CN1944360A - Process for preparing perfluoro nonene - Google Patents
Process for preparing perfluoro nonene Download PDFInfo
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- CN1944360A CN1944360A CN 200610069166 CN200610069166A CN1944360A CN 1944360 A CN1944360 A CN 1944360A CN 200610069166 CN200610069166 CN 200610069166 CN 200610069166 A CN200610069166 A CN 200610069166A CN 1944360 A CN1944360 A CN 1944360A
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Abstract
The process of preparing perfluoro nonene includes the solvent oligomerization of hexafluoro propylene in polar aprotic solvent at 80-120 deg.c and 0.1-1 MPa and in the presence of alkali metal cyanate or thiocyanate catalyst. The process has high yield of perfluoro nonene and nonene selectivity as high as 95 %.
Description
Technical field
The invention belongs to perfluor fine chemicals intermediate field, relate to a kind of method for preparing perfluorinated nonene, relate in particular to a kind of method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene.
Background technology
Perfluorinated nonene is a kind of important fluorine-containing fine chemicals, and it can be used as the raw material of perfluoro solvent, preparation fluorochemical monomer, fluorochemical surfactant, water-refusing oil-refusing finishing agent, remover and potting material.Perfluorinated nonene can prepare by gas phase and the liquid phase oligomerisation that contains multiple catalyzer.
The gas phase oligomerization of hexafluoropropylene prepares the process of perfluorinated nonene and does not use solvent, catalyst system therefor is that alkali-metal fluorochemical is (referring to Dresdner et al., J.Org.Chem.30,3524 (1965)) and be carried on alkali-metal fluorochemical on activated carbon or the nickel oxide (referring to U.S.Pat.NO.4,296,265), these processes are at high temperature direct the contact with catalyzer of gaseous state R 1216 to be carried out oligomerisation.
Liquid phase oligomerization of hexafluoropropylene process refers in polar aprotic solvent and alkali-metal fluorochemical and oxyhydroxide (U.S.PatNo.2,919,501 (Brehm et al)), fluorine-containing ammonium, quaternary ammonium salt (U.S.Pat No.3,917,724) etc. catalyzer exists down, and R 1216 gas carries out oligomerisation reaction in solvent.
U.S.Pat.No.4,042,638 (Ozawa et al) have pointed out that the ratio of perfluor hexene and perfluorinated nonene is determined by solvent and catalyzer in the reaction system in the oligomerization of hexafluoropropene, point out in solvent, to add crown ether simultaneously and more helped the solubleness of catalyzer in solvent, improved speed of response.U.S.Pat.No.4,780,559 have introduced other catalyzer provides fluorion, can be used as the catalyzer of oligomerization of hexafluoropropylene as hydrogen difluoro tetraphenyl phosphoric acid, has also pointed out in this reaction system it must is that the content of water reaches minimum simultaneously.The immediate oligomerisation that is Chinese patent application CN1095367 has introduced a kind of R 1216 prepares the preparation method of perfluor hexene with the present invention, being included in polar aprotic solvent such as acetonitrile exists down, with R 1216 be selected from alkali-metal prussiate, a kind of catalyzer or catalyst mixture in cyanate and the thiocyanogen hydrochlorate contact, and optionally obtain the perfluor hexene of high yield.
Summary of the invention
The purpose of this invention is to provide the method that a kind of simple liquid phase oligomerization of hexafluoropropylene prepares perfluorinated nonene.
A kind of preparation method of perfluorinated nonene is characterized in that, in polar aprotic solvent, under temperature of reaction 50-120 ℃ and the 0.1-1MP pressure, is that catalyzer carries out oligomerization of hexafluoropropylene with alkali metal cyanate or thiocyanate-.
Polar aprotic solvent of the present invention is selected from ethers, carboxylic acid esters, alkyl nitrile, alkylamide, alkyl sulfoxide class, reaches their mixture.Such as but not limited to N, N dimethyl formamide, N, N N,N-DIMETHYLACETAMIDE, acetonitrile, tetramethylene sulfone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether and their mixture.R 1216 carries out oligomerisation in these solvents mainly be the mixture that obtains perfluor hexene and perfluorinated nonene, main highly selective obtains the perfluor hexene in lower temperature of reaction and acetonitrile solvent, and at higher temperature of reaction and N, the N dimethyl formamide, N, but highly selective obtains perfluorinated nonene in the N N,N-DIMETHYLACETAMIDE, tetramethylene sulfone.The preferred N of the present invention, the N dimethyl formamide.
Of the present invention being reflected in the closed reaction kettle carried out, and reactor can bear higher pressure.In advance catalyzer is dissolved in the polar aprotic solvent, fully stirs and carry out activation treatment to improve speed of response, activation temperature is 100 ℃, and soak time is 1～2 hour.
The temperature of answering of the present invention is 50-150 ℃, preferred 50-120 ℃, and more preferably 80-120 ℃, more preferably 100-120 ℃, cross low temperature the ratio of perfluor hexene in the reaction is increased to some extent, reduced the ratio of perfluorinated nonene, too high temperature then can cause other by product.
Counterpressure of the present invention is 0.1-1.0MP, is preferably 0.3-0.5MP, and low excessively pressure can make the ratio of perfluor hexene in the reaction increase to some extent, and too high stress reaction speed causes unsafe factor too soon and easily.Another advantage of this reaction is semi-continuously to carry out, when not allowing to react again, the reactor internal volume can not reduce to room temperature, stop to feed R 1216, standing demix, perfluorinated nonene feeds the product extrusion reactor of high pressure nitrogen with lower floor then in not dissolved each other much larger than solvent and with solvent by density.Reaction next time need not further to handle, and only needs to heat up, and feeds the speed responsing that R 1216 promptly can be same once more, and is inferior surplus reaction system can use ten repeatedly.
The selected catalyzer of the present invention is the cyanate or the thiocyanate-of alkali metal lithium, sodium, potassium, rubidium, caesium.Catalyzer of the present invention has higher solubleness in solvent, particularly under temperature of reaction of the present invention, and conventional catalyzer such as Potassium monofluoride have minimum solubleness in same solvent.Preferred potassium cyanate.The preferred potassium cyanate of catalyzer of the present invention, make catalyzer with it and can obtain colourless perfluorinated nonene, product need not further rectifying can reach higher purity, is that the perfluorinated nonene of Preparation of Catalyst often contains certain impurity and shows red and urge potassium with thiocyanic acid.Catalyst levels of the present invention is a 0.1-300 grams per liter solvent, is preferably 30-50 gram/solvent.
The invention provides the method that a kind of simple liquid phase oligomerization of hexafluoropropylene prepares perfluorinated nonene, in described polar aprotic solvent, reaching under 50-120 ℃ of temperature of reaction and the 0.1-1Mp pressure, is catalyzer with selected alkali metal cyanate or thiocyanate-, and R 1216 is carried out oligomerisation.The present invention is particularly suitable for optionally obtaining the perfluorinated nonene of high yield, and its selection rate is up to more than 95%.Advantage of the present invention is that selected catalyzer is bigger than solubleness in solvent such as conventional Potassium monofluoride, Sodium Fluoride, Fuization Cesium, can reach katalysis with less amount, and need not to add expensive crown ether-like increases solvability.Conventional catalyzer such as Potassium monofluoride, Sodium Fluoride, Fuization Cesium etc. have extremely strong toxicity, and the reaction residue of generation and residue cause serious pollution to environment, and the selected catalyzer of the present invention has very low toxicity.
Embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
Embodiment 1
Present embodiment has been described and has been used potassium sulfocyanate to be catalyzer, and N, dinethylformamide are that solvent carries out the oligomerisation of R 1216 liquid phase and prepares perfluorinated nonene.
With the N of 1L, dinethylformamide is poured in the autoclave that the band of 5L stirs, and adds 30 gram potassium cyanates, and closed reactor vacuumizes repeatedly then, carries out nitrogen and replaces, and makes the interior oxygen level of still less than 20ppm.Open stirring then, be warmed up to 100 ℃ and carry out catalyst activation, after 1 hour, continue to feed lentamente R 1216 gas, the control reaction pressure is about 0.3MP.Speed of response depends on the speed that feeds R 1216 gas, and the speed that feeds R 1216 is too fast to be difficult for, otherwise thermal discharge is wayward.React after 2 hours and finish, cooling was left standstill 24 hours then, with lower floor's product extrusion, kept the solvent in the still with elevated pressure nitrogen institute, in order to secondary response use down.Through gas chromatographic analysis, perfluorinated nonene content accounts for 95% in the product, and perfluor hexene content accounts for 3%, and other impurity accounts for 2%.The productive rate of perfluorinated nonene is about 91% (based on the R 1216 gas volume that adds).
Embodiment 2-8
Embodiment 2-8 has carried out oligomerization of hexafluoropropylene to the present invention at different catalyzer and solvent, and operation is identical with embodiment 1, reaction result such as following table:
| Embodiment | Catalyzer (g) | Temperature (℃) | Pressure (MP) | Solvent | Perfluorinated nonene content (%) | Perfluor hexene content (%) |
| 2 3 4 5 6 7 8 | KCN(30) KSCN(40) KCN(30) KSCN(45) NaCN(30) NaSCN(50) LiCN(30) | 100 110 80 50 100 50 120 | 0.4 0.5 0.3 0.4 0.4 0.5 0.6 | DMF sulfolane acetonitrile diethylene glycol dimethyl ether oxolane ethylene glycol diethyl ether DMF+ sulfolane | 91 93 3 4 86 6 94 | 5 3 96 95 10 91 5 |
DMF:N, dinethylformamide
Claims (6)
1. the preparation method of a perfluorinated nonene is characterized in that, in polar aprotic solvent, under temperature of reaction 50-120 ℃ and the 0.1-1MP pressure, is that catalyzer carries out oligomerization of hexafluoropropylene with alkali metal cyanate or thiocyanate-.
2. the preparation method of perfluorinated nonene as claimed in claim 1 is characterized in that, described polar aprotic solvent is selected from ether, carboxylicesters, alkyl nitrile, alkylamide, alkyl sulfoxide, reaches their mixture.
3. the preparation method of perfluorinated nonene as claimed in claim 1, it is characterized in that, described polar aprotic solvent is selected from N, N dimethyl formamide, N, N N,N-DIMETHYLACETAMIDE, acetonitrile, tetramethylene sulfone, tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, glycol dimethyl ether, ethylene glycol diethyl ether, Propylene Glycol Dimethyl Ether and their mixture.
4. the preparation method of perfluorinated nonene as claimed in claim 1 is characterized in that, described polar aprotic solvent is N, the N dimethyl formamide.
5. the preparation method of perfluorinated nonene as claimed in claim 1 is characterized in that, catalyzer is dissolved in carrying out activation treatment in the polar aprotic solvent in advance, and activation temperature is 100 ℃, and soak time is 1～2 hour.
6. the preparation method of perfluorinated nonene as claimed in claim 1 is characterized in that, described catalyzer is the cyanate or the thiocyanate-of alkali metal lithium, sodium, potassium, caesium, and its consumption is a 0.1-300 grams per liter solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100691664A CN100448823C (en) | 2006-10-17 | 2006-10-17 | Process for preparing perfluoro nonene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100691664A CN100448823C (en) | 2006-10-17 | 2006-10-17 | Process for preparing perfluoro nonene |
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| Publication Number | Publication Date |
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| CN1944360A true CN1944360A (en) | 2007-04-11 |
| CN100448823C CN100448823C (en) | 2009-01-07 |
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| CNB2006100691664A Expired - Fee Related CN100448823C (en) | 2006-10-17 | 2006-10-17 | Process for preparing perfluoro nonene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759522A (en) * | 2008-11-14 | 2010-06-30 | 王凤娇 | Method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene |
| CN111606778A (en) * | 2020-06-29 | 2020-09-01 | 厦门名大科技有限公司 | Catalytic synthesis method of hexafluoropropylene oligomer |
| CN112142578A (en) * | 2020-10-26 | 2020-12-29 | 安徽天辰云泽安全科技有限公司 | Preparation method of perfluorohexanone |
| CN113880685A (en) * | 2021-11-04 | 2022-01-04 | 厦门大学 | Synthesis method of hexafluoropropylene oligomer |
| CN113968770A (en) * | 2021-11-04 | 2022-01-25 | 厦门大学 | Synthesis method of hexafluoropropylene tripolymer with low proportion of T1 isomer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254774A (en) * | 1992-12-28 | 1993-10-19 | Minnesota Mining And Manufacturing Company | Preparation of hexafluoropropene oligomers |
-
2006
- 2006-10-17 CN CNB2006100691664A patent/CN100448823C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759522A (en) * | 2008-11-14 | 2010-06-30 | 王凤娇 | Method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene |
| CN111606778A (en) * | 2020-06-29 | 2020-09-01 | 厦门名大科技有限公司 | Catalytic synthesis method of hexafluoropropylene oligomer |
| CN112142578A (en) * | 2020-10-26 | 2020-12-29 | 安徽天辰云泽安全科技有限公司 | Preparation method of perfluorohexanone |
| CN112142578B (en) * | 2020-10-26 | 2021-04-30 | 安徽航天立安安全科技有限公司 | Preparation method of perfluorohexanone |
| CN113880685A (en) * | 2021-11-04 | 2022-01-04 | 厦门大学 | Synthesis method of hexafluoropropylene oligomer |
| CN113968770A (en) * | 2021-11-04 | 2022-01-25 | 厦门大学 | Synthesis method of hexafluoropropylene tripolymer with low proportion of T1 isomer |
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| CN100448823C (en) | 2009-01-07 |
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