),

##STR00024##

[0170] and

[0171] with or without isolating and/or purifying the (intermediate) fluorination product (TFTFME), (E 227); preferably without isolating and/or purifying the (intermediate) fluorination product (TFTFME), (E 227),

[0172] (B) in a second reaction step an elimination reaction, wherein HF (hydrogen fluoride) is eliminated from the (intermediate) fluorination product (TFTFME), (E 227), of formula (II), obtained in step (A), and the elimination reaction is performed

[0173] (i) as a(n) (exothermic) elimination reaction in the presence of one or more nitrogen-containing organic bases,

[0174] preferably as a non-aqueous (exothermic) elimination reaction in the presence of one or more nitrogen containing organic bases,

[0175] and/or

[0176] in the presence of one or more inorganic bases,

[0177] preferably as a(n) (exothermic) elimination reaction with an aqueous solution containing one or more inorganic bases, more preferably as a(n) (exothermic) elimination reaction with an aqueous solution containing one or more inorganic bases in the presence of one or more phase transfer catalysts,

[0178] wherein the temperature of the (exothermic) elimination reaction is controlled to not exceed a temperature of about 60° C.,

[0179] preferably to not exceed a temperature of about 50° C., more preferably to not exceed a temperature of about 45° C., and even more preferably to not exceed a temperature of about 40° C.,

[0180] and wherein the (exothermic) elimination reaction is carried out at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute,

[0181] preferably at a pressure in the range of from about 4 bar absolute bar to about 20 bar absolute, more preferably at a pressure in the range of from about 4 bar absolute bar to about 15 bar absolute, even more preferably at a pressure in the range of from about 4 bar absolute bar to about 10 bar absolute, and most preferably at a pressure in the range of from about 4 bar absolute bar to about 8 bar absolute,

[0182] or

[0183] (ii) as a, non-catalytic or preferably catalytic, more preferably Ni (nickel) catalytic, thermal elimination reaction at a temperature in the range of about 60° C. to about 120° C.,

[0184] preferably at a temperature in the range of about 70° C. to about 110° C., more preferably at a temperature in the range of about 70° C. to about 100° C., even more preferably at a temperature in the range of about 70° C. to about 90° C.,

[0185] to yield the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I),

[0186] and

[0187] (C) withdrawing and collecting the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I) obtained in step (B) from the reactor or reactor system,

[0188] and

[0189] (D) optionally isolating and/or purifying the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I).

[0190] In another aspect, the invention pertains to a process for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I),

##STR00025##

[0191] wherein the process comprises, in a reactor or reactor system, resistant to elemental fluorine (F.sub.2) and hydrogen fluoride (HF), performing an HF-elimination reaction step (B), wherein in the elimination reaction, HF (hydrogen fluoride) is eliminated from the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II),

##STR00026##

[0192] and the elimination reaction step (B) is performed

[0193] (i) as a(n) (exothermic) elimination reaction in the presence of one or more nitrogen-containing organic bases,

[0194] preferably as a non-aqueous (exothermic) elimination reaction in the presence of one or more nitrogen containing organic bases,

[0195] and/or

[0196] in the presence of one or more inorganic bases,

[0197] preferably as a(n) (exothermic) elimination reaction with an aqueous solution containing one or more inorganic bases, more preferably as a(n) (exothermic) elimination reaction with an aqueous solution containing one or more inorganic bases in the presence of one or more phase transfer catalysts,

[0198] wherein the temperature of the (exothermic) elimination reaction is controlled to not exceed a temperature of about 60° C.,

[0199] preferably to not exceed a temperature of about 50° C., more preferably to not exceed a temperature of about 45° C., and even more preferably to not exceed a temperature of about 40° C.,

[0200] and wherein the (exothermic) elimination reaction is carried out at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute,

[0201] preferably at a pressure in the range of from about 4 bar absolute bar to about 20 bar absolute, more preferably at a pressure in the range of from about 4 bar absolute bar to about 15 bar absolute, even more preferably at a pressure in the range of from about 4 bar absolute bar to about 10 bar absolute, and most preferably at a pressure in the range of from about 4 bar absolute bar to about 8 bar absolute,

[0202] or

[0203] (ii) as a, non-catalytic or preferably catalytic, more preferably Ni (nickel) catalytic, thermal elimination reaction at a temperature in the range of about 60° C. to about 120° C.,

[0204] preferably at a temperature in the range of about 70° C. to about 110° C., more preferably at a temperature in the range of about 70° C. to about 100° C., even more preferably at a temperature in the range of about 70° C. to about 90° C.,

[0205] to yield the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I),

[0206] and

[0207] (C) withdrawing and collecting the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I) obtained in step (B) from the reactor or reactor system, and

[0208] (D) optionally isolating and/or purifying the compound PFMVE (perfluoro(methyl vinyl ether)) of formula (I).

[0209] In a further aspect, the invention pertains to a process for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II),

##STR00027##

[0210] wherein the process comprises, in a reactor or reactor system, resistant to elemental fluorine (F.sub.2) and hydrogen fluoride (HF), performing a direct fluorination reaction step (A), wherein in the direct fluorination reaction the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III),

##STR00028##

[0211] is fluorinated with an about stoichiometric quantity of elemental fluorine (F.sub.2) comprised in a fluorination gas to selectively substitute in the compound of formula (III) the three hydrogen atoms of the 1-(methoxy) group of the compound HFE-254 of formula (III) for fluorine, and wherein the reaction is carried out at temperature in the range of from about 0° C. to about +60° C.,

[0212] preferably at temperature in the range of from about 0° C. to about +60° C., more preferably of at temperature in the range from about 10° C. to about +50° C., even more preferably at temperature in the range of from about 20° C. to about +40° C.,

[0213] and at a pressure in the range of from about 1 bar absolute bar to about 20 bar absolute,

[0214] preferably at a pressure in the range of from about 5 bar absolute bar to about 20 bar absolute, more preferably at a pressure in the range of from about 5 bar absolute bar to about 15 bar absolute, even more preferably at a pressure in the range of from about 5 bar absolute bar to about 12 bar absolute, and most preferably at a pressure in the range of from about 6 bar absolute bar to about 11 bar absolute,

[0215] to yield the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II),

##STR00029##

[0216] and

[0217] (C) withdrawing and collecting the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II) obtained in step (A) from the reactor or reactor system,

[0218] and

[0219] (D) optionally isolating and/or purifying the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II).

[0220] In another aspect, the invention also pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in a (closed) column reactor.

[0221] In yet another aspect, the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or the process according to claim 3 for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the liquid reaction medium of the direct fluorination reaction (A) is circulated in a loop in a (closed) column reactor to perform the fluorination reaction (A), while the fluorination gas comprising elemental fluorine (F.sub.2) is fed into the (closed) column reactor and is passed through the liquid reaction medium to react with the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III); preferably wherein the loop is operated with a circulation velocity in the range of from about 1,000 l/h to about 2,000 l/h, more preferably in the range of from about 1,250 l/h to about 1,750 l/h; still more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+200 l/h; even more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+100 l/h; and most preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h±50 l/h.

[0222] For example, in said yet another aspect of the invention as defined here before, pertains to a process, wherein for the direct fluorination reaction (A) the (closed) column reactor is equipped with at least one of the following:

[0223] (i) at least one heat exchanger (system), at least one liquid reservoir, with inlet and outlet for, and containing the liquid reaction medium,

[0224] e.g., initially comprising or consisting of the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) of formula (III) or as the reaction proceeds increasingly comprising or consisting of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II);

[0225] (ii) a pump for pumping and circulating the liquid reaction medium;

[0226] (iii) one or more (nozzle) jets, preferably wherein the one or more (nozzle) jets are placed at the top of the column reactor, for spraying the circulating reaction medium into the (closed) column reactor;

[0227] (iv) one or more feeding inlets for introducing the fluorination gas comprising or consisting of elemental fluorine (F2) into the (closed) column reactor;

[0228] (v) optionally one or more sieves, preferably two sieves, preferably the one or more sieves placed at the bottom of the (closed) column reactor;

[0229] (vi) and at least one gas outlet equipped with a pressure valve, and at least one outlet for withdrawing the fluorinated compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II) from the (closed) column reactor.

[0230] As already described above, when performing fluorination (A) reactions in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), the fluorination (A) reactions can be performed over the whole wide range of fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas of from about 1% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume.

[0231] In this aspect, for example, the invention pertains to a process for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or a process for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)-ethane), (E 227), of formula (II), wherein the fluorination (A) reaction is performed in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), and wherein the fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is in a range of from about 1% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume;

[0232] preferably wherein

[0233] (i) the fluorine (F2) concentration in the F2-fluorination gas is in a range of from about 1% by volume of elemental fluorine (F2) up to about 30% by volume of elemental fluorine (F2), more preferably of from about 5% by volume of elemental fluorine (F2) up to about 25% by volume of elemental fluorine (F2), even more preferably of from about 5% by volume of elemental fluorine (F2) up to about 20% by volume of elemental fluorine (F2), each range based on the total F2-fluorination gas composition as 100% by volume; or

[0234] (ii) the fluorine (F2) concentration in the F2-fluorination gas is in a range of from about 85% by volume of elemental fluorine (F2) up to about almost 100% by volume of elemental fluorine (F2), more preferably of from about 90% by volume of elemental fluorine (F2) up to about almost 100% by volume of elemental fluorine (F2), based on the total F2-fluorination gas composition as 100% by volume.

[0235] Accordingly, when performing fluorination (A) reactions in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), in one aspect the invention also pertains to a process as defined above, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the lower fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is applied, and wherein the fluorination gas in the direct fluorination reaction step (A) is elemental fluorine (F.sub.2) diluted in one or more inert gases, and wherein the elemental fluorine (F.sub.2) is present in the fluorination gas in a concentration in a range of from about 1% up to about 30% by volume of elemental fluorine (F.sub.2), preferably of from about 5% up to about 25% by volume of elemental fluorine (F.sub.2), more preferably of from about 5% up to about 20% by volume of elemental fluorine (F.sub.2), each range based on the total F.sub.2-fluorination gas composition as 100% by volume. Even more preferably, when performing reactions in said counter-current reactor system, in particular loop reactor system, or counter-current (loop) system (“inverse gas scrubber system”), the fluorination gas in the direct fluorination reaction step (A) is elemental fluorine (F.sub.2) diluted in one or more inert gases, and the elemental fluorine (F.sub.2) is present in the fluorination gas in a concentration in a range of from about 5% up to about 15% by volume of elemental fluorine (F.sub.2), still more preferably in a range of about 8% up to about 15% by volume of elemental fluorine (F.sub.2), and most preferably in a range of about 8% up to about 12% by volume of elemental fluorine (F.sub.2), e.g., the elemental fluorine (F.sub.2) is present in the fluorination gas in a concentration of about 10% by volume (e.g., 10±2% by volume, or 10±1% by volume, respectively). It goes without saying that a skilled person will understand that within any of the above given ranges any intermediate values and intermediate ranges can be selected, too.

[0236] Accordingly, when performing fluorination (A) reactions in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), in another aspect, the invention also pertains to a process as defined above, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the higher fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is applied, and wherein the elemental fluorine (F.sub.2) is present in the fluorination gas in a concentration in a range of from about 85% up to about almost 100% (as defined herein above) by volume of elemental fluorine (F.sub.2), most preferably of from about 90% by volume of elemental fluorine (F.sub.2) up to about almost 100% (as defined herein above) by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume. Even more preferably, when performing reactions in said counter-current reactor system, in particular loop reactor system, or counter-current (loop) system (“inverse gas scrubber system”), the F.sub.2-fluorination gas used in the fluorination process step (A) of the invention, for example, is a fluorine (F.sub.2) gas only to some extent diluted in an inert gas (together then they constitute the F.sub.2-fluorination gas), with fluorine (F.sub.2) concentrations in ranges, for example, with a maximum concentration of up to about almost 100% by volume of elemental fluorine (F.sub.2), in the range of from about 85% by volume, in particular in the range of from about 90% by volume or in particular in the range of from about 92% by volume of elemental fluorine (F.sub.2), especially in the range of from about 94% by volume; each given range based on the fluorine (F.sub.2) gas and the inert gas as 100% by volume, i.e., based on the total F.sub.2-fluorination gas composition as 100% by volume.

[0237] In another aspect, when performing fluorination (A) reactions in a counter-current reactor system, in particular in a loop reactor system, or in a counter-current (loop) system (“inverse gas scrubber system”), the invention also pertains to a process as defined above, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the higher fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is applied, and wherein, in a very practical range, for example, in particular if the F.sub.2-fluorination gas is derived from an F.sub.2-electrolysis reactor (fluorine cell), purified or unpurified, and wherein the fluorine (F.sub.2) gas from the F.sub.2-electrolysis reactor (fluorine cell) is only to some extent diluted in an inert gas (together then they constitute the F.sub.2-fluorination gas), with fluorine (F.sub.2) in a concentration within a range of from about 92% by volume of elemental fluorine (F.sub.2) up to about 99% by volume of elemental fluorine (F.sub.2), and most preferably in a very practical range of from about 94% by volume to about 99% by volume; each given range based on the fluorine (F.sub.2) gas and the inert gas as 100% by volume, i.e., based on the total F.sub.2-fluorination gas composition as 100% by volume.

[0238] It goes without saying that a skilled person will understand that within any of the above given ranges any intermediate values and intermediate ranges can be selected, too.

[0239] In still another aspect, the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), wherein the liquid reaction medium of the HF-elimination reaction (B) is circulated in a loop in a (closed) column reactor to perform the HF-elimination reaction (B), and wherein the loop is operated with a circulation velocity in the range of from about 1,000 l/h to about 2,000 l/h, preferably in the range of from about 1,250 l/h to about 1,750 l/h; more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+200 l/h; even more preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h+100 l/h; and most preferably wherein the loop is operated with a circulation velocity in the range of from about 1,500 l/h±50 l/h.

[0240] For example, in said still another aspect of the invention as defined here before, pertains to a process, wherein for the HF-elimination reaction (B) the (closed) column reactor is equipped with at least one of the following:

[0241] (i) at least one heat exchanger (system), at least one liquid reservoir, with inlet and outlet for, and containing the liquid reaction medium,

[0242] e.g., initially comprising or consisting of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), or as the reaction proceeds increasingly comprising or consisting of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I);

[0243] (ii) a pump for pumping and circulating the liquid reaction medium;

[0244] (iii) one or more (nozzle) jets, preferably wherein the one or more (nozzle) jets are placed at the top of the column reactor, for spraying the circulating reaction medium into the (closed) column reactor;

[0245] (iv) optionally, in case of (i) preferably performing the HF-elimination reaction as a(n) (exothermic) elimination reaction in the presence of one or more nitrogen-containing organic bases, one or more feeding inlets for introducing the one or more nitrogen-containing organic bases into the (closed) column reactor;

[0246] (v) optionally one or more sieves, preferably two sieves, preferably the one or more sieves placed at the bottom of the (closed) column reactor;

[0247] (vi) and at least one gas outlet equipped with a pressure valve, and at least one outlet for withdrawing the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I) from the (closed) column reactor.

[0248] In an aspect of the invention, wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in a (closed) column reactor, the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein column reactor is a packed bed tower reactor, preferably a packed bed tower reactor is packed with fillers resistant to the reactants and especially resistant to elemental fluorine (F.sub.2) and to hydrogen fluoride (HF) such as, e.g., with Raschig fillers, E-TFE fillers, and/or HF-resistant metal fillers, e.g., Hastelloy metal fillers, and/or (preferably) HDPTFE-fillers, more preferably wherein the packed bed tower reactor is a gas scrubber system (tower) which is packed with any of the before mentioned HF-resistant Hastelloy metal fillers and/or HDPTFE-fillers, and preferably with HDPTFE-fillers.

[0249] In yet a further aspect the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in at least one step in a continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm, more preferably in at least one step in a microreactor;

[0250] still more preferably wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in at least in one step as a continuous processes, wherein the continuous process is performed in at least one continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm;

[0251] even more preferably wherein the direct fluorination reaction (A) and/or the HF-elimination reaction (B) is carried out in at least in one step as a continuous processes, wherein the continuous process is performed in at least one microreactor.

[0252] In still a further aspect the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), characterized in that prior to starting any of the process steps (A) and (B) one or more of the reactors used, preferably each and any of the reactors used, are purged with an inert gas or a mixture of inert gases, preferably with He (helium) and/or N.sub.2 (nitrogen) as the inert gas, more preferably with N.sub.2 (nitrogen) as the inert gas.

[0253] In a particular aspect the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), characterized in that in the fluorination reaction step (A) the reaction is performed in a SiC-reactor; preferably in that in the fluorination reaction step (A) the reaction is performed in a SiC-microreactor.

[0254] In another particular aspect the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), characterized in that in the HF-elimination step (B) the reaction is performed in a nickel-reactor (Ni-reactor) or in a reactor with an inner surface with high nickel-content (Ni-content); preferably in that in the HF-elimination step (B) the reaction is performed in a nickel-microreactor (Ni-microreactor) or in a microreactor with an inner surface with high nickel-content (Ni-content).

[0255] In a further particular aspect the invention pertains to a process as defined here before, for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), characterized in that, independently, the product yielding from fluorination reaction step (A) and/or the product yielding from HF-elimination step (B) are subjected to distillation.

[0256] In still another aspect, the invention pertains also to any one of the above defined processes for the manufacture of PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or also to any one of the above defined processes for the manufacture of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) having the formula (II), characterized in that in step (B) in the second reactor the elimination reaction is performed in a nickel-reactor (Ni-reactor) or in a reactor with an inner surface with high nickel-content (Ni-content). Preferably, in the context of the present invention the term “high nickel-content” means a nickel (Ni) content of at least 50% in the metal alloy the nickel-reactor is made of Particularly preferred is a nickel-reactor made out of Hastelloy C4 nickel alloy. The Hastelloy C4 nickel alloy is known in the state of the art to be a nickel alloy comprising a combination of chromium with high molybdenum content. Such Hastelloy C4 nickel alloy shows exceptional resistance to a large number of chemical media such as contaminated, reducing mineral acids, chlorides and organic and inorganic media contaminated with chloride.

[0257] Hastelloy C4 nickel alloy is commercially available, for example, under the tradenames Nicrofer® 6616 hMo or Hastelloy C-4®, respectively. The density of Hastelloy C4 nickel alloy is 8.6 g/cm.sup.3, and the melting temperature range is 1335 to 1380° C.

[0258] Due to its special chemical composition of C4, the Hastelloy C4 nickel alloy has good structural stability and high resistance to sensitization.

[0259] The chemical composition of Hastelloy C4 (nickel alloy), for example, is in the following Table 1, wherein the nickel (Ni) content is at least 50% in the metal alloy, and the nickel (Ni) content is adding up the Hastelloy C4 nickel alloy compositions to a total of 100% metal alloy.

TABLE-US-00001 TABLE 1 Chemical composition of Hastelloy C4 (nickel alloy). C Si Mn P S Cr Mo Co Fe Ti % ≤% ≤% ≤% ≤% % % ≤% % % 0-0.009 0-0.05 0-1.0 0-0.02 0-0.01 14.5-17.5 14.0-17.0 0-2.0 0-3 0-0.7 and nickel (Ni) as the remainder for adding up to 100% metal alloy.

[0260] In a further aspect, the invention pertains also to any one of the above defined processes for the manufacture of PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or also to any one of the above defined processes for the manufacture of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) having the formula (II), characterized in that in step (A) the fluorination reaction is performed in a continuous manner, preferably in a continuous manner in a microreactor.

[0261] In another particular and preferred aspect, the invention pertains also to any one of the above defined processes for the manufacture of PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), characterized in that in step (B) the elimination reaction is performed in a continuous manner, preferably in a continuous manner in a microreactor.

[0262] In yet another particular and preferred aspect, the invention pertains also to any one of the above defined processes for the manufacture of PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or also to any one of the above defined processes for the manufacture of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) having the formula (II), characterized in that, independently the reaction in at least one reaction step of (A) and (B) is carried as a continuous processes, wherein the continuous process in the at least one reaction step of (A) and (B) is performed in at least one continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm, preferably wherein at least one of the continuous flow reactor is a microreactor.

[0263] In a more preferred aspect, the invention pertains also to any one of the above defined processes for the manufacture of PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or also to any one of the above defined processes for the manufacture of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) having the formula (II), characterized in that the reaction is carried out in at least one reaction step of (A) and (B) as a continuous processes, wherein the continuous process is performed in at least one continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm, preferably in at least one microreactor;

[0264] more preferably wherein of the said steps of (A) and (B) at least the step (A) of a fluorination reaction is a continuous process in at least one microreactor under one or more of the following conditions: [0265] flow rate: of from about 10 ml/h up to about 400 l/h; [0266] temperature: ranging of from about −20° C. or of from about −10° C. or of from about 0° C. or of from about 10° C., or of from about 20° C. or of from about 30° C., respectively, each ranging to up to about 150° C.; [0267] pressure: of from about 1 bar (1 atm abs.) up to about 50 bar; preferably of from about 1 bar (1 atm abs.) up to about 20 bar, more preferably at about 1 bar (1 atm abs.) up to about 5 bar; most preferably at about 1 bar (1 atm abs.) up to about 4 bar; in an example the pressure is about 3 bar; [0268] residence time: of from about 1 second, preferably from about 1 minute, up to about 60 minutes.

[0269] In a further aspect, the invention pertains also to any one of the above defined processes for the manufacture of PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or also to any one of the above defined processes for the manufacture of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) having the formula (II), characterized in that, independently, the product yielding from step (A) and/or the product yielding from step (B) are subjected to distillation.

[0270] Batch Process:

[0271] The invention also may pertain to a process for the manufacture of a fluorinated compound, comprising a particular process step which is performed batchwise, preferably wherein the batchwise process step is carried out in a column reactor. Although, in the following column reactor setting the process is described as a batch process, optionally the process can be performed in the said column reactor setting also as a continuous process. In case of a continuous process in the said column reactor setting, then, it goes without saying, the additional inlet(s) and outlet(s) are foreseen, for feeding the starting compound and withdrawing the product compound, respectively, and/or if desired any intermediate compound. Reference is made to Example 9.

[0272] If the invention pertains to a batchwise process, preferably wherein the batchwise process is carried out in a column reactor, the process for manufacturing of perfluoro(methylvinylether) (PFMVE), and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), which is a suitable intermediate in the manufacture of perfluoro(methylvinylether) (PFMVE), most preferably the reaction is carried out in a (closed) column reactor (system), wherein the liquid medium comprising or consisting of a liquid starting compound, e.g., the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) or TFTFME (E 227), respectively, as a liquid medium is circulated in a loop; preferably wherein the loop in the column reactor is operated with a circulation velocity of from 1,500 l/h to 5,000 l/h, more preferably of from 3,500 l/h to 4,500 l/h.

[0273] If the invention pertains to such a batchwise process, the process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) according to the invention can be carried out such that the mentioned liquid medium is circulated in the column reactor in a turbulent stream or in laminar stream, preferably in a turbulent stream.

[0274] In general, a gaseous starting compound, e.g., the F.sub.2-fluorination gas, respectively, is fed into the loop in accordance with the required stoichiometry for the targeted product compound and/or if desired any intermediate compound, and adapted to the reaction rate.

[0275] For example, the said process for the manufacture of a compound PFMVE and/or TFTFME (E 227) according to the invention, may be performed, e.g., batchwise, wherein the column reactor is equipped with at least one of the following: at least one cooler (system), at least one liquid reservoir for the liquid medium comprising or consisting of a liquid starting compound, a pump (for pumping/circulating the liquid medium), one or more (nozzle) jets, preferably placed at the top of the column reactor, for spraying the circulating medium into the column reactor, one or more feeding inlets for introducing a gaseous starting compound, e.g., F.sub.2-fluorination gas, optionally one or more sieves, preferably two sieves, preferably the one or more sieves placed at the bottom of the column reactor, and at least one gas outlet equipped with a pressure valve.

[0276] Accordingly, the process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) compound according to the invention, can be performed in column reactor which is equipped with at least one of the following:

[0277] (i) at least one cooler (system), at least one liquid reservoir, with inlet and outlet for, and containing the liquid medium comprising or consisting of a starting compound; preferably the compound HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) or TFTFME (E 227), respectively;

[0278] (ii) a pump for pumping and circulating the liquid medium in the column reactor;

[0279] (iii) one or more (nozzle) jets, preferably wherein the one or more (nozzle) jets are placed at the top of the column reactor, for spraying the circulating liquid medium into the column reactor;

[0280] (iv) one or more feeding inlets for introducing a gaseous compound, e.g., inert gas or a F2-fluorination gas, respectively into the column reactor;

[0281] (v) optionally one or more sieves, preferably two sieves, preferably the one or more sieves placed at the bottom of the column reactor;

[0282] (vi) and at least one gas outlet equipped with a pressure valve, and at least one outlet for withdrawing the product compound, respectively, and/or if desired any intermediate compound.

[0283] In one embodiment, the process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) compound according to the invention can be performed in a column reactor which is a packed bed tower reactor, preferably a packed bed tower reactor which is packed with fillers (the terms “filler” and “filling”, are meant synonymously in the context of the invention) resistant to the reactants and especially resistant to hydrogen fluoride (HF). Fillers resistant to the reactants and especially resistant to hydrogen fluoride (HF) suitable in the context of the present invention are in particular HF-resistant plastic fillers and/or HF-resistant metal fillers. For example, under certain circumstances the packed bed tower reactor may be packed with stainless steel (1.4571) fillers, but stainless steel (1.4571) fillers are less suitable than other fillers mentioned herein after, because of possible risk of (minor) traces of humidity in the reactor system. Preferably, for example, in the invention the packed bed tower reactor is packed with fillers resistant to the reactants and especially resistant to hydrogen fluoride (HF) such as, e.g., with Raschig fillers, E-TFE fillers, and/or HF-resistant metal fillers, e.g., Hastelloy metal fillers, and/or (preferably) HDPTFE-fillers, more preferably wherein the packed bed tower reactor is a gas scrubber system (tower) which is packed with any of the before mentioned HF-resistant Hastelloy metal fillers and/or HDPTFE-fillers, and preferably with HDPTFE-fillers.

[0284] In a further embodiment, the process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) compound according to the invention, the reaction is carried out with a counter-current flow of the circulating liquid medium comprising or consisting of the liquid starting compound and of the F.sub.2-fluorination gas, respectively, that are fed into the column reactor.

[0285] The pressure valve functions to keep the pressure, as required in the reaction, and to release any effluent gas, e.g. inert carrier gas contained in the fluorination gas, if applicable together with any hydrogen halogenide gas released from the reaction.

[0286] The said process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) compound according to the invention, may be performed, e.g., batchwise, such that in the said process the column reactor is a packed bed tower reactor as mentioned before, preferably a packed bed tower reactor which is packed with HDPTFE-fillers.

[0287] The packed tower according to FIG. 1 can have a diameter of 100 or 200 mm (depending on the circulating flow rate and scale) made out of Hastelloy C4 (nickel alloy)(known to the person skilled in the art), and has a length of 3 meters for the 100 mm and a length of 6 meters for the 200 mm diameter tower (latter if higher capacities are needed). The tower made out of Hastelloy is filled either with any of the fillings as mentioned before, or with the preferred HDPTFE-fillers, each of 10 mm diameter as commercially available. The size of fillings is quite flexible. The type of fillings is also quite flexible, within the boundaries of properties as stated herein above, i.e., the HDPTFE-fillers (or HDPTFE-fillings, respectively) were used in the trials disclosed hereunder in Example 1, and showed same performance, not causing much pressure reduction (pressure loss) while feeding any gaseous (starting) compound in counter-current manner.

[0288] Methods in a Continuous Flow Reactor System, e.g., Microreactor System:

[0289] The methods of the present invention as preferably described with microreactor are applicable to a continuous flow reactor system, as well as to a tube reactor system, and also applicable also to variants with coiled reactor system.

[0290] As already described above, when performing fluorination (A) reactions in a tube reactor system, in a continuous flow reactor system, in a coil reactor system, or in a microreactor system, preferably in a microreactor system, preferably the higher fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas (as defined above) is adjusted when performing the fluorination (A) reactions.

[0291] In this aspect, for example, the invention pertains to a process for the manufacture of the compound PFMVE (perfluoro(methyl vinyl ether)) having the formula (I), or the process for the manufacture of the compound TFTFME (1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane), (E 227), of formula (II), wherein the fluorination (A) reaction is performed in a tube reactor system, in a continuous flow reactor system, in a coil reactor system, or in a microreactor system, preferably in a microreactor system, and wherein the fluorine (F.sub.2) concentration in the F.sub.2-fluorination gas is in a range of from about 85% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), more preferably of from about 90% by volume of elemental fluorine (F.sub.2) up to about almost 100% by volume of elemental fluorine (F.sub.2), based on the total F.sub.2-fluorination gas composition as 100% by volume.

[0292] Accordingly, when performing fluorination (A) reactions in a tube reactor system, in a continuous flow reactor system, in a coil reactor system, or in a microreactor system, preferably in a microreactor system, the F.sub.2-fluorination gas used in the fluorination process step (A) of the invention, for example, is a fluorine (F.sub.2) gas only to some extent diluted in an inert gas (together then they constitute the F.sub.2-fluorination gas), with fluorine (F.sub.2) concentrations in ranges, for example, with a maximum concentration of up to about almost 100% by volume of elemental fluorine (F.sub.2), in the range of from about 85% by volume, in particular in the range of from about 90% by volume or in particular in the range of from about 92% by volume of elemental fluorine (F.sub.2), especially in the range of from about 94% by volume; each given range based on the fluorine (F.sub.2) gas and the inert gas as 100% by volume, i.e., based on the total F.sub.2-fluorination gas composition as 100% by volume.

[0293] Accordingly, when performing fluorination (A) reactions in a tube reactor system, in a continuous flow reactor system, in a coil reactor system, or in a microreactor system, preferably in a microreactor system, the said fluorination process step (A) of the invention, for example, a fluorine (F.sub.2) gas is only to some extent diluted in an inert gas (together then they constitute the F.sub.2-fluorination gas), with fluorine (F.sub.2) in a concentration more preferably within a range of from about 92% by volume to about almost 100% by volume, even more preferably within a range of from about 94% by volume to about almost 100% by volume, still more preferably in a very practical range, for example, in particular if the F.sub.2-fluorination gas is derived from an F.sub.2-electrolysis reactor (fluorine cell), purified or unpurified, of from about 92% by volume of elemental fluorine (F.sub.2) up to about 99% by volume of elemental fluorine (F.sub.2), and most preferably in a very practical range of from about 94% by volume to about 99% by volume; each given range based on the fluorine (F.sub.2) gas and the inert gas as 100% by volume, i.e., based on the total F.sub.2-fluorination gas composition as 100% by volume.

[0294] According to a preferred embodiment of the present invention, the compound perfluoro(methylvinylether) (PFMVE) and/or the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), respectively, can also be prepared in a continuous manner. More preferably, the compound perfluoro(methyl vinyl ether) (PFMVE) and/or the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), respectively, in microreactor reaction.

[0295] Optionally, any intermediate in the process for manufacturing of perfluoro(methylvinylether) (PFMVE) and/or 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) compound according to the invention may be isolated and/or purified, and then such isolated and/or purified may be further processed, as desired. For example, the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), which is a suitable intermediate in the manufacture of perfluoro(methyl vinyl ether) (PFMVE), may be isolated and/or purified. For example, the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) is prepared in a first microreactor by fluorination (A) is optionally isolated and/or purified, and then the compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) is transferred into another (second) microreactor to be further reacted in reaction step (B) for HF-elimination.

[0296] The intermediate compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) produced in the mentioned first microreactor sequence by fluorination (A) and HF-elimination (B) reaction, optionally may be isolated and/or purified, and then can also constitute the final product in isolated and/or purified form.

[0297] Alternatively, (intermediate) compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) produced in a first microreactor by fluorination (A) reaction, as a crude compound as obtained (e.g., not further purified), is transferred into the mentioned another (second) microreactor, to be further reacted in the HF-elimination (B) reaction to yield the final target compound perfluoro(methyl vinyl ether) (PFMVE).

[0298] In a further variant of the present invention, see for example, Example 2 and reaction Scheme 3, the final target compound perfluoro(methylvinylether) (PFMVE) can also be prepared out of the (intermediate) compound 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), and described herein above in more detail. Preferably, the reaction can be performed in a continuous manner.

[0299] Microreactor Process:

[0300] The invention also may pertain to a process for manufacturing of perfluoro(methylvinylether) (PFMVE), and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), which is a suitable intermediate in the manufacture of perfluoro(methylvinylether) (PFMVE), wherein the process is a continuous process, preferably wherein the continuous process is carried out in a microreactor.

[0301] The invention may employ more than a single microreactor, i.e., the invention may employ two, three, four, five or more microreactors, for either extending the capacity or residence time, for example, to up to ten microreactors in parallel or four microreactors in series. If more than a single microreactor is employed, then the plurality of microreactors can be arranged either sequentially or in parallel, and if three or more microreactors are employed, these may be arranged sequentially, in parallel or both.

[0302] The invention is also very advantageous, in to embodiments wherein the process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227) according to the invention optionally is performed in a continuous flow reactor system, or preferably in a microreactor system.

[0303] In an preferred embodiment the invention relates to a process for manufacturing of perfluoro(methyl vinyl ether) (PFMVE) and/or of 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane (TFTFME) (E 227), wherein in at least one reaction step of (A) and (B) is carried out as a continuous processes, wherein the continuous process is performed in at least one continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm,

[0304] preferably in at least one microreactor; more preferably wherein of the said at least one reaction step is a continuous process in at least one microreactor under one or more of the following conditions: [0305] flow rate: of from about 10 ml/h up to about 400 l/h; [0306] temperature: of from about 0° C. up to about 150° C.; [0307] pressure: of from about 4 bar up to about 50 bar; [0308] residence time: of from about 1 second, preferably from about 1 minute, up to about 60 minutes.

[0309] In another preferred embodiment the invention relates to such a process of preparing a compound according to the invention, wherein at least one of the said continuous flow reactors, preferably at least one of the microreactors, independently is a SiC-continuous flow reactor, preferably independently is a SiC-microreactor.

[0310] The Continuous Flow Reactors and Microreactors:

[0311] In addition to the above, according to one aspect of the invention, also a plant engineering invention is provided, as used in the process invention and described herein, pertaining to the optional, and in some embodiments of the process invention, the process even preferred implementation in microreactors.

[0312] As to the term “microreactor”: A “microreactor” or “microstructured reactor” or “microchannel reactor”, in one embodiment of the invention, is a device in which chemical reactions take place in a confinement with typical lateral dimensions of about ≤1 mm; an example of a typical form of such confinement are microchannels. Generally, in the context of the invention, the term “microreactor”: A “microreactor” or “microstructured reactor” or “microchannel reactor”, denotes a device in which chemical reactions take place in a confinement with typical lateral dimensions of about ≤5 mm.

[0313] Microreactors are studied in the field of micro process engineering, together with other devices (such as micro heat exchangers) in which physical processes occur. The microreactor is usually a continuous flow reactor (contrast with/to a batch reactor). Microreactors offer many advantages over conventional scale reactors, including vast improvements in energy efficiency, reaction speed and yield, safety, reliability, scalability, on-site/on-demand production, and a much finer degree of process control.

[0314] Microreactors are used in “flow chemistry” to perform chemical reactions.

[0315] In flow chemistry, wherein often microreactors are used, a chemical reaction is run in a continuously flowing stream rather than in batch production. Batch production is a technique used in manufacturing, in which the object in question is created stage by stage over a series of workstations, and different batches of products are made. Together with job production (one-off production) and mass production (flow production or continuous production) it is one of the three main production methods. In contrast, in flow chemistry the chemical reaction is run in a continuously flowing stream, wherein pumps move fluid into a tube, and where tubes join one another, the fluids contact one another. If these fluids are reactive, a reaction takes place. Flow chemistry is a well-established technique for use at a large scale when manufacturing large quantities of a given material. However, the term has only been coined recently for its application on a laboratory scale.

[0316] Continuous flow reactors, e.g. such as used as microreactor, are typically tube like and manufactured from non-reactive materials, such known in the prior art and depending on the specific purpose and nature of possibly aggressive agents and/or reactants. Mixing methods include diffusion alone, e.g. if the diameter of the reactor is narrow, e.g. <1 mm, such as in microreactors, and static mixers. Continuous flow reactors allow good control over reaction conditions including heat transfer, time and mixing. The residence time of the reagents in the reactor, i.e. the amount of time that the reaction is heated or cooled, is calculated from the volume of the reactor and the flow rate through it: Residence time=Reactor Volume/Flow Rate. Therefore, to achieve a longer residence time, reagents can be pumped more slowly, just a larger volume reactor can be used and/or even several microreactors can be placed in series, optionally just having some cylinders in between for increasing residence time if necessary for completion of reaction steps. In this later case, cyclones after each microreactor help to let escape some low boiling substances, e.g., any formed PFVME together with (potentially present) inert gas and so far to positively influence the reaction performance. Production rates can vary from milliliters per minute to liters per hour.

[0317] Some examples of flow reactors are spinning disk reactors (Colin Ramshaw); spinning tube reactors; multi-cell flow reactors; oscillatory flow reactors; microreactors; hex reactors; and aspirator reactors. In an aspirator reactor a pump propels one reagent, which causes a reactant to be sucked in. Also to be mentioned are plug flow reactors and tubular flow reactors.

[0318] In the present invention, in one embodiment it is particularly preferred to employ a microreactor.

[0319] In the use and processes according to the invention in a preferred embodiment the invention is using a microreactor. But it is to be noted in a more general embodiment of the invention, apart from the said preferred embodiment of the invention that is using a microreactor, any other, e.g. preferentially pipe-like, continuous flow reactor with upper lateral dimensions of up to about 1 cm, and as defined herein, can be employed. Thus, such a continuous flow reactor preferably with upper lateral dimensions of up to about ≤5 mm, or of about ≤4 mm, refers to a preferred embodiment of the invention, e.g. preferably to a microreactor. Continuously operated series of STRs is another option, but less preferred than using a microreactor.

[0320] In the before said embodiments of the invention, the minimal lateral dimensions of the, e.g. preferentially pipe-like, continuous flow reactor can be about >5 mm; but is usually not exceeding about 1 cm. Thus, the lateral dimensions of the, e.g. preferentially pipe-like, continuous flow reactor can be in the range of from about >5 mm up to about 1 cm, and can be of any value therein between. For example, the lateral dimensions of the, e.g. preferentially pipe-like, continuous flow reactor can be about 5.1 mm, about 5.5 mm, about 6 mm, about 6.5 mm, about 7 mm, about 7.5 mm, about 8 mm, about 8.5 mm, about 9 mm, about 9.5 mm, and about 10 mm, or can be can be of any value intermediate between the said values.

[0321] In the before said embodiments of the invention using a microreactor preferentially the minimal lateral dimensions of the microreactor can be at least about 0.25 mm, and preferably at least about 0.5 mm; but the maximum lateral dimensions of the microreactor does not exceed about ≤5 mm. Thus, the lateral dimensions of the, e.g. preferential microreactor can be in the range of from about 0.25 mm up to about ≤5 mm, and preferably from about 0.5 mm up to about ≤5 mm, and can be of any value therein between. For example, the lateral dimensions of the preferential microreactor can be about 0.25 mm, about 0.3 mm, about 0.35 mm, about 0.4 mm, about 0.45 mm, and about 5 mm, or can be can be of any value intermediate between the said values.

[0322] As stated here before in the embodiments of the invention in its broadest meaning is employing, preferentially pipe-like, continuous flow reactor with upper lateral dimensions of up to about 1 cm. Such continuous flow reactor, for example is a plug flow reactor (PFR).

[0323] The plug flow reactor (PFR), sometimes called continuous tubular reactor, CTR, or piston flow reactors, is a reactor used to perform and describe chemical reactions in continuous, flowing systems of cylindrical geometry. The PFR reactor model is used to predict the behavior of chemical reactors of such design, so that key reactor variables, such as the dimensions of the reactor, can be estimated.

[0324] Fluid going through a PFR may be modeled as flowing through the reactor as a series of infinitely thin coherent “plugs”, each with a uniform composition, traveling in the axial direction of the reactor, with each plug having a different composition from the ones before and after it. The key assumption is that as a plug flows through a PFR, the fluid is perfectly mixed in the radial direction (i.e. in the lateral direction) but not in the axial direction (forwards or backwards).

[0325] Accordingly, the terms used herein to define the reactor type used in the context of the invention such like “continuous flow reactor”, “plug flow reactor”, “tubular reactor”, “continuous flow reactor system”, “plug flow reactor system”, “tubular reactor system”, “continuous flow system”, “plug flow system”, “tubular system” are synonymous to each other and interchangeably by each other.

[0326] The reactor or system may be arranged as a multitude of tubes, which may be, for example, linear, looped, meandering, circled, coiled, or combinations thereof. If coiled, for example, then the reactor or system is also called “coiled reactor” or “coiled system”.

[0327] In the radial direction, i.e. in the lateral direction, such reactor or system may have an inner diameter or an inner cross-section dimension (i.e. radial dimension or lateral dimension, respectively) of up to about 1 cm. Thus, in an embodiment the lateral dimension of the reactor or system may be in the range of from about 0.25 mm up to about 1 cm, preferably of from about 0.5 mm up to about 1 cm, and more preferably of from about 1 mm up to about 1 cm.

[0328] In further embodiments the lateral dimension of the reactor or system may be in the range of from about >5 mm to about 1 cm, or of from about 5.1 mm to about 1 cm.

[0329] If the lateral dimension at maximum of up to about ≤5 mm, or of up to about ≤4 mm, then the reactor is called “microreactor”. Thus, in still further microreactor embodiments the lateral dimension of the reactor or system may be in the range of from about 0.25 mm up to about ≤5 mm, preferably of from about 0.5 mm up to about ≤5 mm, and more preferably of from about 1 mm up to about ≤5 mm; or the lateral dimension of the reactor or system may be in the range of from about 0.25 mm up to about ≤4 mm, preferably of from about 0.5 mm up to about ≤4 mm, and more preferably of from about 1 mm up to about ≤4 mm.

[0330] In an alternative embodiment of the invention, it is also optionally desired to employ another continuous flow reactor than a microreactor, preferably if, for example, the (halogenation promoting, e.g. the halogenation or preferably the halogenation) catalyst composition used in the halogenation or fluorination tends to get viscous during reaction or is viscous already as a said catalyst as such. In such case, a continuous flow reactor, i.e. a device in which chemical reactions take place in a confinement with lower lateral dimensions of greater than that indicated above for a microreactor, i.e. of greater than about 1 mm, but wherein the upper lateral dimensions are about ≤4 mm. Accordingly, in this alternative embodiment of the invention, employing a continuous flow reactor, the term “continuous flow reactor” preferably denotes a device in which chemical reactions take place in a confinement with typical lateral dimensions of from about ≥1 mm up to about ≤4 mm. In such an embodiment of the invention it is particularly preferred to employ as a continuous flow reactor a plug flow reactor and/or a tubular flow reactor, with the said lateral dimensions. Also, in such an embodiment of the invention, as compared to the embodiment employing a microreactor, it is particularly preferred to employ higher flow rates in the continuous flow reactor, preferably in the plug flow reactor and/or a tubular flow reactor, with the said lateral dimensions. For example, such higher flow rates, are up to about 2 times higher, up to about 3 times higher, up to about 4 times higher, up to about 5 times higher, up to about 6 times higher, up to about 7 times higher, or any intermediate flow rate of from about ≥1 up to about ≤7 times higher, of from about ≥1 up to about ≤6 times higher, of from about ≥1 up to about ≤5 times higher, of from about ≥1 up to about ≤4 times higher, of from about ≥1 up to about ≤3 times higher, or of from about ≥1 up to about ≤2 times higher, each as compared to the typical flow rates indicated herein for a microreactor. Preferably, the said continuous flow reactor, more preferably the plug flow reactor and/or a tubular flow reactor, employed in this embodiment of the invention is configured with the construction materials as defined herein for the microreactors. For example, such construction materials are silicon carbide (SiC) and/or are alloys such as a highly corrosion resistant nickel-chromium-molybdenum-tungsten alloy, e.g. Hastelloy®, as described herein for the microreactors.

[0331] A very particular advantage of the present invention employing a microreactor, or a continuous flow reactor with the before said lateral dimensions, the number of separating steps can be reduced and simplified, and may be devoid of time and energy consuming, e.g. intermediate, distillation steps. Especially, it is a particular advantage of the present invention employing a microreactor, or a continuous flow reactor with the before said lateral dimensions, that for separating simply phase separation methods can be employed, and the non-consumed reaction components may be recycled into the process, or otherwise be used as a product itself, as applicable or desired.

[0332] In addition to the preferred embodiments of the present invention using a microreactor according to the invention, in addition or alternatively to using a microreactor, it is also possible to employ a plug flow reactor or a tubular flow reactor, respectively.

[0333] Plug flow reactor or tubular flow reactor, respectively, and their operation conditions, are well known to those skilled in the field.

[0334] Although the use of a continuous flow reactor with upper lateral dimensions of about ≤5 mm, or of about ≤4 mm, respectively, and in particular of a microreactor, is particularly preferred in the present invention, depending on the circumstances, it could be imagined that somebody dispenses with an microreactor, then of course with yield losses and higher residence time, higher temperature, and instead takes a plug flow reactor or turbulent flow reactor, respectively. However, this could have a potential advantage, taking note of the mentioned possibly disadvantageous yield losses, namely the advantage that the probability of possible blockages (tar particle formation by non-ideal driving style) could be reduced because the diameters of the tubes or channels of a plug flow reactor are greater than those of a microreactor.

[0335] The possibly allegeable disadvantage of this variant using a plug flow reactor or a tubular flow reactor, however, may also be seen only as subjective point of view, but on the other hand under certain process constraints in a region or at a production facility may still be appropriate, and loss of yields be considered of less importance or even being acceptable in view of other advantages or avoidance of constraints.

[0336] In the following, the invention is more particularly described in the context of using a microreactor. Preferentially, a microreactor used according to the invention is a ceramic continuous flow reactor, more preferably an SiC (silicon carbide) continuous flow reactor, and can be used for material production at a multi-to scale. Within integrated heat exchangers and SiC materials of construction, it gives optimal control of challenging flow chemistry application. The compact, modular construction of the flow production reactor enables, advantageously for: long term flexibility towards different process types; access to a range of production volumes (5 to 400 l/h); intensified chemical production where space is limited; unrivalled chemical compatibility and thermal control.

[0337] Ceramic (SiC) microreactors, are e.g. advantageously diffusion bonded 3M SiC reactors, especially braze and metal free, provide for excellent heat and mass transfer, superior chemical compatibility, of FDA certified materials of construction, or of other drug regulatory authority (e.g. EMA) certified materials of construction. Silicon carbide (SiC), also known as carborundum, is a containing silicon and carbon, and is well known to those skilled in the art. For example, synthetic SiC powder is been mass-produced and processed for many technical applications.

[0338] For example, in the embodiments of the invention the objects are achieved by a method in which at least one reaction step takes place in a microreactor. Particularly, in preferred embodiments of the invention the objects are achieved by a method in which at least one reaction step takes place in a microreactor that is comprising or is made of SiC (“SiC-microreactor”), or in a microreactor that is comprising or is made of an alloy, e.g. such as Hastelloy C, as it is each defined herein after in more detail.

[0339] Preferred Hastelloy C4 nickel alloys are already described further above. See, for example, Table 1.

[0340] Thus, without being limited to, for example, in an embodiment of the invention the microreactor suitable for, preferably for industrial, production an “SiC-microreactor” that is comprising or is made of SiC (silicon carbide; e.g. SiC as offered by Dow Corning as Type G1SiC or by Chemtrix MR555 Plantrix), e.g. providing a production capacity of from about 5 up to about 400 kg per hour; or without being limited to, for example, in another embodiment of the invention the microreactor suitable for industrial production is comprising or is made of Hastelloy C, as offered by Ehrfeld. Such microreactors are particularly suitable for the, preferably industrial, production of fluorinated products according to the invention.

[0341] In order to meet both the mechanical and chemical demands placed on production scale flow reactors, Plantrix modules are fabricated from 3M™SiC (Grade C). Produced using the patented 3M (EP 1 637 271 Bi and foreign patents) diffusion bonding technology, the resulting monolithic reactors are hermetically sealed and are free from welding lines/joints and brazing agents. More technical information on the Chemtrix MR555 Plantrix can be found in the brochure “CHEMTRIX—Scalable Flow Chemistry—Technical Information Plantrix® MR555 Series, published by Chemtrix BV in 2017, which technical information is incorporated herein by reference in its entirety.

[0342] Apart from the before said example, in other embodiments of the invention, in general SiC from other manufactures, and as known to the skilled person, of course can be employed in the present invention.

[0343] Accordingly, in the present invention as microreactor also the Protrix® of by Chemtrix can be used. Protrix® is a modular, continuous flow reactor fabricated from 3M® silicon carbide, offering superior chemical resistance and heat transfer. In order to meet both the mechanical and chemical demands placed on flow reactors, Protrix® modules are fabricated from 3M® SiC (Grade C). Produced using the patented 3M (EP 1 637 271 Bi and foreign patents) diffusion bonding technology, the resulting monolithic reactors are hermetically sealed and are free from welding lines/joints and brazing agents. This fabrication technique is a production method that gives solid SiC reactors (thermal expansion coefficient=4.1×10.sup.−6K.sup.−1).

[0344] Designed for flow rates ranging from 0.2 to 20 ml/min and pressures up to 25 bar, Protrix® allows the user to develop continuous flow processes at the lab-scale, later transitioning to Plantrix® MR555 (×340 scale factor) for material production. The Protrix® reactor is a unique flow reactor with the following advantages: diffusion bonded 3M® SiC modules with integrated heat exchangers that offer unrivaled thermal control and superior chemical resistance; safe employment of extreme reaction conditions on a g scale in a standard fume hood; efficient, flexible production in terms of number of reagent inputs, capacity or reaction time. The general specifications for the Protrix® flow reactors are summarized as follows; possible reaction types are, e.g. A+B.fwdarw.P1+Q (or C).fwdarw.P, wherein the terms “A”, “B” and “C” represent educts, “P” and “P1” products, and “Q” quencher; throughput (ml/min) of from about 0.2 up to about 20; channel dimensions (mm) of 1×1 (pre-heat and mixer zone), 1.4×1.4 (residence channel); reagent feeds of 1 to 3; module dimensions (width×height) (mm) of 110×260; frame dimensions (width×height×length) (mm) approximately 400×300×250; number of modules/frame is one (minimum) up to four (max.). More technical information on the ChemtrixProtrix® reactor can be found in the brochure “CHEMTRIX—Scalable Flow Chemistry—Technical Information Protrix®, published by Chemtrix BV in 2017, which technical information is incorporated herein by reference in its entirety.

[0345] The Dow Corning as Type G1SiC microreactor, which is scalable for industrial production, and as well suitable for process development and small production can be characterized in terms of dimensions as follows: typical reactor size (length×width×height) of 88 cm×38 cm×72 cm; typical fluidic module size of 188 mm×162 mm. The features of the Dow Corning as Type G1SiC microreactor can be summarized as follows: outstanding mixing and heat exchange: patented HEART design; small internal volume; high residence time; highly flexible and multipurpose; high chemical durability which makes it suitable for high pH compounds and especially hydrofluoric acid; hybrid glass/SiC solution for construction material; seamless scale-up with other advanced-flow reactors. Typical specifications of the Dow Corning as Type G1SiC microreactor are as follows: flow rate of from about 30 ml/min up to about 200 ml/min; operating temperature in the range of from about −60° C. up to about 200° C., operating pressure up to about 18 barg (“barg” is a unit of gauge pressure, i.e. pressure in bars above ambient or atmospheric pressure); materials used are silicon carbide, PFA (perfluoroalkoxy alkanes), perfluoroelastomer; fluidic module of 10 ml internal volume; options: regulatory authority certifications, e.g. FDA or EMA, respectively. The reactor configuration of Dow Corning as Type G1SiC microreactor is characterized as multipurpose and configuration can be customized. Injection points may be added anywhere on the said reactor.

[0346] Hastelloy® C is an alloy represented by the formula NiCr21Mol4W, alternatively also known as “alloy 22” or “Hastelloy® C-22. The said alloy is well known as a highly corrosion resistant nickel-chromium-molybdenum-tungsten alloy and has excellent resistance to oxidizing reducing and mixed acids. The said alloy is used in flue gas desulphurization plants, in the chemical industry, environmental protection systems, waste incineration plants, sewage plants. Apart from the before said example, in other embodiments of the invention, in general nickel-chromium-molybdenum-tungsten alloy from other manufactures, and as known to the skilled person, of course can be employed in the present invention. A typical chemical composition (all in weight-%) of such nickel-chromium-molybdenum-tungsten alloy is, each percentage based on the total alloy composition as 100%: Ni (nickel) as the main component (balance) of at least about 51.0%, e.g. in a range of from about 51.0% to about 63.0%; Cr (chromium) in a range of from about 20.0 to about 22.5%, Mo (molybdenum) in a range of from about 12.5 to about 14.5%, W (tungsten or wolfram, respectively) in a range of from about 2.5 to about 3.5%; and Fe (iron) in an amount of up to about 6.0%, e.g. in a range of from about 1.0% to about 6.0%, preferably in a range of from about 1.5% to about 6.0%, more preferably in a range of from about 2.0% to about 6.0%. Optionally, the percentage based on the total alloy composition as 100%, Co (cobalt) can be present in the alloy in an amount of up to about 2.5%, e.g. in a range of from about 0.1% to about 2.5%. Optionally, the percentage based on the total alloy composition as 100%, V (vanadium) can be present in the alloy in an amount of up to about 0.35%, e.g. in a range of from about 0.1% to about 0,35%. Also, the percentage based on the total alloy composition as 100%, optionally low amounts (i.e. ≤0.1%) of other element traces, e.g. independently of C (carbon), Si (silicon), Mn (manganese), P (phosphor), and/or S (sulfur). In such case of low amounts (i.e. ≤0.1%) of other elements, the said elements e.g. of C (carbon), Si (silicon), Mn (manganese), P (phosphor), and/or S (sulfur), the percentage based on the total alloy composition as 100%, each independently can be present in an amount of up to about 0.1%, e.g. each independently in a range of from about 0.01 to about 0.1%, preferably each independently in an amount of up to about 0.08%, e.g. each independently in a range of from about 0.01 to about 0.08%. For example, said elements e.g. of C (carbon), Si (silicon), Mn (manganese), P (phosphor), and/or S (sulfur), the percentage based on the total alloy composition as 100%, each independently can be present in an amount of, each value as an about value: C≤0.01%, Si 0.08%, Mn≤0.05%, P≤0.015%, S≤0.02%. Normally, no traceable amounts of any of the following elements are found in the alloy compositions indicated above: Nb (niobium), Ti (titanium), Al (aluminum), Cu (copper), N (nitrogen), and Ce (cerium).

[0347] Hastelloy® C-276 alloy was the first wrought, nickel-chromium-molybdenum material to alleviate concerns over welding (by virtue of extremely low carbon and silicon contents). As such, it was widely accepted in the chemical process and associated industries, and now has a 50-year-old track record of proven performance in a vast number of corrosive chemicals. Like other nickel alloys, it is ductile, easy to form and weld, and possesses exceptional resistance to stress corrosion cracking in chloride-bearing solutions (a form of degradation to which the austenitic stainless steels are prone). With its high chromium and molybdenum contents, it is able to withstand both oxidizing and non-oxidizing acids, and exhibits outstanding resistance to pitting and crevice attack in the presence of chlorides and other halides. The nominal composition in weight-% is, based on the total composition as 100%: Ni (nickel) 57% (balance); Co (cobalt) 2.5% (max.); Cr (chromium) 16%; Mo (molybdenum) 16%; Fe (iron) 5%; W (tungsten or wolfram, respectively) 4%; further components in lower amounts can be Mn (manganese) up to 1% (max.); V (vanadium) up to 0.35% (max.); Si (silicon) up to 0.08% (max.); C (carbon) 0.01 (max.); Cu (copper) up to 0.5% (max.).

[0348] In another embodiments of the invention, without being limited to, for example, the microreactor suitable for the said production, preferably for the said industrial production, is an SiC-microreactor that is comprising or is made only of SiC as the construction material (silicon carbide; e.g. SiC as offered by Dow Corning as Type G1SiC or by Chemtrix MR555 Plantrix), e.g. providing a production capacity of from about 5 up to about 400 kg per hour.

[0349] It is of course possible according to the invention to use one or more microreactors, preferably one or more SiC-microreactors, in the production, preferably in the industrial production, of the fluorinated products according to the invention. If more than one microreactor, preferably more than one SiC-microreactor, are used in the production, preferably in the industrial production, of the fluorinated products according to the invention, then these microreactors, preferably these SiC-microreactors, can be used in parallel and/or subsequent arrangements. For example, two, three, four, or more microreactors, preferably two, three, four, or more SiC-microreactors, can be used in parallel and/or subsequent arrangements.

[0350] For laboratory search, e.g. on applicable reaction and/or upscaling conditions, without being limited to, for example, as a microreactor the reactor type Plantrix of the company Chemtrix is suitable. Sometimes, if gaskets of a microreactor are made out of other material than HDPTFE, leakage might occur quite soon after short time of operation because of some swelling, so HDPTFE gaskets secure long operating time of microreactor and involved other equipment parts like settler and distillation columns.

[0351] For example, an industrial flow reactor (“IFR”, e.g. Plantrix® MR555) comprises of SiC modules (e.g. 3M® SiC) housed within a (non-wetted) stainless steel frame, through which connection of feed lines and service media are made using standard Swagelok fittings. The process fluids are heated or cooled within the modules using integrated heat exchangers, when used in conjunction with a service medium (thermal fluid or steam), and reacted in zig-zag or double zig-zag, meso-channel structures that are designed to give plug flow and have a high heat exchange capacity. A basic IFR (e.g. Plantrix® MR555) system comprises of one SiC module (e.g. 3M® SiC), a mixer (“MRX”) that affords access to A+B.fwdarw.P type reactions. Increasing the number of modules leads to increased reaction times and/or system productivity. The addition of a quench Q/C module extends reaction types to A+B.fwdarw.P1+Q (or C).fwdarw.P and a blanking plate gives two temperature zones. Herein the terms “A”, “B” and “C” represent educts, “P” and “P1” products, and “Q” quencher.

[0352] Typical dimensions of an industrial flow reactor (“IFR”, e.g. Plantrix® MR555) are, for example: channel dimensions in (mm) of 4×4 (“MRX”, mixer) and 5×5 (MRH-I/MRH-II; “MR” denotes residence module); module dimensions (width×height) of 200 mm×555 mm; frame dimensions (width×height) of 322 mm×811 mm. A typical throughput of an industrial flow reactor (“IFR”, e.g. Plantrix® MR555) is, for example, in the range of from about 50 l/h to about 400 l/h. in addition, depending on fluid properties and process conditions used, the throughput of an industrial flow reactor (“IFR”, e.g. Plantrix® MR555), for example, can also be >400 l/h. The residence modules can be placed in series in order to deliver the required reaction volume or productivity. The number of modules that can be placed in series depends on the fluid properties and targeted flow rate.

[0353] Typical operating or process conditions of an industrial flow reactor (“IFR”, e.g. Plantrix® MR555) are, for example: temperature range of from about −30° C. to about 200° C.; temperature difference (service—process)<70° C.; reagent feeds of 1 to 3; maximum operating pressure (service fluid) of about 5 bar at a temperature of about 200° C.; maximum operating pressure (process fluid) of about 25 bar at a temperature of about ≤200° C.

[0354] The following examples are intended to further illustrate the invention without limiting its scope.

EXAMPLES

[0355] The following examples are intended to further illustrate the invention without limiting its scope.

Example 1

[0356] Fluorination of HFE-254 to E 227 (TFTFME) in a counter-current system with diluted F.sub.2-gas (first step), and base initiated HF-elimination from E 227 (TFTFME) to obtain PFMVE (second step).

[0357] Apparatus:

[0358] A column made out of Hastelloy C4 with a length of 30 cm and with HDPTFE fillings and a diameter of 5 cm was used according to the drawing below. The liquid reservoir had a volume of 2 l. The pump was a centrifugal pump from company Schmitt. A pressure valve on top of the tower was installed to regulate the pressure. A heat exchanger for heating and cooling was installed into the loop as drawn in FIG. 1.

Example 1a (First Step)

[0359] Selective direct fluorination of HFE-254 to E 227 (TFTFME).

[0360] The reservoir was filled with 1000 g (7.57 mol) HFE-254 (1,1,2,2-tetrafluoro-1-(methoxy)ethane) and the pump was started (flow of about 1500 l/h). 10% F.sub.2-gas (dilution in N.sub.2) was fed over a Bronkhorst mass flow meter into the tower so that the reaction temperature was kept at 30° C. while the pressure on the tower was kept at 10 bar abs. by the pressure valve. After 1 h 893 g (23.5 mol) F.sub.2 (10% F.sub.2 in N.sub.2 as inert gas) were fed into the system while the inert N.sub.2 together with some traces of formed HF and traces of E 227 left the apparatus over the pressure valve over the top into an efficient scrubber. After 10 min of further looping without any dosage, the pump was stopped. A sample was taken with a high grade stainless steel cylinder out of the reservoir to which after stopping of the pump all material has fallen down. This reservoir now is containing mainly the product E 227 (TFTFME) (as intermediate or final product) and most of the HF formed in the fluorination reaction (some of the HF may already have escaped together with the inert gas). The material in the cylinder carefully was poured into ice water into another pressure vessel (volume 2 l) and shaken for 5 min to remove HF into the water phase, the GC-analysis (GC=gas chromatography) of a vaporized organic phase showed an E 227 (TFTFME) concentration of 96%.

[0361] The phases were separated and the organic phase (not further dried) containing the E 227 (TFTFME) as an intermediate product was re-introduced into the countercurrent system for the next step. See Example 1b.

[0362] Alternatively, the organic phase containing the E 227 (TFTFME) was further worked up and optionally further purified to yield an isolated and/or further purified E 227 (TFTFME) as the final product. See Example 3.

Example 1b (Second Step)

[0363] Base initiated HF-elimination from E 227 (TFTFME) to obtain PFMVE.

[0364] In the next step, the pump was restarted and 921 g (9.1 mol) NEt.sub.3 were fed before the heat exchanger into the looping reaction mixture by using a piston dosage pump.

[0365] Remark on the quantity (9.1 mol) of NEt.sub.3 used in this Example: Since three mol of HF formed in the fluorination step have already been removed with the ice water in Example 1a, based on the quantity of 1000 g (7.57 mol) HFE-254), per se only 7.57 mol of NEt.sub.3 should be necessary in view of (1:1) stoichiometry for the HF-elimination step. As NEt.sub.3 even can take up three HF (complex formation) theoretically only 2.52 mol NEt.sub.3 would be necessary instead of 7.57 mol NEt.sub.3 stoichiometry (1:1). Since here, however, a phase separation was desired, the base NEt.sub.3 was used in high excess NEt.sub.3 as compared to (1:1) stoichiometry.

[0366] For this second step, the pressure was reduced to 7 bar abs. and the NEt.sub.3 feed was adjusted such that the temperature of the exothermic elimination reaction did not exceed 40° C. After 40 min, all NEt.sub.3 was fed in. After 10 min of further looping without any dosage, the Schmitt pump was stopped and after further 10 min (temperature of the mixture has reached 20° C.), a second phase was observed, analysis of the lower phase indicated a PFMVE concentration of 96% which after distillation in a 20 cm Vigreux column gave 1.17 kg PFMVE (corresponding to a yield of 93%) with a purity of 98.6% (GC). The sample for GC was taken into a gas mouse and injected into the GC as gas sample (GC column: 50 m Angilent CP-SIL 8)

Example 2

[0367] Synthesis of PFMVE by treatment of (crude) E 227 (TFTFME) with NEt.sub.3.

[0368] In this Example 2 a base initiated HF-elimination from E 227 (TFTFME) is performed to obtain PFMVE, and the PFMVE is further isolated and purified by distillation.

[0369] The compound E 227 (TFTFME) raw material was prepared in a countercurrent system as described in Example 1a, but instead of work up with ice water, the material in the reservoir after fluorination (containing E 227 and the formed HF) was transferred into a pressure distillation column made out of Hastelloy C4, and which was equipped with a condenser. Then, the raw material containing the crude E 227 carefully treated with a slow feed of NEt.sub.3 (11 mol) at maximum temperature of 40° C. until no exothermic activity could be observed anymore. The product E 227 finally was distilled off at 5 bar abs., and at a transition temperature of −1° C. to yield 1,029 g (82%) PFMVE as yellow liquid.

[0370] Remark on the quantity (11 mol) of NEt.sub.3 used in this Example: for four mol HF to be consumed, in view of (1:1) stoichiometry a quantity of 30.28 mol of NEt.sub.3 should be necessary. Since here, in this Example no phase separation was to be performed a quantity of only 11 mol of NEt.sub.3 was sufficient to be used, corresponding to a 10% excess of base NEt.sub.3. Alternatively, of course, this treatment and distillation described in this Example 2, instead of treating crude E 227 still containing HF, can also be performed with isolated and purified E 227 (i.e., E 227 not containing HF anymore).

Example 3

[0371] Isolation and further purification of E 227 (TFTFME) by distillation.

[0372] The compound E 227 (TFTFME) raw material was prepared in a countercurrent system as described in Example 1a. After the work up with ice water, the organic phase containing the crude compound E 227 (TFTFME) was dried for 30 min over Na.sub.2SO.sub.4. Then, the dried organic phase containing the crude compound E 227 (TFTFME) was transferred into a pressure distillation column made out of Hastelloy C4, and which was equipped with a condenser and kept at a temperature of −20° C.

[0373] The product E 227 finally was distilled off at 5 bar abs., and at a transition temperature of 18° C. to yield 1,310 g (93%) with a purity of 98.4% (GC)

Example 4

[0374] Continuous conversion of HFC 254 to PFMVE in a two-step microreactor system.

[0375] Apparatus:

[0376] For the first step (fluorination) a 27 ml microreactor (microreactor I) made out of SiC (silicium carbide) was used. For the elimination step, a second microreactor (microreactor II) made out of Ni (nickel) with a volume of 54 ml was installed in series; the first microreactor was kept at room temperature (ambient temperature, e.g., about 25° C.) by cooling, the second microreactor was heated to 80° C. After the first microreactor, there is a cyclone (not shown in the FIG. 2) allowing some inert gas to leave the system over a pressure valve installed at the cyclone. A buffer tank with filling level measurement is also installed between first and second microreactor allowing regulating and balancing the feed between the reactors by a Swagelok hand valve. There is a cooler installed after the second microreactor (also not shown in the FIG. 2) to cool down the reaction mixture to 0° C. which is fed after microreactor II into the cooled trap (kept at −40° C.) over a deep pipe (the trap is a stainless steel cylinder with deep pipe, gas outlet and pressure valve at gas outlet).

Example 4a (First Step)

[0377] Selective direct fluorination of HFE-254 to E 227 (TFTFME).

[0378] Reaction: Before start of reaction, the system is continuously floated with a Nitrogen inert gas purge which was fast reduced to about 5 vol % (vs. F.sub.2) once the feeding of raw materials has started. A fast reduction of inert gas feed is essential as inert gas reduces sharply the heat exchange efficiency in the microchannel reactors. Into this installation F.sub.2 was fed directly out of a Fluorine electrolysis cell over a Bronkhorst mass flow controller together with 150 g (1.14 mol) liquid HFC 254 per hour (h), the pressure in the first microreactor was adjusted to 7 bar abs. at the pressure valve. The liquid phase obtained in the buffer tank contained the E 227 (TFTFME) and HF.

Example 4b (Second Step)

[0379] Ni-catalyzed HF-elimination from E 227 (TFTFME) to obtain PFMVE.

[0380] The liquid phase obtained in Example 4a containing the product E 227 (TFTFME) was heated to 80° C. in the second microreactor (made out of Ni) for performing the final HF-elimination which was done at 5 bar abs. to result in PFMVE which was collected in the trap at −30° C. together with the HF formed. Final distillation of PFMVE was done in a pressure column at 5 bar abs. made out of Hastelloy C4 yielding 89% of PFMVE (99.9% GC-purity) as light boiling substance based on HFC 254 starting material, and leaving the HF as bottom product in the column.

Example 5

[0381] Continuous conversion of HFC 254 to PFMVE in a two-step microreactor system, and quenching with NEt.sub.3 (base initiated HF-elimination).

[0382] The first reaction step of selective direct fluorination of HFC 254 to yield product E 227 (TFTFME) in HF (as intermediate or final product) was performed as in Example 4. But for the second reaction step, i.e., the quenching or base initiated HF-elimination, the organic base NEt.sub.3 (triethylamine) was fed into the reaction after the buffer tank before the second microreactor (microreactor II) in 1.33 equivalent amounts vs. HFC 254 in the first step (each NEt.sub.3 scavenges 3 equivalents HF), and the thermostat at the second microreactor was switched from heating now to cooling to a temperature of 20° C. in the second microreactor. Pressure was adjusted to 5 bar abs. using a pressure valve at the gas exit of the trap (kept at −30° C.). Efficient cooling is necessary as HF-quenching and HF-elimination with NEt.sub.3 as base is an exothermic process. A second phase was formed immediately in the trap, and in which the lower phase contained the product PFMVE. The product PFMVE was obtained without any further purification necessary, and with a purity of 97.9% (GC) and 95% yield.

Example 6

[0383] Continuous conversion of HFC 254 to PFMVE in a two-step microreactor system, and quenching with NBu.sub.3 (base initiated HF-elimination).

[0384] Example 5 was repeated but using as the organic base NBu.sub.3 (tributylamine) instead of NEt.sub.3. The phase separation took up to 1 h, and the crude PFMVE phase (94% purity) also contained some amine compounds.

[0385] Final purification of the crude PFMVE phase was done by distillation in a short Vigreux column at 5 bar abs. (like described in Example 4) yielding 82% PFMVE as the product.