CN101306977A - Process for preparing perfluoroalkyl group by telomerization - Google Patents
Process for preparing perfluoroalkyl group by telomerization Download PDFInfo
- Publication number
- CN101306977A CN101306977A CNA2008100616732A CN200810061673A CN101306977A CN 101306977 A CN101306977 A CN 101306977A CN A2008100616732 A CNA2008100616732 A CN A2008100616732A CN 200810061673 A CN200810061673 A CN 200810061673A CN 101306977 A CN101306977 A CN 101306977A
- Authority
- CN
- China
- Prior art keywords
- telomerization
- alkyl iodide
- perfluoroalkyl group
- carbon chain
- extraction column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000605 extraction Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 26
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000011737 fluorine Substances 0.000 claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 23
- 238000011049 filling Methods 0.000 claims description 16
- -1 perfluoroalkyl iodides Chemical class 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 43
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000282326 Felis catus Species 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 5
- 239000003507 refrigerant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000010606 normalization Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 241001253206 Andrias Species 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing perfluoro-alkyl iodide through telomerization. The method is as follows: short-carbon chain perfluoro-alkyl iodide and tetrafluoroethylene are added in an extraction column reactor filled with catalyst filler inside an extraction tower or a rectification tower reactor taking catalyst as filler so as to carry out reaction with the molar ratio between short-carbon chain perfluoro-alkyl iodide and tetrafluoroethylene of between 3:1 and 50:1 at a reaction temperature of between 40 and 200 DEG C, thereby obtaining perfluoro-alkyl iodide. The method takes the lead in taking the extraction column filled with catalyst filler inside the extraction tower or the rectification tower taking catalyst as filler as a reactor which is used in the telomerization of perfluoro-alkyl iodide; moreover, compared with the prior disclosed art, the method has the advantages of simple production equipment, easily controlled technological parameter, better operational safety, ideal reaction selectivity, high product purity and no hydrogen-containing byproducts, etc.
Description
Technical field
The present invention relates to polyreaction, relate in particular to a kind of method of preparing perfluoroalkyl group by telomerization.
Background technology
Carbon number is the straight chain full-fluorine alkyl iodide R of 6-12
f(CF
2CF
2)
nI is a key intermediate of producing fluorochemical surfactant, fluorine-contained finishing agent and other fluorine-containing fine chemicals.Its derived product has high surface, high thermal stability, high chemical stability and excellent characteristics such as hydrophobic and lyophobic property.
Full-fluorine alkyl iodide R
f(CF
2CF
2)
nI is normally by the full-fluorine alkyl iodide R of short carbon chain
fI and tetrafluoroethylene telomerize and form.R wherein
fBe C
1-6Perfluoroalkyl, n are 1～4 integer.
This telomerization can cause or initiator carries out under causing at thermal initiation, light-initiated, catalyzer.
The kick off temperature of thermal initiation between 200 ℃～400 ℃, is the simplest a kind of initiation mode generally.As US 3,226,449 disclose a kind of method of thermal initiation preparing perfluoroalkyl group by telomerization thing.Reaction is carried out under 200 ℃～250 ℃, 2.5MPa～5.5MPa.But the telomer carbon chain length distribution broad that thermal initiation produces, long carbochain telomer content is higher; At high temperature the iodine that generates in the reaction process can cause problems such as equipment corrosion; At high temperature use tetrafluoroethylene also to cause safety problem easily.
US 3,234,294, and US 4,067,916 and US 5,068,471 grades the method for utilizing radical initiator to cause the preparing perfluoroalkyl group by telomerization thing is disclosed.But in these methods, perfluoroalkyl radical generates by product together with radical initiator or the reaction of its fragment.US 5,929, and 292 disclose a kind of method of utilizing radical initiator to cause the telomerization synthesizing perfluoroalkyl iodide in the rectifying tower reactor.But the amount of initiator of using in the method is bigger, and hydrogeneous content of by-products is also just higher relatively.
CN 1,379,008, and CN 1,356,302 and US 5,240,574 grades the method for utilizing light-initiated preparing perfluoroalkyl group by telomerization thing is disclosed.Though photochemical catalysis can obtain the good telomer of quality,, equipment used difficult processing little because of light source power, the restriction of factors such as reaction time consumption length is difficult to industrialization.
US 5,639,923, and US 3,557,224 and US 3,883,604 grades the method for utilizing catalyzer to cause the preparing perfluoroalkyl group by telomerization thing is disclosed.When utilizing catalyzer to telomerize, the selectivity of reaction is still unsatisfactory, in order to improve the selectivity of reaction, must improve the raw materials components mole ratio of short carbon chain full-fluorine alkyl iodide with tetrafluoroethylene.CN 1,535,258 disclose a kind of in the tubular reactor of catalyst filling filler the method for continuous production full-fluorine alkyl iodide, though it is better to telomerize product quality, reaction raw materials short carbon chain perfluoroalkyl iodides need reach 25: 1 with the raw materials components mole ratio of tetrafluoroethylene.Nonetheless, the transformation efficiency of tetrafluoroethylene is also unsatisfactory.
There is following defective in present disclosed technology:
The degree that telomerizes of tank reactor is restive, and the telomer product carbochain that obtains distributes very wide; The tubular reactor reaction efficiency is low, and operation easier is big; Hydrogeneous by-products content is big in the product that the rectifying tower reactor that initiator causes obtains, and the initiator usage quantity is big.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of preparing perfluoroalkyl group by telomerization is provided.
It is that short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene are joined extraction tower reactor that catalyst filling is housed in the extraction column or is to react in the distillation column reactor device of filler with the catalyzer, short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene mol ratio are 3: 1～50: 1, temperature of reaction is 40 ℃～200 ℃, obtains perfluoroalkyl iodides.
Described extraction tower reactor comprises product collection still, adapting pipe, extraction column, reflux cooling tower, siphon pipe, be provided with product collection still, extraction tube, reflux cooling pipe from top to bottom successively, product collection still upper end is connected with the extraction column upper end through adapting pipe, the extraction column bottom is connected with the product collection still through siphon pipe, is filled with catalyzer in the extraction column.
Described perfluoroalkyl iodides general formula is R
f(CF
2CF
2)
nI, wherein R
fBe C
1-4Perfluoroalkyl, n are 1～4 integer.Short carbon chain full-fluorine alkyl iodide general formula is R
fI.R wherein
fBe C
1-4Perfluoroalkyl.Catalyzer is one or more in copper, nickel, tin, zinc, magnesium, silver, iron, chromium, cobalt, tungsten and the alloy thereof.The particle diameter of catalyzer is 2 orders～300 orders, preferred 5 orders～50 orders.The slick spherical powder of catalyzer preferred surface.The height of catalyst filling layer is 5: 1～800: 1 with the internal diameter ratio, is preferably 10: 1～200: 1.Catalyst filling layer internal diameter is preferably 5cm～50cm.Preferred 5: 1～30: 1 of short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene mol ratio.The reaction mainly occur in the catalyzer filled section: for the distillation column reactor device at rectifying section, for extraction tower in extraction column.The R that generates in the reaction
f(CF
2CF
2)
nI discharges reactor continuously or off and on via the bottom that product is collected still.Short carbon chain full-fluorine alkyl iodide R
fI or tetrafluoroethylene are for mixing reinforced or separate charging.Short carbon chain full-fluorine alkyl iodide R
fI or tetrafluoroethylene are continuously feeding or intermittent feeding.The catalyst filling temperature is 40 ℃-200 ℃, preferred 80-120 ℃.Product collection still temperature is lower than under the reaction pressure 0 ℃～15 ℃ of product boiling points.
The present invention takes the lead in comparing with disclosed technology the extraction tower of catalyst filling being housed in the extraction column or being that the rectifying tower of filler is applied to as reactor in the telomerization of perfluoroalkyl iodides with the catalyzer, and it is simple to have a production unit; Processing parameter control easily; Processing safety is better; Good reaction selectivity; The product purity height; There are not advantages such as hydrogeneous by product.
Description of drawings
Accompanying drawing is an extraction tower structure of reactor synoptic diagram of the present invention, among the figure: product collection still 1, adapting pipe 2, extraction column 3, reflux cooling tower 4, siphon pipe 5.
Embodiment
The method of preparing perfluoroalkyl group by telomerization is that short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene are joined extraction tower reactor that catalyst filling is housed in the extraction column or is to react in the distillation column reactor device of filler with the catalyzer, short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene mol ratio are 3: 1-50: 1, temperature of reaction is 40 ℃～200 ℃, generate the full-fluorine alkyl iodide of certain chain lengths efficiently, and do not produce impurity such as hydrogenous organic compound.
As shown in drawings, the extraction tower reactor comprises product collection still 1, adapting pipe 2, extraction column 3, reflux cooling tower 4, siphon pipe 5, be provided with product collection still 1, extraction tube 3, reflux cooling pipe 4 from top to bottom successively, product collection still 1 upper end is connected with extraction column 3 upper ends through adapting pipe 2, extraction column 3 bottoms are connected with product collection still 1 through siphon pipe 5, are filled with catalyzer in the extraction column 3.
Described perfluoroalkyl iodides general formula is R
f(CF
2CF
2)
nI, wherein R
fBe C
1-4Perfluoroalkyl, n are 1～4 integer.Short carbon chain full-fluorine alkyl iodide general formula is R
fI.R wherein
fBe C
1-4Perfluoroalkyl.Catalyzer is one or more in copper, nickel, tin, zinc, magnesium, silver, iron, chromium, cobalt, tungsten and the alloy thereof.The particle diameter of catalyzer is 2 orders～300 orders, preferred 5 orders～50 orders.The slick spherical powder of catalyzer preferred surface.The height of catalyst filling layer is 5: 1～800: 1 with the internal diameter ratio, is preferably 10: 1～50: 1.Catalyst filling layer internal diameter is preferably 5cm～50cm.Preferred 5: 1～30: 1 of short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene mol ratio.The reaction mainly occur in the catalyzer filled section: for the distillation column reactor device at rectifying section, for extraction tower in extraction column.The R that generates in the reaction
f(CF
2CF
2)
nI discharges reactor continuously or off and on via the bottom that product is collected still.Short carbon chain full-fluorine alkyl iodide R
fI or tetrafluoroethylene are for mixing reinforced or separate charging.Short carbon chain full-fluorine alkyl iodide R
fI or tetrafluoroethylene are continuously feeding or intermittent feeding.The catalyst filling temperature is 40 ℃-200 ℃, preferred 80-120 ℃.Product collection still temperature is lower than under the reaction pressure 0 ℃～15 ℃ of product boiling points.
When utilizing the extraction tower preparing perfluoroalkyl group by telomerization, at first with a certain amount of short carbon chain full-fluorine alkyl iodide R
fI is warming up to temperature of reaction with extraction column after joining in the product collection still again, product is collected still be warmed up to the product collection temperature, and lead to refrigerant in reflux cooling pipe clamp cover.And then in system, add short carbon chain full-fluorine alkyl iodide R
fI and tetrafluoroethylene.Carbon number is less than the full-fluorine alkyl iodide of the short carbon of target after the cooling of reflux cooling pipe, carrying tetrafluoroethylene enters extraction column and carries out telomerization, after reaction solution reaches the siphon liquid level, flowing into product through siphon pipe collects in the still, the aim carbon chain length and more full-fluorine alkyl iodide enrichment in collector of high carbon chain length, the full-fluorine alkyl iodide that is lower than the aim carbon chain length then enters extraction column through pipe connecting, continues circulating reaction.
When utilizing the rectifying tower preparing perfluoroalkyl group by telomerization, at first with a certain amount of short carbon chain full-fluorine alkyl iodide R
fI joins in the rectifying tower, again the catalyzer filled section is warming up to temperature of reaction, and rectifying Tata still is warmed up to the product collection temperature, and leads to refrigerant in rectifying tower reflux cooling pipe clamp cover.And then in system, add short carbon chain full-fluorine alkyl iodide R
fI and tetrafluoroethylene.Carbon number is less than the full-fluorine alkyl iodide of the short carbon of target after the cooling of reflux cooling pipe, carrying tetrafluoroethylene enters the catalyzer filled section and carries out telomerization, reaction solution is back to the tower still through rectifying tower, the aim carbon chain length and more the full-fluorine alkyl iodide of high carbon chain length is in the enrichment of tower still, the full-fluorine alkyl iodide that is lower than the aim carbon chain length is circulating reaction in rectifying tower then.
By the following examples the present invention is carried out more specific description, but the present invention is not limited to described embodiment.
Embodiment 1
Stainless steel by internal diameter 10mm, the reflux cooling pipe of high 800mm; Internal diameter 40mm, the extraction column of high 400mm, volume are that the product of 1.2L is collected in the extraction tower reactor that still forms and telomerized test.Catalyst filling is the spherical active copper catalyzer of 5 purposes, and the catalyst bed layer height is 300mm.The reflux cooling pipe is furnished with external jacket, interior logical refrigerant cooling, and extraction column and product are collected still and also are furnished with external jacket, use the low-pressure water steam-heated cal(l)andria.Collect to product earlier during reaction and add 1500g C in the still
2F
5I.Logical service water in reflux cooling pipe clamp cover leads to the low-pressure water steam in extraction column and product collector chuck then, and with reflux cooling pipe middle part, the temperature that extraction column and product are collected still is controlled at 40 ℃, 80 ℃ and 140 ℃ respectively.Speed with 10g/h adds C again
2F
4, continuing feed 2h, behind the reinforced end 2h, stopped reaction is collected still with reaction solution by product and is taken out.Analyze with the GC area normalization method.Remove unreacted C
2F
5I, product component is: C
4F
9I 71.5%, C
6F
13I 21.2%, C
8F
17I 4.9%, C
10F
21I 1.3%, C
12F
25I 0.4%, other high boiling material 0.7%.
Embodiment 2
Stainless steel by internal diameter 10mm, the reflux cooling pipe of high 1500mm; Internal diameter 10mm, the extraction column of high 1300mm, volume are that the product of 1.2L is collected in the extraction tower reactor that still forms and telomerized test.Catalyst filling is the spherical active copper catalyzer of 50 purposes, and the catalyst bed layer height is 1000mm.The reflux cooling pipe is furnished with external jacket, interior logical refrigerant cooling, and extraction column and product are collected still and also are furnished with the external jacket pipe, use the low-pressure water steam-heated cal(l)andria.Add 1500g C by cat head
2F
5I.Logical service water in the reflux cooling pipe clamp cover, extraction column and product are collected logical low-pressure water steam in the still chuck, and with reflux cooling pipe middle part, the temperature that extraction column and product are collected still is controlled at 40 ℃, 120 ℃ and 140 ℃ respectively.And then add C with the speed of 30g/h
2F
4, continuing feed 4h, behind the reinforced end 2h, stopped reaction is collected still with reaction solution by product and is taken out.Analyze with the GC area normalization method.Remove unreacted C
2F
5I, product component is: C
4F
9I 59.1%, C
6F
13I30.9%, C
8F
17I 5.3%, C
10F
21I 2.0%, C
12F
25I 0.9%, other high boiling material 1.8%.
Embodiment 3
Stainless steel by internal diameter 10mm, the reflux cooling pipe of high 800mm; Internal diameter 40mm, the extraction column of high 400mm, volume are that the product of 1.2L is collected in the extraction tower reactor that still forms and telomerized test.Catalyst filling is the spherical active copper-nickel alloy catalysts of 10 purposes, and the mass ratio of copper nickel is 3: 7, and the catalyst bed layer height is 300mm.The reflux cooling pipe is furnished with the external jacket pipe, interior logical refrigerant cooling, and extraction column and product are collected still and also are furnished with the external jacket pipe, use the low-pressure water steam-heated cal(l)andria.Behind the oxygen with high purity nitrogen exchange system, add 800g C by cat head
2F
5I.Logical service water in the reflux cooling pipe clamp cover, extraction column and product are collected logical low-pressure water steam in the still chuck, and with reflux cooling pipe middle part, the temperature that extraction column and product are collected still is controlled at 40 ℃, 100 ℃ and 120 ℃ respectively.And then add C with the speed of 25g/h
2F
4, add C by cat head with the speed of 125g/h
2F
5I, the reinforced time all continues 4h, reinforced finish 2h after, stopped reaction takes out at the bottom of reaction solution collected the still still by product.Analyze with the GC area normalization method.Remove unreacted PFEI, product component is: C
4F
9I 82.5%, C
6F
13I 10.7%, C
8F
17I 3.8%, C
10F
21I 1.0%, C
12F
25I 0.8%, other high boiling material 1.2%.
Embodiment 4
Stainless steel by internal diameter 40mm, the body of the tower of long 1000mm and volume are to telomerize test in the distillation column reactor device formed of the tower still of 1.2L.Catalyst filling is the spherical active copper catalyzer of 10 purposes, and the catalyst bed layer height is 300mm, and bed top is apart from cat head 300mm.C
2F
5I is by cat head charging, C
2F
4Position by beds bottom 100mm adds.Behind the oxygen with high purity nitrogen exchange system, add 1000g C by cat head
2F
5I.The following 150mm of control cat head, the temperature at 450mm and 800mm place is 70 ℃, 100 ℃ and 130 ℃, tower still temperature is 160 ℃.And then add tetrafluoroethylene with the speed of 25g/h, continue feed 4h, reinforced finish 2h after, stopped reaction takes out reaction solution at the bottom of by tower.Analyze with the GC area normalization method.Remove C for reaction
2F
5I, product component is: C
4F
9I 40.3%, C
6F
13I 30.8%, C
8F
17I18.2%, C
10F
21I 6.3%, C
12F
25I 1.9%, other high boiling material 2.5%.
Claims (10)
1. the method for a preparing perfluoroalkyl group by telomerization, it is characterized in that, it is that short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene are joined extraction tower reactor that catalyst filling is housed in the extraction column or is to react in the distillation column reactor device of filler with the catalyzer, short carbon chain full-fluorine alkyl iodide and tetrafluoroethylene mol ratio are 3: 1-50: 1, temperature of reaction is 40 ℃～200 ℃, obtains perfluoroalkyl iodides.
2. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1, it is characterized in that described extraction tower reactor comprises product collection still (1), adapting pipe (2), extraction column (3), reflux cooling tower (4), siphon pipe (5), be provided with product collection still (1), extraction column (3), reflux cooling pipe (4) from top to bottom successively, product collection still (1) upper end is connected with extraction column (3) upper end through adapting pipe (2), extraction column (3) bottom is connected with product collection still (1) through siphon pipe (5), and extraction column is filled with catalyzer in (3).
3. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1 is characterized in that described perfluoroalkyl iodides general formula is R
f(CF
2CF
2)
nI, wherein R
fBe C
1-4Perfluoroalkyl, n are 1～4 integer.
4. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1 is characterized in that, described short carbon chain full-fluorine alkyl iodide general formula is R
fI.R wherein
fBe C
1-4Perfluoroalkyl.
5. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1 is characterized in that, described catalyzer is one or more in copper, nickel, tin, zinc, magnesium, silver, iron, chromium, cobalt, tungsten and the alloy thereof.
6. a kind of method of preparing perfluoroalkyl group by telomerization according to claim 1 or 5 is characterized in that the particle diameter of described catalyzer is 2 orders～300 orders.
7. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1 is characterized in that, the height of described catalyst filling layer is 5: 1～800: 1 with the internal diameter ratio.
8. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1 is characterized in that, described short carbon chain full-fluorine alkyl iodide R
fI or tetrafluoroethylene are for mixing reinforced or separate charging.
9. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 1 is characterized in that, described short carbon chain full-fluorine alkyl iodide R
fI or tetrafluoroethylene are continuously feeding or intermittent feeding.
10. the method for a kind of preparing perfluoroalkyl group by telomerization according to claim 2 is characterized in that, described product collection still (1) temperature is lower than under the reaction pressure 0 ℃～15 ℃ of product boiling points.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100616732A CN101306977A (en) | 2008-05-23 | 2008-05-23 | Process for preparing perfluoroalkyl group by telomerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100616732A CN101306977A (en) | 2008-05-23 | 2008-05-23 | Process for preparing perfluoroalkyl group by telomerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101306977A true CN101306977A (en) | 2008-11-19 |
Family
ID=40123684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100616732A Pending CN101306977A (en) | 2008-05-23 | 2008-05-23 | Process for preparing perfluoroalkyl group by telomerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101306977A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774883B (en) * | 2010-02-08 | 2013-04-10 | 太仓中化环保化工有限公司 | Preparation method for perfluoroalkyl iodide |
| CN103524294A (en) * | 2013-09-18 | 2014-01-22 | 巨化集团技术中心 | Continuous synthesis method of low-carbon-chain perfluoroalkyl iodide |
| CN103880588A (en) * | 2014-02-26 | 2014-06-25 | 巨化集团技术中心 | Method for preparing perfluoroalkyl iodine through catalytic distillation telomerization |
| CN105924375A (en) * | 2016-04-19 | 2016-09-07 | 巨化集团技术中心 | Preparation method for fluorine-containing emulsifier |
| CN112898117A (en) * | 2021-01-27 | 2021-06-04 | 济南齐氟新材料技术有限公司 | Preparation method of perfluoroalkyl iodide |
-
2008
- 2008-05-23 CN CNA2008100616732A patent/CN101306977A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774883B (en) * | 2010-02-08 | 2013-04-10 | 太仓中化环保化工有限公司 | Preparation method for perfluoroalkyl iodide |
| CN103524294A (en) * | 2013-09-18 | 2014-01-22 | 巨化集团技术中心 | Continuous synthesis method of low-carbon-chain perfluoroalkyl iodide |
| CN103524294B (en) * | 2013-09-18 | 2015-02-25 | 巨化集团技术中心 | Continuous synthesis method of low-carbon-chain perfluoroalkyl iodide |
| CN103880588A (en) * | 2014-02-26 | 2014-06-25 | 巨化集团技术中心 | Method for preparing perfluoroalkyl iodine through catalytic distillation telomerization |
| CN105924375A (en) * | 2016-04-19 | 2016-09-07 | 巨化集团技术中心 | Preparation method for fluorine-containing emulsifier |
| CN105924375B (en) * | 2016-04-19 | 2018-04-20 | 巨化集团技术中心 | A kind of preparation method of fluorine-containing emulsifier |
| CN112898117A (en) * | 2021-01-27 | 2021-06-04 | 济南齐氟新材料技术有限公司 | Preparation method of perfluoroalkyl iodide |
| CN112898117B (en) * | 2021-01-27 | 2023-10-10 | 济南齐氟新材料技术有限公司 | Preparation method of perfluoroalkyl iodide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI770558B (en) | Process for preparing a highly pure 1,1,1,2,3-pentachloropropane product | |
| CN103415496B (en) | Low temperature production of 2-chloro-3,3,3-trifluoropropene | |
| CN101306977A (en) | Process for preparing perfluoroalkyl group by telomerization | |
| CN107011113A (en) | The integrated approach of Joint Production trifluoro propene, tetrafluoropropene and pentafluoropropane | |
| CN102164881A (en) | Process for producing 1,3,3,3-tetrafluoropropene | |
| KR20120023007A (en) | Process for preparing 2-chloro-3,3,3-trifluoropropene | |
| CN103209942A (en) | Process for producing trans-1,3,3,3-tetrafluoropropene | |
| CN104185616A (en) | Integrated process to coproduce trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane | |
| JP6183370B2 (en) | Process for producing 1,2-dichloro-3,3,3-trifluoropropene | |
| CN101497572B (en) | A method for producing tert-butylamine based on reaction-separation coupling | |
| CN112645793B (en) | Process system and method for producing trans-1-chloro-3, 3-trifluoropropene | |
| TWI421234B (en) | Method for producing 2-propanol | |
| CN1270575A (en) | Method for producing perhalogenated cyclopentene | |
| CN107614464A (en) | Method for producing conjugated diene | |
| CN107759440B (en) | Method for replacing fluorine on double bond of fluorine-containing olefin by hydrogen | |
| CN213222199U (en) | Reaction device of vinyl ether compound | |
| CN105272859A (en) | Production method for alkyl nitrite | |
| WO2008068927A1 (en) | Process and equipment for the production of mono(lower alkyl)monoalkanolamines | |
| CN104151268A (en) | Method for continuously synthesizing N-aminoethylmorpholine in fixed-bed reactor | |
| CN101628849A (en) | Preparation method of Z-1,2,3,3,3-pentafluoropropylene | |
| CN106565413B (en) | A kind of method of gas phase catalysis dehydrochlorination preparation chlorotrifluoroethylene | |
| KR102708180B1 (en) | Method for producing of the high purity hexafluoroisobutylene | |
| CN110227543B (en) | Ionic liquid loaded transition metal catalyst, preparation thereof and application thereof in olefin oligomerization reaction | |
| CN104703954A (en) | Method for producing difluoromethane | |
| CN209597140U (en) | Fluidized bed reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081119 |