CN100420660C - Telomerisation method of preparing full-fluorine alkyl iodide by redox initiation - Google Patents
Telomerisation method of preparing full-fluorine alkyl iodide by redox initiation Download PDFInfo
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- CN100420660C CN100420660C CNB2006100689518A CN200610068951A CN100420660C CN 100420660 C CN100420660 C CN 100420660C CN B2006100689518 A CNB2006100689518 A CN B2006100689518A CN 200610068951 A CN200610068951 A CN 200610068951A CN 100420660 C CN100420660 C CN 100420660C
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- perfluoroalkyl
- telomerization
- telogen
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Abstract
The present invention relates to the telomerization process of perfluoro alkyl iodide in the general expression of Rf(CF2CF2)nI. By using fluoric olefin as the taxogen and RfI as the telogen, the present invention completes telomerization at the pressure of 0.1-2 MPa. The present invention features the initiation of the telomerization through the redox reaction between perfluoro hydrogen peroxide and Fe(II) and Cu(I) ions at 20-60 deg.c. The present invention produces perfluoro alkyl iodide through telomerization at relatively low temperature and has high safety. The telomerization is completed in a kettle type or tubular reactor intermittently or continuously. The present invention has high selectivity of producing perfluoro alkyl iodide in the medium chain length.
Description
Technical field
The invention belongs to perfluor fine chemicals intermediate field, relate to a kind of preparation method of perfluoroalkyl iodine compound, relate in particular to the telomerization method that a kind of redox initiation prepares perfluoroalkyl iodides.
Background technology
As everyone knows, full-fluorine alkyl iodide is the single iodo perfluoro alkane compound that hydrogen atom is replaced fully by fluorine atom, general perfluoroalkyl by a series of different chain length constitutes, what have using value mainly is that carbonatoms is 6～12 perfluoroalkyl iodides, and wherein carbonatoms is perfluor iodo-octane performance the best of 8.Perfluoroalkyl iodides is a key intermediate of producing fluorine-contained finishing agent, fluorochemical surfactant and other fluorine-containing fine chemicals, its derived product all has important purposes at aspects such as light-water fire-fighting medium, magnetic pipe recording material, water and oil repellant fabric finishing agent, paper finishing composition, oilfield chemistry, sensitive materials, high-grade releasing agent, metal antirusting agent, plastic, rubber auxiliary agent and medical materials.With PFEI, seven fluorine isopropyl iodides is telogen, and to carry out telomerization under light, heat, free radical or catalysis are drawn be known in order to telomerize monomer for tetrafluoroethylene or R 1216.U.S. Pat 5650545 has been introduced and has a kind ofly been carried out the method that thermal initiation prepares perfluoroalkyl iodides in 344 ℃ formula reactor, this method will be mouthful feeding that induces one of 2/3 pipe range at the port of reactor with from reactor head from tetrafluoroethylene, can reduce high carbon number product, but the shortcoming of thermal initiation is that at high temperature the easy initial ring consor of tetrafluoroethylene becomes Perfluorocyclobutane, accumulation causes the tetrafluoroethylene transformation efficiency low in reactor, and by product is many under the high temperature, the selectivity of target product descends, and molecular weight distribution is wide.European patent EP 1380557 has been introduced a kind of mixed catalyst catalysis with copper powder, gunmetal powder, sintered copper powder and copper powder and glass putty and has been caused the technology that perfluoroalkyl iodide telomerizes.At internal diameter is 9.5mm, and length-to-diameter ratio is in 10～200 tubular reactors, at 120 ℃, 1.9 carry out telomerization under the～3.0MPa, though the relative molecular mass narrowly distributing of the telomer that this method obtains, foreign matter content is low, but this method is reacted with tubule, is unfavorable for realizing suitability for industrialized production.U.S. Pat 3226449 has been introduced a kind of telomerization method that causes the preparation perfluoroalkyl iodides with tertiary alkyl superoxide, propylene superoxide, acetone superoxide etc., this method need be reacted under High Temperature High Pressure, system is explosive, has introduced hydrocarbon group, and by product is many and molecular weight distribution is wide.Chinese patent CN1379008A has introduced the method that a kind of light-initiated telomerizing prepares alkyl iodide, and this method is with C
2F
5I and C
2F
4Mixture, add with low-voltage light source and carry out telomerization as the reactor that causes light source.Though this method has lower reaction pressure and higher speed of reaction, light source is aggregated thing easily and covers, and can't proceed initiation reaction again and causes throughput little, can't realize large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide the telomerization method that a kind of redox initiation prepares perfluoroalkyl iodides.
A kind of redox initiation prepares the telomerization method of perfluoroalkyl iodides, is taxogen with the Fluorine containing olefine, R
fI is a telogen, regulates polymerization under the 0.1-3MP pressure condition; It is characterized in that, under the redox reaction of perfluor initiator and reductive agent, cause that temperature of reaction is 20-60 ℃; The general structure of described perfluoroalkyl iodides is R
f(CF
2CF
2)
nI; R
fFor containing 1-4 carbon, structure is the perfluoroalkyl of straight or branched, and n is the integer of 2-4.
Telogen R in this method
fI is for containing 1-4 carbon, and structure is the perfluoroalkyl of straight or branched, is preferably as follows structure C F
3-, CF
3CF
2-, (CF
3)
2CF-, CF
3(CF
2)
2CF
2-, more preferably CF
3CF
2-, (CF
3)
2CF-.
The taxogen Fluorine containing olefine is mainly perfluor or chloride perfluoroolefine in this method, preferred tetrafluoroethylene, vinylidene, trifluorochloroethylene, R 1216, more preferably tetrafluoroethylene, R 1216.
Preferably, the mass ratio of taxogen and telogen is 1: 1-4, more preferably 1: 2.
The perfluor initiator is perfluoroalkyl or assorted oxygen perfluoroalkyl superoxide in this method, and its structural formula is R '
fC-OO-CR '
fR '
fBe perfluoroalkyl or assorted oxygen perfluoroalkyl, preferred C
8F
16C-OO-CC
8F
16, C
6F
5C-OO-CC
6F
5, CF
3CF
2CF
2OCF (CF
3) CF
2COOCCF
2(CF
3) CFOCF
2CF
2CF
3
Reductive agent is Fe (II) in this method, Cu (I) ion, preferred FeCl
2, CuCl.Reductive agent with the amount of substance ratio of perfluor superoxide is: 0.6-0.9: 1, be preferably 0.8: 1.
Preferably, total consumption of perfluor superoxide and reduction initiator accounts for the 0.1-5.0% of telogen quality.
The telomerization temperature is 20-60 ℃ in this method, preferred 30-40 ℃.
Adopt tank reactor in this method, material is a stainless steel, preferred Hastelloy stainless steel.
Of the present inventionly under low temperature, carry out, avoid high temperature to cause that the ring of tetrafluoroethylene is poly-, adopt the perfluor initiator can avoid bringing into hydrocarbon group, reduce difficult isolating hydrogeneous perfluoroalkyl impurity.
Embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
Embodiment 1
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds CuCl 1.2g with still process high temperature drying.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen C in still
2F
5I 500g, the perfluor peroxide C
8F
16C-OO-CC
8F
16Be dissolved in the telogen, concentration is 0.3%, opens stirring, feed TFE5g, react under 30 degree, pressure is about 1.0MP, when treating that pressure drops to a certain degree in the still, feed TFE5g once more, repeatedly several times, be 200 grams up to the TFE total mass that feeds, react to pressure and no longer change, unreacted C is reclaimed in cooling
2F
5I obtains product C
2F
5(CF
2CF
2)
nI is totally 412.5 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 1:
Table 1 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 12.5 |
| 2 | 17.9 |
| 3 | 25.6 |
| 4 | 23.4 |
| n≥5 | 20.6 |
| Add up to | 100 |
Embodiment 2
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds FeCl with still process high temperature drying
28.8g.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen (CF in still
3)
2CFI 550g, the perfluor peroxide C
6F
5C-OO-CC
6F
5Be dissolved in the telogen, concentration is 2%, opens stirring, feed TFE5g, react under 30 ℃, pressure is about 1.2MP, when treating that pressure drops to a certain degree in the still, feed TFE5g once more, repeatedly several times, be 200 grams up to the TFE total mass that feeds, react to pressure and no longer change, unreacted C is reclaimed in cooling
2F
5I obtains product R
f(CF
2CF
2)
nI is totally 472.5 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 2:
Table 2 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 10.3 |
| 2 | 15.7 |
| 3 | 28.2 |
| 4 | 23.4 |
| n≥5 | 22.4 |
| Add up to | 100 |
Embodiment 3
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds FeCl with still process high temperature drying
24.4g.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen (CF in still
3)
2CFI 550g, perfluor peroxide C F
3CF
2CF
2OCF (CF
3) CF
2COOCCF
2(CF
3) CFOCF
2CF
2CF
3Be dissolved in the telogen, concentration is 1%, opens stirring, feed TFE5g, react under 30 ℃, pressure is about 1.2MP, when treating that pressure drops to a certain degree in the still, feed TFE5g once more, repeatedly several times, be 200 grams up to the TFE total mass that feeds, react to pressure and no longer change, unreacted C is reclaimed in cooling
2F
5I obtains product (CF
3)
2CF (CF
2CF
2)
nI is totally 502.6 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 3:
Table 3 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 15.1 |
| 2 | 18.8 |
| 3 | 24.3 |
| 4 | 21.5 |
| n≥5 | 20.3 |
| Add up to | 100 |
Embodiment 4
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds CuCl 10g with still process high temperature drying.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen CF in still
3I 500g, the perfluor peroxide C
8F
16C-OO-CC
8F
16Be dissolved in the telogen, concentration is 2%, opens stirring, feed R 1216 5g, 20 ℃ are reacted, and pressure is about 1.0MP, when treating that pressure drops to a certain degree in the still, feed R 1216 5g once more, repeatedly several times, be 500 grams up to the R 1216 total mass that feeds, react to pressure and no longer change, unreacted CF is reclaimed in cooling
3I obtains product C F
3(CFCF
3CF
2)
nI is totally 486.5 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 4:
Table 4 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 13.4 |
| 2 | 16.7 |
| 3 | 25.2 |
| 4 | 24.0 |
| n≥5 | 20.7 |
| Add up to | 100 |
Embodiment 5
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds FeCl with still process high temperature drying
215g.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen C in still
4F
9I 500g, the perfluor peroxide C
6F
5C-OO-CC
6F
5Be dissolved in the telogen, concentration is 5%, opens stirring, feed vinylidene 5g, 40 ℃ are reacted, and pressure is about 1.2MP, when treating that pressure drops to a certain degree in the still, feed vinylidene 5g once more, repeatedly several times, be 200 grams up to the vinylidene total mass that feeds, react to pressure and no longer change, unreacted C is reclaimed in cooling
4F
9I obtains product C
4F
9(CH
2CF
2)
nI is totally 437.0 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 5:
Table 5 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 8.9 |
| 2 | 12.4 |
| 3 | 27.6 |
| 4 | 30.0 |
| n≥5 | 21.1 |
| Add up to | 100 |
Embodiment 6
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds CuCl6.8g with still process high temperature drying.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen C in still
2F
5I 500g, the perfluor peroxide C
8F
16C-OO-CC
8F
16Be dissolved in the telogen, concentration is 1.5%, opens stirring, feed trichlorine vinyl fluoride 5g, 30 ℃ are reacted, and pressure is about 1.0MP, when treating that pressure drops to a certain degree in the still, feed trichlorine vinyl fluoride 5g once more, repeatedly several times, be 250 grams up to the trichlorine vinyl fluoride total mass that feeds, react to pressure and no longer change, unreacted C is reclaimed in cooling
2F
5I obtains product C
2F
5(CFClCF
2)
nI is totally 526.7 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 6:
Table 6 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 9.5 |
| 2 | 13.6 |
| 3 | 21.8 |
| 4 | 28.4 |
| n≥5 | 26.7 |
| Add up to | 100 |
Embodiment 7
The Hastelloy stainless steel cauldron of 500mL except that anhydrating, adds CuCl 4.0g with still process high temperature drying.Find time to use N with nitrogen replacement again after then still being found time
2The displacement deoxygenation, oxygen level reaches below the 10ppm.At room temperature the used additives pump adds telogen C in still
2F
5I 500g, perfluor peroxide C F
3CF
2CF
2OCF (CF
3) CF
2COOCCF
2(CF
3) CFOCF
2CF
2CF
3Be dissolved in the telogen, concentration is 1.0%, opens stirring, feed TFE5g, 40 ℃ are reacted, and pressure is about 1.0MP, when treating that pressure drops to a certain degree in the still, feed TFE5g once more, repeatedly several times, be 125 grams up to the TFE total mass that feeds, react to pressure and no longer change, unreacted C is reclaimed in cooling
2F
5I obtains product C
2F
5(CF
2CF
2)
nI is totally 438.0 grams, n 〉=1.Product after filtration, alkali cleaning, each component ratio after the processed in the chromatographically product sees Table 7:
Table 7 products distribution table
| Chain length (n) | Ratio (%) |
| 1 | 3.4 |
| 2 | 15.7 |
| 3 | 24.9 |
| 4 | 26.0 |
| n≥5 | 29.7 |
| Add up to | 100 |
Claims (5)
1. a redox initiation prepares the telomerization method of perfluoroalkyl iodides, is taxogen with the Fluorine containing olefine, R
fI is a telogen, regulates polymerization under the 0.1-3MP pressure condition; It is characterized in that, under the redox reaction of perfluor initiator and reductive agent, cause that temperature of reaction is 20-60 ℃;
The general structure of described perfluoroalkyl iodides is R
f(CF
2CF
2)
nI; R
fFor containing 1-4 carbon, structure is the perfluoroalkyl of straight or branched, and n is the integer of 2-4; Fluorine containing olefine is a taxogen, and the mass ratio of taxogen and telogen is 1: 1-4; The perfluor initiator is perfluoroalkyl or assorted oxygen perfluoroalkyl superoxide, its structural formula such as R '
fC-OO-CR '
fR '
fBe perfluoroalkyl or assorted oxygen perfluoroalkyl.
2. redox initiation as claimed in claim 1 prepares the telomerization method of perfluoroalkyl iodides, it is characterized in that reductive agent is Fe (II), Cu (I) ion.
3. redox initiation as claimed in claim 1 prepares the telomerization method of perfluoroalkyl iodides, it is characterized in that the reductive agent and the amount of substance ratio of perfluor superoxide are 0.6-0.9: 1.
4. redox initiation as claimed in claim 1 prepares the telomerization method of perfluoroalkyl iodides, it is characterized in that total consumption of perfluor superoxide and reduction initiator accounts for the 0.1-5.0% of telogen quality.
5. redox initiation as claimed in claim 1 prepares the telomerization method of perfluoroalkyl iodides, it is characterized in that adopting tank reactor.
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|---|---|---|---|
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| US7951983B2 (en) | 2009-11-04 | 2011-05-31 | E.I. Du Pont De Nemours And Company | Catalyzed olefin insertion |
| US7888538B1 (en) | 2009-11-04 | 2011-02-15 | E.I. Du Pont De Nemours And Company | Catalyzed olefin insertion |
| CN109988058B (en) * | 2017-12-29 | 2021-07-20 | 山东东岳高分子材料有限公司 | Synthesis method of perfluoroalkyl iodide telomer with shorter chain length |
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Non-Patent Citations (2)
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|---|
| 全氟碘代烷调聚反应的机理与工艺研究进展. 席先锋等人.现代化工，第25卷第6期. 2005 |
| 全氟碘代烷调聚反应的机理与工艺研究进展. 席先锋等人.现代化工，第25卷第6期. 2005 * |
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