CN1438980A - Process for producing fluoroalcohol - Google Patents
Process for producing fluoroalcohol Download PDFInfo
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- CN1438980A CN1438980A CN 01810870 CN01810870A CN1438980A CN 1438980 A CN1438980 A CN 1438980A CN 01810870 CN01810870 CN 01810870 CN 01810870 A CN01810870 A CN 01810870A CN 1438980 A CN1438980 A CN 1438980A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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Abstract
A process for producing a fluoroalcohol represented by the general formula (1) from methanol and tetrafluoroethylene or the like as starting materials in the presence of a free-radical generator and an acid acceptor, characterized by comprising the steps of: (i) reacting methanol with tetrafluoroethylene or the like; (ii) removing both a product of the reaction of the acid acceptor and the acid acceptor remaining unreacted from the crude reaction product obtained; (iii) introducing the crude reaction product treated in the step (ii) into a distillation column to distill off the methanol through the column top together with the free-radical generator remaining in the crude reaction product and take out a bottom containing the fluoroalcohol represented by the general formula (1) through the column bottom; (iv) returning the distillate obtained through the column top to the reactor to reuse it; and (v) purifying the bottom to recover the fluoroalcohol represented by the general formula (1).
Description
Technical field
The present invention relates to prepare general formula (1)
H(CFR
1CF
2)
nCH
2OH (1)
(n=1 or 2; During n=1, R
1Expression F or CF
3, during n=2, R
1Expression F) method of the fluorine-containing alcohol of expression.
Background technology
As H (CF
2CF
2)
nCH
2The preparation method of OH (n=1,2) opens in No. 2559628, clear 54-154707 communique and the United States Patent (USP) as the spy and to disclose, and reacts in the presence of free-radical generating agent tertiary butyl octyl group superoxide by methyl alcohol and tetrafluoroethylene, obtains H (CF
2CF
2)
nCH
2The telomer mixture of OH (n is up to 12).
In this method,, utilize again so wish to reclaim the methyl alcohol that is contained in the reacting coarse product because of using excessive methyl alcohol.For example, No. 302804 communique of patent discloses and comprises that methyl alcohol utilizes the fluorine-containing alcohol preparation method of step again.On the other hand, the residual state that undecomposed free-radical generating agent is arranged in reacting coarse product, or use in the reaction when being subjected to sour agent and residually in the reacting coarse product to have under the unreacted state that is subjected to sour agent etc., when distillation telomer mixture obtained as the fluorine-containing alcohol of purpose, evaporation of residual part, UV absorbed the impurity that becomes to grade and are contained in the fluorine-containing alcohol of recovery.Therefore, during solvent when for example being provided with the carrier of the recording layer that can information be write and/or read by laser as substrates such as making CD-R or DVD-R, existence can't be applicable to the shortcoming of making high-quality carrier.
The purpose of this invention is to provide the free from foreign meter in fact and recycling general formula of methyl alcohol (1) of a kind of preparation
H(CFR
1CF
2)
nCH
2OH (1)
(n=1 or 2; During n=1, R
1Expression F or CF
3, during n=2, R
1Expression F) method of the fluorine-containing alcohol of expression.
The announcement of invention
The present invention relates to the following method for preparing fluorine-containing alcohol shown in every.
The 1st a kind of method for preparing fluorine-containing alcohol is in free-radical generating agent and be subjected in the presence of the sour agent, is starting raw material with methyl alcohol and tetrafluoroethylene or R 1216, preparation general formula (1)
H(CFR
1CF
2)nCH
2OH (1)
(n=1 or 2; During n=1, R
1Expression F or CF
3, during n=2, R
1Expression F) method of fluorine-containing alcohol of expression, it is characterized in that comprising the steps (i) to (v):
(i) step that methyl alcohol and tetrafluoroethylene or R 1216 are reacted,
(ii) from the reacting coarse product of gained, remove the resultant of reaction and the unreacted step that is subjected to sour agent that are subjected to sour agent,
(iii) will import in the distillation tower, free-radical generating agent residual in methyl alcohol and this reacting coarse product will be distillated from cat head simultaneously, take out the step of composition at the bottom of the tower that contains the fluorine-containing alcohol that general formula (1) represents at the bottom of the tower through reacting coarse product that above-mentioned steps is (ii) handled,
(iv) will be back to the step of utilizing again the reactor from the cut of cat head gained, and
(v) composition at the bottom of the aforementioned tower of purifying reclaims the step of the fluorine-containing alcohol of general formula (1) expression.
The 2nd a kind of preparation HCF
2CF
2CH
2The method of OH, be free-radical generating agent and be subjected to sour agent in the presence of, be starting raw material with methyl alcohol and tetrafluoroethylene, the preparation HCF
2CF
2CH
2The method of OH, it is characterized in that comprising the steps (i) to (vi):
(i) step that methyl alcohol and tetrafluoroethylene are reacted,
(ii) from the reacting coarse product of gained, remove the resultant of reaction that is subjected to sour agent and be subjected to the step of the lingering section of sour agent,
(iii) will import through the reacting coarse product that above-mentioned steps is (ii) handled in first distillation tower, free-radical generating agent residual in methyl alcohol and this reacting coarse product is distillated from cat head simultaneously, and take out at the bottom of the tower and contain general formula (2)
H(CF
2CF
2)
lCH
2OH (2)
The step of composition at the bottom of the tower of the fluorine-containing alcohol of (integer of l=1 to 5) expression,
(iv) will be back to the step of utilizing again the reactor from the cut of cat head gained,
(v) with abovementioned steps (iii) at the bottom of the tower of gained composition import in the second column, distillate HCF from cat head
2CF
2CH
2OH takes out the step that contains composition at the bottom of the tower that l general formula (2) is the fluorine-containing alcohol more than 2 at the bottom of the tower, reaches
(vi) with above-mentioned steps (v) from cat head distilled HCF
2CF
2CH
2OH contacts the back or distillation in the presence of alkali with alkali, reclaim HCF
2CF
2CH
2The step of OH.
The 3rd the 2nd preparation HCF
2CF
2CH
2The method of OH, wherein (HCF is reclaimed in distillation to step vi)
2CF
2CH
2The method of OH is that distillation contains HCF
2CF
2CH
2The composition of OH and after removing low boiling point component, distill the HCF that contains once more as composition gained at the bottom of the tower
2CF
2CH
2The composition of OH reclaims HCF
2CF
2CH
2The method of OH.
In the step that methyl alcohol and tetrafluoroethylene or R 1216 react in the presence of free-radical generating agent, Paratetrafluoroethylene or R 1216 use excessive methyl alcohol.Temperature of reaction is 40 to 140 ℃, and the reaction times is 3 to 12 hours, and reaction pressure is 0.2 to 1.2MPa.Reaction can be carried out in the such autoclave of for example autoclave.Preferred in the reaction system with inert gas replacements such as nitrogen, argon gas.
As free-radical generating agent, when using distillation can with the common distilled free-radical generating agent of methyl alcohol.These free-radical generating agent can distillate jointly with methyl alcohol and get final product, even resolvently in still-process also can.
Particularly, can preferably enumerate superoxide such as ditertiary butyl peroxide (109 to 110 ℃ of boiling points) (can trade(brand)name " Perbutyl D " (Japanese grease (strain) system) obtain), t-butylperoxy-2-ethylhexanoate (can trade(brand)name " Perbutyl O " (Japanese grease (strain) system) obtain), t-butylperoxy sec.-propyl carbonic ether (can trade(brand)name " Perbutyl I " (Japanese grease (strain) system) acquisition).Wherein, preferably use ditertiary butyl peroxide.
For every mole tetrafluoroethylene or R 1216, the usage quantity of free-radical generating agent is generally 0.005 to 0.1 mole.
Above-mentioned being reflected at is subjected to carry out under the sour agent existence.As being subjected to sour agent, can enumerate the carbonate of basic metal such as lime carbonate, magnesiumcarbonate, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or alkaline-earth metal or supercarbonate, calcium oxide, calcium hydroxide, soda-lime, barium carbonate etc.Preferably be subjected to sour agent not make reaction be tied to form strong basicity, and can hold back the acid such as HF that produce when reacting.
Though be not particularly limited by the usage quantity of sour agent, for per 1 mole tetrafluoroethylene or R 1216, be 0.001 to 0.1 mole and get final product.
The reaction of methyl alcohol and tetrafluoroethylene or R 1216 is generally carried out with the intermittent type step, but this reacted step all can with intermittent type step or consecutive steps.
By the reacting coarse product of aforesaid method gained, import distillation tower from reactor as shown in Figure 1, for being distillated from cat head, methyl alcohol heats distillation tower.If react under these conditions; though the undecomposed free-radical generating agent of the common residual some of meeting in the reacting coarse product; but free-radical generating agent used in the present invention be when distillation can with methyl alcohol simultaneously by the distilled free-radical generating agent; so general distillation condition of methyl alcohol; for example the pressure-controlling of distillation tower (is represented with gauge pressure for-0.05 to 0.1MPa; adding thermal still down together) distills; when distillating methyl alcohol under 40 to 90 ℃, free-radical generating agent and methyl alcohol residual in the reacting coarse product distillate simultaneously.Therefore can from reacting coarse product, remove residual undecomposed free-radical generating agent.
As long as the undecomposed free-radical generating agent that residues in the reacting coarse product can be removed from reacting coarse product among the present invention, free-radical generating agent can distillate simultaneously with methyl alcohol, or free-radical generating agent is decomposed in still-process, and its resolvent can distillate simultaneously with methyl alcohol also can.Therefore, contain in the cut of methyl alcohol and also can contain undecomposed free-radical generating agent, also can contain the resolvent of free-radical generating agent, or contain both and also can.In for example above-mentioned free-radical generating agent that exemplifies, when using tert-butyl peroxide, in still-process, almost do not decompose, so tert-butyl peroxide and methyl alcohol distillate simultaneously.
In the reacting coarse product of methyl alcohol and tetrafluoroethylene or R 1216, though there is the situation that contains HF and water, these materials are concentrated in the stage casing of distillation tower.The layer that HF and water are concentrated as shown in Figure 2, can be used as side stream and takes out from distillation tower.The temperature of side stream is 80 to 120 ℃/0.1MPa.
Among the present invention, reacting coarse product imported distillation tower before, from reacting coarse product, remove CaF
2, NaF etc. the resultant of reaction that is subjected to sour agent and unreactedly be subjected to sour agent.This operation is not particularly limited, and gets final product so long as can remove the resultant of reaction and the unreacted method of sour agent that is subjected to that are subjected to sour agent from reacting coarse product, for example, as shown in Figure 1, can use separating centrifuge and removes effectively.
As illustrated in fig. 1 and 2, the cut that obtains from cat head is back to the reactor and utilizes.When containing undecomposed free-radical generating agent in this cut, free-radical generating agent is also recycling.Even contain the situation of the resolvent of free-radical generating agent in this cut, also this cut directly can be back in the reactor and utilize again.
After the methyl alcohol distillation, preferably at the bottom of the tower that contains the fluorine-containing alcohol mixture that remains in the still kettle in the composition, remove residual free-radical generating agent fully, as long as but the amount that is contained in the free-radical generating agent in the composition at the bottom of the tower is below the 1000 quality ppm, be preferably that 50 quality ppm are following to get final product.
Take out composition at the bottom of the tower at the bottom of the tower, as shown in Figures 1 and 2, import purification step, remove the H (CF that is present in the reacting coarse product through distillation
2CF
2)
xCH
2OH (x is more than 3), H (CF (CF
3) CF
2)
yCH
2OH impurity such as (y are more than 2) reclaims general formula (1)
H(CFR
1CF
2)
nCH
2OH (1)
(n=1 or 2; During n=1, R
1Expression F or CF
3, during n=2, R
1Expression F) fluorine-containing alcohol of expression.And, when using tetrafluoroethylene, because of containing HCF in the composition at the bottom of the tower as raw material
2CF
2CH
2OH and H (CF
2CF
2)
2CH
2OH, thus in purification step at the bottom of the tower composition with HCF
2CF
2CH
2OH and H (CF
2CF
2)
2CH
2OH separates successively also can.
In the methods of the invention, behind above-mentioned purification step, contain general formula (1)
H(CFR
1CF
2)
nCH
2OH (1)
(n and R
1Identical with above-mentioned definition) cut of fluorine-containing alcohol of expression, can be with after alkali contact, or in the presence of alkali, distill recovery.By carrying out described operation, can obtain the fluorine-containing alcohol of the few general formula of foreign matter content (1).At this moment, can be directly in the stage casing of distillation tower or still kettle, add alkali, or can be before distillation tower set handling groove (alkaline purification groove).When the alkaline purification groove is set,, generally after adding alkali, contacts 0.5 to 3 hour down at 20 to 150 ℃ and get final product though be not particularly limited for the operational condition of this treatment trough.Use methyl alcohol and tetrafluoroethylene to be feedstock production HCF
2CF
2CH
2During OH, from the reacting coarse product of methyl alcohol and tetrafluoroethylene reaction gained, remove and be subjected to sour agent, distillate methyl alcohol and residual free-radical generating agent from cat head in first distillation tower, at the bottom of tower, take out general formula (2)
H(CF
2CF
2)
lCH
2OH (2)
Composition at the bottom of the tower of (integer of l=1 to 5) expression will contain at the bottom of the tower of fluorine-containing alcohol of general formula (2) expression composition afterwards and import second column and distill, and distillate HCF from cat head
2CF
2CH
2OH contacts this cut the back or distill recyclable HCF in the presence of alkali with alkali
2CF
2CH
2OH.And take out at the bottom of the tower and contain composition at the bottom of the tower that l the general formula (2) is the fluorine-containing alcohol more than 2.
As alkali, preferred pKb is the alkali below 2.As alkali so, can enumerate alkali-metal carbonate such as yellow soda ash, salt of wormwood; Alkali-metal supercarbonate such as sodium bicarbonate, saleratus; Alkali metal alcoholates such as sodium methylate, sodium ethylate, sodium propylate, potassium tert.-butoxide, lithium ethoxide; Alkali-metal oxyhydroxide such as sodium hydroxide, magnesium hydroxide, lithium hydroxide; The oxyhydroxide of alkaline-earth metal such as calcium hydroxide, magnesium hydroxide, hydrated barta; Aluminium hydroxide, soda-lime etc.These alkali can use separately, or are used in combination more than 2 kinds and also can.Alkali generally can use pure solution such as methyl alcohol.
The usage quantity of alkali can be set aptly, but for the fluorine-containing alcohol of the general formula that contacts with alkali (1) of every 1kg weight, is generally 0.05 to 1.0 mole, is preferably 0.1 to 0.5 mole.
When using alkaline purification, can generate resultant of reaction such as alcohol, water, this resultant of reaction and can sneak in the fluorine-containing alcohol of general formula (1) as the low boiling point components such as alcohol of the solvent of alkali according to the alkali kind of using.Therefore, for obtaining the fluorine-containing alcohol of highly purified general formula (1), at first as the distillation procedure of fs, carry out from the fluorine-containing alcohol of general formula (1), separating the distillation procedure of removing low boiling point component alcohol, water etc., then as subordinate phase, in the distillation procedure of preferred distillation fs as composition at the bottom of the tower and the composition of the fluorine-containing alcohol that contains general formula (1), reclaim the fluorine-containing alcohol of general formula (1).An embodiment of the invention that comprise such distillating method as shown in Figure 3.By such distillating method, do not sneak into alcohol or water, can obtain the fluorine-containing alcohol of general formula free from foreign meter in fact (1).
In addition, replace such two-stage distillation procedure, also can distill low boiling point components such as removing alcohol, water successively after, reclaim the fluorine-containing alcohol of general formula (1) from the cat head of distillation tower or stage casing.
In the method for the present invention, can adopt any distillating method, but the distillating method of two-stage can reclaim the fluorine-containing alcohol of highly purified general formula (1) simply.
Can obtain the evaporation of residual composition by preparation method of the present invention is below the 50 quality ppm, below the preferred 25 quality ppm, and the more preferably fluorine-containing alcohol of the following general formula (1) of 10 quality ppm.
The evaporation of residual composition can be tried to achieve by following method.That is, fluorine-containing alcohol is measured the weight of its residual component down during evaporation at 40 ℃, 5mmHg (0.665kPa), be expressed as quality ppm fluorine-containing alcohol.
The UV absorbancy (205nm) of the general formula of gained of the present invention (1) fluorine-containing alcohol in methyl alcohol be below the 0.1abs, be preferably-below the 0.1abs, more preferably-below the 0.2abs.UV absorbancy in the methyl alcohol uses methyl alcohol to measure as a reference to add 3ml methyl alcohol gained material as measuring sample in the fluorine-containing alcohol of 1ml general formula (1).
The what is called " free from foreign meter in fact " of the fluorine-containing alcohol by preparation method's gained of the present invention means, (i) the evaporation of residual composition of fluorine-containing alcohol is below the 50 quality ppm, be preferably below the 25 quality ppm, more preferably below the 10 quality ppm, and/or (ii) the UV absorbancy (205nm) in the methyl alcohol is below the 0.1abs, preferably-below the 0.1abs, more preferably-below the 0.2abs.
The carrier that substrate is provided with the recording layer that can information be write and/or read by laser can make by following method: at the solvent of the fluorine-containing alcohol that contains general formula of the present invention (1), be preferably in the fluorine series solvent that contains this fluorine-containing alcohol and dissolve pigment, with ordinary method with the solution coat of gained on substrate, carry out drying, form the recording layer that contains pigment.As this pigment, can enumerate cyanines and be pigment, phthalocyanine and be pigment, pyrans father-in-law and be pigment, sulfo-pyrans father-in-law and be pigment, spiny dogfish father-in-law (squalilium) methane series pigment, Azulene (azurenium) is that pigment, indigo fen are that pigment, indoaniline (indoaniline) are that pigment, triphenyl methane are that pigment, quinone are that pigment, ammonium father-in-law (aminium) are that pigment, diimmonium (diimmonium) are that pigment, metallic complex salt are pigment etc.As substrate, can enumerate plastics such as polycarbonate, polymethylmethacrylate, Resins, epoxy, amorphous polyolefin, polyester, polyvinyl chloride, glass, pottery etc.And, to improve planarity, improve clinging power, to prevent that the rotten etc. of recording layer from being purpose, undercoat can be set between recording layer and substrate also, or protective layer is set on recording layer also can.
By the present invention, can easily prepare the carrier (CDs such as CD-R, DVD-R etc.) that is suitable for making substrate and is provided with the recording layer that can information be write and/or read by laser, photoreceptor of egative film etc., HCF free from foreign meter in fact
2CF
2CH
2OH, H (CF
2CF
2)
2CH
2OH and HCF (CF
3) CF
2CH
2OH, and can effectively utilize the cut of the methyl alcohol that contains recovery and be contained in free-radical generating agent in this cut.
The accompanying drawing simple declaration
Fig. 1 is the figure of expression an embodiment of the invention.
Fig. 2 is the figure that expression comprises an embodiment of the invention that propose the side stream step.
Fig. 3 is the figure that expression comprises an embodiment of the invention of two-stage alkalescence distilation steps.
Among the figure, symbol 1 is that first distillation tower, symbol 5 for second column, symbol 6 for alkaline purification groove, symbol 7 and 8 be alkaline distillation tower for distillation tower, symbol 3 for separating centrifuge, symbol 4 for reactor, symbol 2.
The best mode that carries out an invention
Below enumerate embodiment and illustrate in greater detail the present invention.
Embodiment 1-1
In autoclave, add methyl alcohol (1500g), Perbutyl D (ditertiary butyl peroxide, 31.25g) and lime carbonate (6.5g).After in the nitrogen replacement reactor, be warming up to 125 ℃, to be 0.85MPa add the limit with tetrafluoroethylene makes it carry out reaction in 2.6 hours at control pressure on the limit.Behind the cooling reacting coarse product, gravimetry is 2270g, uses the gas chromatograph analysis, and the result learns that undecomposed and residual Perbutyl D is 15.5g.
For the reacting coarse product of gained,, handle by the following method by schema shown in Figure 3.
At first, reacting coarse product is imported separating centrifuge 3 from reactor 1, through centrifugation will be subjected to sour agent reaction product and unreacted removed by sour agent after, import first distillation tower 4.
Then, the pressure-controlling with distillation tower adds thermal still under 0.1MPa.Cat head from first distillation tower 4 under 80 to 90 ℃ recovered temperature distillates methyl alcohol.The cut of gained is 1261.5g.Analyze this cut and learn and contain 13.0g Perbutyl D, remain in the Perbutyl D in the reacting coarse product, decompose ground hardly and distillate jointly with methyl alcohol.Do not contain Perbutyl D at the bottom of the tower in the composition fully.
Afterwards, take out composition at the bottom of the tower at the bottom of the tower of first distillation tower 4, import purification step through distillation.Composition is fed to second column 5 at the bottom of the tower, distillates HCF from cat head
2CF
2CH
2OH (648.3g) takes out H (CF at the bottom of tower
2CF
2)
lCH
2OH (l represents the integer more than 2).Take out the HCF of gained
2CF
2CH
2The part of OH (150g) imports in the alkaline purification groove 6, adds sodium methylate (6g, about 0.03 mole in this cut; Form with 28% methanol solution).Then, will be through the HCF of alkaline purification
2CF
2CH
2OH imports alkaline distillation tower 7, through distillation methyl alcohol and water is distillated from cat head, will contain HCF
2CF
2CH
2Composition is delivered to alkaline distillation tower 8 at the bottom of the tower of OH.In alkaline distillation tower 8, distill at last, reclaim HCF as the stage casing cut
2CF
2CH
2OH.The HCF of gained
2CF
2CH
2The distillation residual component of OH is 10 quality ppm, UV absorbancy (205nm) is-and below the 0.2abs.
Embodiment 1-2
To be back in the reactor 1 at the 1261.5g methyl alcohol that contains Perbutyl D (13.0g) that embodiment 1-1 reclaims and utilize again.That is, add the 254g fresh methanol in the methyl alcohol of recovery, add Perbutyl D (15.75g) and lime carbonate (6.5g) again, similarly react with embodiment 1-1.Reaction times is 2.7 hours.Reaction end of a period postcooling reacting coarse product, gravimetry is 2265g, learns the undecomposed Perbutyl D of residual 15.1g with the gas chromatograph analysis.
For the reacting coarse product of gained, also similarly handle by schema shown in Figure 3 with the foregoing description 1-1.
That is, at first reacting coarse product is imported separating centrifuge 3 from reactor 1, remove the reaction product and unreacted being subjected to that are subjected to sour agent and import first distillation tower 4 after the sour agent.
Then, the limit is 0.1MPa with the pressure-controlling of distillation tower, and the limit adds thermal still.Cat head from first distillation tower 4 under 80 to 90 ℃ of recovered temperatures distillates methyl alcohol.The gained cut is 1262.3g.Analyze this cut and learn, contain 12.6g Perbutyl D, the Perbutyl D that remains in reacting coarse product distillates with methyl alcohol with decomposing hardly simultaneously.Do not contain Perbutyl D at the bottom of the tower in the composition fully.
Afterwards, take out composition at the bottom of the tower at the bottom of the tower of first distillation tower 4, import purification step through distillation.Composition is imported into second column 5 at the bottom of the tower, distillates HCF from cat head
2CF
2CH
2OH (644.1g) takes out at the bottom of the tower and contains H (CF
2CF
2)
lCH
2Composition at the bottom of the tower of OH (l represents the integer more than 2).Take out the HCF of gained
2CF
2CH
2The part of OH (150g) imports alkaline purification groove 6, adds 28% sodium methylate (6g, about 0.03 mole) in this cut.Then, will be through the HCF of alkaline purification
2CF
2CH
2OH imports alkaline distillation tower 7, distillates the first alcohol and water by distillation from cat head, will contain HCF
2CF
2CH
2Composition is delivered to alkaline distillation tower 8 at the bottom of the tower of OH.At last, by in alkaline distillation tower 8, distilling, reclaim HCF as the stage casing cut
2CF
2CH
2OH.The HCF of gained
2CF
2CH
2The evaporation of residual composition of OH is 10 quality ppm, UV absorbancy (205nm) is-and below the 0.2abs.
Claims (3)
1. method for preparing fluorine-containing alcohol is in free-radical generating agent and be subjected in the presence of the sour agent, is starting raw material with methyl alcohol and tetrafluoroethylene or R 1216, prepares following general formula (1)
H(CFR
1CF
2)
nCH
2OH (1)
(n=1 or 2; During n=1, R
1Expression F or CF
3, during n=2, R
1Expression F) method of fluorine-containing alcohol of expression, it is characterized by be to comprise the steps (i) to (v):
(i) step that methyl alcohol and tetrafluoroethylene or R 1216 are reacted,
(ii) from the reacting coarse product of gained, remove the resultant of reaction and the unreacted step that is subjected to sour agent that are subjected to sour agent,
(iii) will import in the distillation tower, free-radical generating agent residual in methyl alcohol and this reacting coarse product will be distillated from cat head simultaneously, take out the step of composition at the bottom of the tower that contains the fluorine-containing alcohol that general formula (1) represents at the bottom of the tower through reacting coarse product that above-mentioned steps is (ii) handled,
(iv) will be back to the step of utilizing again the reactor from the cut of cat head gained, and
(v) composition at the bottom of the aforementioned tower of purifying reclaims the step of the fluorine-containing alcohol of general formula (1) expression.
2. one kind prepares HCF
2CF
2CH
2The method of OH, be free-radical generating agent and be subjected to sour agent in the presence of, be starting raw material with methyl alcohol and tetrafluoroethylene, the preparation HCF
2CF
2CH
2The method of OH, it is characterized in that comprising the steps (i) to (vi):
(i) step that methyl alcohol and tetrafluoroethylene are reacted,
(ii) from the reacting coarse product of gained, remove the resultant of reaction that is subjected to sour agent and be subjected to the step of the lingering section of sour agent,
(iii) will import through the reacting coarse product that above-mentioned steps is (ii) handled in first distillation tower, free-radical generating agent residual in methyl alcohol and this reacting coarse product is distillated from cat head simultaneously, and take out at the bottom of the tower and contain general formula (2)
H(CF
2CF
2)
lCH
2OH (2)
The step of composition at the bottom of the tower of the fluorine-containing alcohol of (integer of l=1 to 5) expression,
(iv) will be back to the step of utilizing again the reactor from the cut of cat head gained,
(v) with abovementioned steps (iii) at the bottom of the tower of gained composition import in the second column, distillate HCF from cat head
2CF
2CH
2OH takes out at the bottom of the tower and contains that l is the step of the tower bottom branch of the fluorine-containing alcohol 2 or more general formula (2), reaches
(vi) with above-mentioned steps (v) from cat head distilled HCF
2CF
2CH
2OH contacts the back or distillation in the presence of alkali with alkali, reclaim HCF
2CF
2CH
2The step of OH.
3. the preparation HCF of claim 2
2CF
2CH
2The method of OH, wherein (HCF is reclaimed in distillation to step vi)
2CF
2CH
2The method of OH is that distillation contains HCF
2CF
2CH
2The composition of OH and after removing low boiling point component, distill the HCF that contains once more as composition gained at the bottom of the tower
2CF
2CH
2The composition of OH reclaims HCF
2CF
2CH
2The method of OH.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000257838A JP2002069017A (en) | 2000-08-28 | 2000-08-28 | Method for producing fluorinated alcohol |
| JP257838/2000 | 2000-08-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1438980A true CN1438980A (en) | 2003-08-27 |
Family
ID=18746237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01810870 Pending CN1438980A (en) | 2000-08-28 | 2001-07-13 | Process for producing fluoroalcohol |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2002069017A (en) |
| CN (1) | CN1438980A (en) |
| TW (1) | TWI250975B (en) |
| WO (1) | WO2002018306A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825528A (en) * | 2020-06-15 | 2020-10-27 | 三明市海斯福化工有限责任公司 | Method for purifying fluorine-containing alcohol |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3915759A1 (en) * | 1989-05-13 | 1990-11-15 | Hoechst Ag | METHOD FOR PRODUCING TELOMERAL ALCOHOLS |
| JP3029618B1 (en) * | 1998-12-28 | 2000-04-04 | ダイキン工業株式会社 | Manufacturing method of fluorine alcohol |
| JP3026804B1 (en) * | 1999-03-15 | 2000-03-27 | ダイキン工業株式会社 | Manufacturing method of fluorine alcohol |
-
2000
- 2000-08-28 JP JP2000257838A patent/JP2002069017A/en active Pending
-
2001
- 2001-07-13 CN CN 01810870 patent/CN1438980A/en active Pending
- 2001-07-13 WO PCT/JP2001/006072 patent/WO2002018306A1/en active Application Filing
- 2001-08-03 TW TW90119029A patent/TWI250975B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825528A (en) * | 2020-06-15 | 2020-10-27 | 三明市海斯福化工有限责任公司 | Method for purifying fluorine-containing alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002018306A1 (en) | 2002-03-07 |
| TWI250975B (en) | 2006-03-11 |
| JP2002069017A (en) | 2002-03-08 |
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