CN102241561A - One-step preparation method of perfluoroalkyl iodide - Google Patents
One-step preparation method of perfluoroalkyl iodide Download PDFInfo
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- CN102241561A CN102241561A CN 201110122417 CN201110122417A CN102241561A CN 102241561 A CN102241561 A CN 102241561A CN 201110122417 CN201110122417 CN 201110122417 CN 201110122417 A CN201110122417 A CN 201110122417A CN 102241561 A CN102241561 A CN 102241561A
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Abstract
The invention relates to a one-step preparation method of perfluoroalkyl iodide, belonging to the field of fluoride product intermediates. The preparation method comprises the following steps: adding iodine, iodine pentafluoride and a composite catalyst into a reaction vessel, vacuumizing to -0.095 MPa, replacing air in the reaction vessel with high-purity nitrogen gas for times until the water content is not more than 100 ppm and the oxygen content is not more than 30 ppm, heating the reaction vessel until the internal temperature is 60-80 DEG C, adding tetrafluoroethylene, and maintaining the pressure at 0.5-0.7 MPa for reaction; and raising the reaction temperature to 130-150 DEG C when the pressure does not decrease after adding tetrafluoroethylene, continuing introducing tetrafluoroethylene, and controlling the pressure at 2.8 MPa for reaction to obtain the perfluoroalkyl iodide. In the preparation method, the perfluoroalkyl iodide is synthesized by one-step reaction from iodine pentafluoride, two-step reaction is continuously carried out in the reaction vessel, and the reaction effect is greatly enhanced by using the composite catalyst; and the original two-step reaction is changed into a one-step reaction, thus reducing the production steps, simplifying the production process and equipment and lowering the production investment.
Description
Technical field
The present invention relates to fluorine goods intermediate field, particularly a kind of single stage method prepares the method for perfluoroalkyl iodides.
Background technology
The method for preparing at present perfluoroalkyl iodides mainly is to be undertaken by two steps: at first with iodine pentafluoride, iodine and tetrafluoroethylene synthetic PFEI under the effect of catalyzer, obtain PFEI through separating to purify again; PFEI and tetrafluoroethylene synthesize the perfluoroalkyl iodides that contains many carbon numbers under the effect of another kind of catalyzer then.
This method is the present method that everybody generally adopts.The at first synthetic PFEI of this method, with PFEI and the synthetic perfluoroalkyl iodides that contains many carbon numbers of tetrafluoroethylene, synthesis technique need be finished by two steps again.Need to use two cover conversion units, two cover rectifying devices to synthesize like this, increased the production process step, strengthened facility investment, improved production cost.
Summary of the invention
In order to overcome the above problems, the invention provides a kind of with iodine pentafluoride, iodine and tetrafluoroethylene method at next step synthesizing perfluoroalkyl iodine of effect of composite catalyst.
With iodine pentafluoride, iodine and tetrafluoroethylene next step synthesizing perfluoroalkyl iodine of effect, compare the control that the problem that need overcome is a temperature, pressure in selection of catalysts, the reaction process with two-step approach at catalyzer.Owing to be reflected in the reactor and carry out continuously, the catalyzer of selecting for use needs to satisfy simultaneously the effect of catalyse two-step reaction.By experiment, we select the mixture of metal fluoride and transition metal as composite catalyst.
The present invention is achieved by the following measures:
A kind of single stage method prepares the method for perfluoroalkyl iodides, may further comprise the steps:
(1) in reaction vessel, adds iodine, iodine pentafluoride and composite catalyst, vacuumize and with nitrogen replacement repeatedly, the water content≤100ppm to the reaction vessel is behind oxygen level≤30ppm, making the interior temperature of container is 60 ~ 80 ℃, and it is 0.5 ~ 0.7Mpa reaction that the adding tetrafluoroethylene keep-ups pressure;
When (2) pressure does not have decline after adding tetrafluoroethylene, temperature of reaction is risen to 130-150 ℃, continue to feed tetrafluoroethylene, control pressure is that 2.8MPa reacts, and obtains perfluoroalkyl iodides.
Reaction formula is as follows:
1/5?IF
5 + 2/5?I
2 + n?CF
2=CF
2 →F(CF
2CF
2)nI
N=1 wherein, 2,3,4,5
Described composite catalyst is the composite catalyst that transition metal alloy and metal fluoride are formed, described transition metal alloy is the alloy of the two or more compositions in manganese, chromium, copper, nickel, zinc and the cobalt, and described metal fluoride is aluminum fluoride, magnesium fluoride, chromium fluoride or antimonic fluoride.
Transition metal is Ti-Ni alloy or titanium nichrome, and titanium nickel weight ratio is 30:70 in the Ti-Ni alloy, and titanium nickel chromium triangle weight ratio is 30:60:10 in the titanium nichrome, and the preferable alloy fluorochemical is an antimonic fluoride.
The amount of described composite catalyst accounts for 6.6 ~ 11% of iodine pentafluoride weight,
The mol ratio of iodine and iodine pentafluoride is 2:1.
The mol ratio of tetrafluoroethylene and iodine pentafluoride is 6.5-10:1.
The weight ratio of transition metal alloy and metal fluoride is 1-1.5:1.
Total reaction time is 12～16 hours, is influenced by the add-on of reaction efficiency and tetrafluoroethylene, and the time is shorter, and synthetic target product is few and uneconomical, and overlong time then can produce a large amount of high carbon number wastes.
The adding of tetrafluoroethylene is adopted and is added continuously or the gradation adding, and gradation adds the fashionable 15 ~ 40g that at every turn adds.
Reactor is acid-alkali-corrosive-resisting, powerful oxidation corrosion resistance, can select stainless steel 304,316L material, and perhaps Hastelloy material etc. can be born certain high pressure simultaneously.
The molar ratio of iodine pentafluoride and iodine is undertaken by 1:2.For improving speed of response, iodine should be selected pulverulence, but not the macrobead crystal.
Composite catalyst select metal fluoride and transition metal alloy composite, be the raising reaction efficiency, the selection fine-powder in the best state of catalyzer.
Reaction is carried out under air-tight state, and moisture content, oxygen content are had strict demand, generally controls moisture content≤100ppm, oxygen level≤30ppm.
Reaction finishes, and through alkali cleaning, washing, removes the acidic substance in the reactant.Remove by filter catalyzer, remove light constituent C2, C4 or C6 through rectifying again, obtain the product that main component is C6～C12, can obtain the single component product through purifying once more.
The invention has the beneficial effects as follows:
(1) catalyzer is selected composite catalyst for use, and by iodine pentafluoride one-step synthesis perfluoroalkyl iodides, two-step reaction carries out in a reactor continuously, and the use of this composite catalyst improves reaction effect greatly;
(2) make original two-step reaction become single step reaction and carry out, reduced production stage, simplified production technique and equipment, reduced and produced investment.
Embodiment
Embodiment 1
In the 2L material is in the withstand voltage reactor of stainless steel 316L, adds iodine 762g(3mol), iodine pentafluoride 333g(1.5mol), antimony pentafluoride 11g, Ti-Ni alloy powder 11g(titanium/nickel=30/70).To-0.095MPa, high pure nitrogen replace repeatedly with reaction kettle for vacuumizing, makes the interior moisture content≤100ppm of still, oxygen level≤30ppm.Open to stir, heat temperature raising to 60 ℃, gradation adds tetrafluoroethylene, makes the still internal pressure remain on 0.5 ~ 0.7MPa, adds 15 ~ 40g at every turn.When pressure no longer descends after feeding tetrafluoroethylene, temperature of reaction is risen to 130 ℃, tetrafluoroethylene pressure rises to 2.8MPa.After entire reaction continues 12 hours, add tetrafluoroethylene 1050g(10.5mol altogether), stopped reaction is cooled to-5 ℃, emits reaction mass, after KOH solution and pure water washing, filters out catalyzer, obtains the perfluoroalkyl iodides crude product.With crude product diameter 3cm, C2, C4 are removed in the rectifying column rectifying of high 160cm, and rectification under vacuum obtains long-chain perfluoroalkyl iodides mixture 253g again, and detected result sees Table 1:
Each component content table of table 1 perfluoroalkyl iodides
| Carbon atom quantity | ≤C4 | C6 | C8 | C10 | C12 | ≥C14 |
| Content (%) | 1.5 | 42.5 | 24.2 | 13.4 | 8.9 | 6 |
With the rectification under vacuum of long-chain perfluoroalkyl iodides mixture, tell that to contain carbon number be 6 perfluoroalkyl iodides.Residue perfluoroalkyl iodides 131.7g, detected result sees Table 2:
Each component content table of perfluoroalkyl iodides after table 2 rectifying
Embodiment 2
Identical with embodiment 1 each raw material consumption and parameter, just total reaction times is extended to 16 hours, add tetrafluoroethylene 1360g(13.6mol altogether), after C2, C4 were fallen in rectifying, rectification under vacuum obtained long-chain perfluoroalkyl iodides mixture 425g.Each component content detected result sees Table 3.
Each component content table of table 3 perfluoroalkyl iodides
| Carbon atom quantity | ≤C4 | C6 | C8 | C10 | C12 | ≥C14 |
| Content (%) | 1.1 | 38.2 | 27.7 | 16.9 | 8.5 | 6.6 |
Embodiment 3
In the 10L material is in the withstand voltage reactor of stainless steel 316L, adds iodine 3810g(15mol), iodine pentafluoride 1665g(7.5mol), antimony pentafluoride 73g, Ti-Ni alloy 110g(titanium/nickel=30/70).Be evacuated to-0.095MPa, high pure nitrogen is replaced repeatedly, makes moisture content≤100ppm in the still, oxygen level≤30ppm.Open to stir, heat temperature raising to 80 ℃, gradation adds tetrafluoroethylene, makes the still internal pressure remain on 0.5 ~ 0.7Mpa, adds 15 ~ 40g at every turn.When pressure no longer descends after feeding tetrafluoroethylene, temperature of reaction is risen to 150 ℃, tetrafluoroethylene pressure rises to the 2.8MPa sustained reaction.After 12 hours, add tetrafluoroethylene 5088g(50.88mol altogether), stopped reaction is cooled to-5 ℃, emits reaction mass, after KOH solution and pure water washing, filters out catalyzer.With material diameter 3cm, C2, C4 are removed in the rectifying column rectifying of high 160cm, and rectification under vacuum obtains long-chain perfluoroalkyl iodides mixture 1338g again, and each component content detected result sees Table 4.
Each component content table of table 4 perfluoroalkyl iodides
| Carbon atom quantity | ≤C4 | C6 | C8 | C10 | C12 | ≥C14 |
| Content (%) | 1.8 | 54.3 | 21.5 | 11.4 | 4.1 | 3.2 |
Embodiment 5
In the 2L material is in the withstand voltage reactor of stainless steel 316L, adds iodine 762g(3mol), iodine pentafluoride 333g(1.5mol), antimony pentafluoride 11g, titanium nichrome 11g(titanium/nickel/chromium=30/60/10).Be evacuated to-0.095MPa, high pure nitrogen is replaced repeatedly, makes moisture content≤100ppm in the still, oxygen level≤30ppm.Open to stir, heat temperature raising to 70 ℃, gradation adds tetrafluoroethylene, makes the still internal pressure remain on 0.5 ~ 0.7Mpa, adds 15 ~ 40g at every turn.When pressure no longer descends after feeding tetrafluoroethylene, temperature of reaction is risen to 140 ℃, tetrafluoroethylene pressure rises to the 2.8MPa sustained reaction.After 18 hours, add tetrafluoroethylene 1460g(14.6mol altogether), stopped reaction is cooled to-5 ℃, emits reaction mass, after KOH solution and pure water washing, filters out catalyzer.With material diameter 3cm, C2, C4 are removed in the rectifying column rectifying of high 160cm, and rectification under vacuum obtains long-chain perfluoroalkyl iodides mixture 544g again, and each component content detected result sees Table 5.
Each component content table of table 5 perfluoroalkyl iodides
| Carbon atom quantity | ≤C4 | C6 | C8 | C10 | C12 | ≥C14 |
| Content (%) | 1.25 | 32.4 | 25.3 | 17.1 | 12.5 | 8.2 |
Because transition metal similar performance, Catalysis Principles is basic identical, so transition metal fluorides and transition metal alloy only experimentize as catalyzer with antimony pentafluoride and nickel, titanium, Chrome metal powder in this patent, and other composite catalyzer are given an example no longer one by one.
Claims (10)
1. a single stage method prepares the method for perfluoroalkyl iodides, it is characterized in that may further comprise the steps:
(1) add iodine, iodine pentafluoride and composite catalyst in reaction vessel, be evacuated to-0.095MPa, making the interior temperature of container is 60 ~ 80 ℃, and it is 0.5 ~ 0.7Mpa reaction that water content≤100ppm, oxygen level≤30ppm, adding tetrafluoroethylene keep-up pressure;
When (2) pressure does not have decline after adding tetrafluoroethylene, temperature of reaction is risen to 130-150 ℃, continue to feed tetrafluoroethylene, control pressure is that 2.8MPa reacts, and obtains perfluoroalkyl iodides.
2. method according to claim 1, it is characterized in that described composite catalyst is the composite catalyst that transition metal alloy and metal fluoride are formed, described transition metal alloy is the alloy of the two or more compositions in manganese, chromium, copper, nickel, zinc and the cobalt, and described metal fluoride is aluminum fluoride, magnesium fluoride, chromium fluoride or antimonic fluoride.
3. method according to claim 2 is characterized in that transition metal is Ti-Ni alloy or titanium nichrome, and titanium nickel weight ratio is 30:70 in the Ti-Ni alloy, and titanium nickel chromium triangle weight ratio is 30:60:10 in the titanium nichrome, and the preferable alloy fluorochemical is an antimonic fluoride.
4. according to each described method among the claim 1-3, it is characterized in that the amount of described composite catalyst accounts for 6.6 ~ 11% of iodine pentafluoride weight.
5. according to each described method among the claim 1-3, the mol ratio that it is characterized in that iodine and iodine pentafluoride is 2:1.
6. according to each described method among the claim 1-3, the mol ratio that it is characterized in that tetrafluoroethylene and iodine pentafluoride is 6.5-10:1.
7. method according to claim 4, the weight ratio that it is characterized in that transition metal alloy and metal fluoride is 1-1.5:1.
8. according to claim 2 or 3 described methods, it is characterized in that total reaction time is 12～16 hours.
9. according to each described method among the claim 1-3, it is characterized in that the adding of tetrafluoroethylene adopts adding continuously or gradation to add, gradation adds the fashionable 15 ~ 40g that at every turn adds.
10. according to each described method among the claim 1-3, it is Powdered to it is characterized in that employed iodine is preferably; Reaction vessel is the withstand voltage reactor of corrosion resistant stainless steel; The perfluoroalkyl iodides that obtains is through rectification process.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643159A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Method for preparing perfluoroalkyl iodide by composite catalyst |
| CN105481638A (en) * | 2015-11-19 | 2016-04-13 | 巨化集团技术中心 | Synthetic method for 1,3,3,3-tetrafluoropropene |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3132185A (en) * | 1962-05-02 | 1964-05-05 | Du Pont | Improvement in the preparation of perfluoroalkyl iodides from tetrafluoroethylene |
| CN101805240A (en) * | 2010-03-29 | 2010-08-18 | 中化国际（苏州）新材料研发有限公司 | Telomerization method of perfluoroalkyl iodide |
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2011
- 2011-05-12 CN CN2011101224171A patent/CN102241561B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3132185A (en) * | 1962-05-02 | 1964-05-05 | Du Pont | Improvement in the preparation of perfluoroalkyl iodides from tetrafluoroethylene |
| CN101805240A (en) * | 2010-03-29 | 2010-08-18 | 中化国际（苏州）新材料研发有限公司 | Telomerization method of perfluoroalkyl iodide |
Non-Patent Citations (1)
| Title |
|---|
| 《浙江化工》 20070615 耿为利 "五氟碘乙烷的合成方法" 第16-17、24页 1-10 第38卷, 第6期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643159A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Method for preparing perfluoroalkyl iodide by composite catalyst |
| CN102643159B (en) * | 2012-04-13 | 2014-06-18 | 阜新恒通氟化学有限公司 | Method for preparing perfluoroalkyl iodide by composite catalyst |
| CN105481638A (en) * | 2015-11-19 | 2016-04-13 | 巨化集团技术中心 | Synthetic method for 1,3,3,3-tetrafluoropropene |
| CN105481638B (en) * | 2015-11-19 | 2019-05-14 | 巨化集团技术中心 | A kind of synthetic method of 1,3,3,3- tetrafluoropropene |
| 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 |
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