CN105330513A - High-selectivity method for catalytically synthesizing cyclic hydrofluoroolefin - Google Patents
High-selectivity method for catalytically synthesizing cyclic hydrofluoroolefin Download PDFInfo
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- CN105330513A CN105330513A CN201510689891.0A CN201510689891A CN105330513A CN 105330513 A CN105330513 A CN 105330513A CN 201510689891 A CN201510689891 A CN 201510689891A CN 105330513 A CN105330513 A CN 105330513A
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- fluoroolefin
- reaction
- cycloalkyl hydroperoxide
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- rectifying tower
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- TYOSEWMRNVIYNB-UHFFFAOYSA-N IC1=CCCC1 Chemical compound IC1=CCCC1 TYOSEWMRNVIYNB-UHFFFAOYSA-N 0.000 description 1
- YNVGPFBSWACROW-UHFFFAOYSA-N NC(CCC1)(C1I)F Chemical compound NC(CCC1)(C1I)F YNVGPFBSWACROW-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a high-selectivity method for catalytically synthesizing cyclic hydrofluoroolefin. Concretely, the method comprises taking a cyclic hydrofluoroalkane and a defluorination agent as raw materials, taking a Lewis base as a solvent, under the effect of a catalyst, heating to 150 DEG C-300 DEG C, so as to remove molecular hydrogen fluoride and obtain the cyclic hydrofluoroolefin. The method is high in cyclic hydrofluoroolefin selectivity, high in reaction efficiency, easy for purification and suitable for continuous production, and is suitable for industrial production of cyclic hydrofluoroolefin. The method is simple in technology, low in production cost, high in selectivity, free of byproducts and suitable for industrial production, and accords with our country twelfth five-year guideline and long-range guidance policy for energy saving and emission reduction.
Description
Technical field
The present invention is that one utilizes ring-type ring-type hydro fluoroalkanes and defluorinating agent, is warming up to 150 DEG C in a solvent at 300 DEG C, under catalyst action, generates the method for ring-type ring-type HF hydrocarbon.
Background technology
Cycloalkyl hydroperoxide fluoroolefin is the basic raw material producing fluoride-containing PMMA and macromolecular material, and cycloalkyl hydroperoxide fluoroolefin has important economy, environment and using value.2007 patent (US2007/0098646A1) describe the mixture of cycloalkyl hydroperoxide fluoroolefin replacement fluorine muriate as rocket propulsion, to reduce brokenization of fluorochloride to ozonosphere.Patent (US8758641B2) and patent (US8188323B2) all describe cycloalkyl hydroperoxide fluoroolefin and rely on its high energy gamma source utilization ratio and good thermal conductance effect, are used in refrigerator, in the heat-exchange systems such as air-conditioning as mixture.Patent (CN101356217A) and patent (8558040B2) report cycloalkyl hydroperoxide fluoroolefin simultaneously and mix with polyvalent alcohol or isocyanic ester and be applied to as whipping agent the industry that foams.2013 patent (CN101573316B) disclose by adding alkane, chlorocarbon, Chlorofluorocarbons (CFCs), the separation method of the separating fluorine hydrides such as hydrogen fluorohydrocarbon and cycloalkyl hydroperoxide fluoroolefin.2010 patent (CN101680691A) disclose fluoroolefin and act in vapor compression heat transfer system as working fluid.Patent (CN102089400A) discloses absorption agent/working fluid that pyridine plasma liquid and cycloalkyl hydroperoxide fluoroolefin compositions can be used in absorption cycle system for 2011 and cools or heat effect providing.Patent (EP2194569A1) disclosed cycloalkyl hydroperoxide fluoroolefin as etching agent for etching silicon dioxide film in 2010.Patent (US7846355B2) disclosed dissolving power that cycloalkyl hydroperoxide fluoroolefin utilizes it excellent in 2010 and environment friendly is applied to cleaning field as clean-out system.In 2012, patent (US8287752B2) reported because cycloalkyl hydroperoxide fluoroolefin environment friendly and flame retardant resistance are applied to fire extinguishing field.Patent (US2010/0154419A1) describes cycloalkyl hydroperoxide fluoroolefin and in thermoelectric cycle system, is applied to absorption cycle field as a kind of working fluid.Patent (US2013/0280178A1) discloses cycloalkyl hydroperoxide fluoroolefin and forms spraying mixture as a kind of pressurized gas together with the medicine improving thiozell, and application in daily life.
In addition, the synthetic method about cycloalkyl hydroperoxide fluoroolefin is also reported to some extent.As far back as non-patent literature (Tetrahedron in 1966,1966, vol, 22, pp.433to439) report and utilize liquid phase method, in Lithium Aluminium Hydride (LAH) and ether solvent, utilize perhaloalkenes and sodium borohydride under cryogenic, carry out the method for hydrogen chlorine exchange system for cycloalkyl hydroperoxide fluoroolefin, but the method complex process, harsh to equipment requirements, and aftertreatment is complicated.Non-patent literature (RussianJournalofOrganicChemistry, 2010, vol.46, No.9, pp.1290-1295) method that described vapor phase process prepare cycloalkyl hydroperoxide fluoroolefin in 2010, in quartz reactor, utilize Cr-Ni catalyzer, perhaloalkenes and hydrogen carry out the exchange of hydrogen chlorine, but the by product of this kind of method generation is more, and separation difficulty.2012 patent (US8318991B2) disclose the catalyzer utilizing active ingredient to be palladium, by ring-type perhaloalkenes and hydrogen in fixed-bed reactor, under hot conditions, the method being prepared cycloalkyl hydroperoxide fluoroolefin is exchanged by hydrogen chlorine, but the method is for the selectivity preparing cycloalkyl hydroperoxide fluoroolefin lower (being less than 70%), and by product is more, difficult separation.Patent (US8558040B2) also reported in 2013 and remove hydrogen fluoride by ring-type hydro fluoroalkanes in strong base solution, produce the method for cycloalkyl hydroperoxide fluoroolefin, but the method preparation cycle is longer and selectivity is lower (50%-70%), and easily produce isomers, purification difficult.
In sum, all there is some problems in the method preparing cycloalkyl hydroperoxide fluoroolefin, utilizes highly basic to eliminate hydrogen fluoride to ring-type hydro fluoroalkanes, easily produce isomers, purification difficult, harsh to equipment requirements.Utilize vapor phase process to prepare the method for hydrogen fluorohydrocarbon, selectivity is lower, and by product is more.
Summary of the invention
The object of the invention is, in order to overcome above prior art defect, to design a kind of selectivity high; Reaction efficiency is high; Purify easy and can serialization be realized, being applicable to the industrial method preparing cycloalkyl hydroperoxide fluoroolefin.
A method for synthesis of cyclic cycloalkyl hydroperoxide fluoroolefin, with ring-type hydro fluoroalkanes for raw material, with Lewis alkali for solvent, reacts, sloughs a part hydrogen fluoride and obtain cycloalkyl hydroperoxide fluorine monoolefine at temperature 150 DEG C-300 DEG C;
The structure of described ring-type hydro fluoroalkanes is such as formula I, and wherein n is 0-3, and the structural formula of described ring-type ring-type HF hydrocarbon is such as formula II;
Described Lewis alkali is nitrogen-nitrogen dimethyl formamide, nitrogen-nitrogen N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), triethylamine, one or more in DIPEA.
The mol ratio of described cycloalkyl hydroperoxide fluoroolefin and Lewis alkali is 1:1-5.
The mol ratio of described cycloalkyl hydroperoxide fluoroolefin and Lewis alkali is 1:1-3.
The mol ratio of described cycloalkyl hydroperoxide fluoroolefin and Lewis alkali is 1:1-2.
Described temperature of reaction is 150-170 DEG C, and the reaction times is 20-40 hour.
Described reaction, at rectifying tower, is carried out in steel cylinder or reactor.
Described reaction is carried out in rectifying tower, utilizes rectifying tower to realize successive reaction, and tower top gathers cycloalkyl hydroperoxide fluoroolefin.
Described rectifying tower, the material of steel cylinder or reactor is nickelalloy, breathe out formula alloy, Monel metal, because of Kang Hejin or stainless steel.
Principle of the present invention: utilize ring-type hydro fluoroalkanes and defluorinating agent to be raw material, under the effect of catalyzer, with Lewis alkali for solvent, heats up 150 DEG C-300 DEG C, and de-a part hydrogen fluoride, obtains cycloalkyl hydroperoxide fluoroolefin.Lewis alkali had both been defluorinating agent in above-mentioned reaction, catalyzer, was again solvent simultaneously, the hydrogen fluoride molecule generated in neutralization reaction while of also.The mol ratio of ring-type hydro fluoroalkanes and catalyzer is 1:0.1-0.5, and the mol ratio of ring-type hydro fluoroalkanes and defluorinating agent is 1:1-2, and the mol ratio of ring-type hydro fluoroalkanes and solvent is 1:1-2.
This speed of reaction is fast, can complete in a set of rectifier unit inside, rectifying tower reactor loads above-mentioned Lewis alkali and ring-type hydro fluoroalkanes, reaction occurs with distillation simultaneously, in tower drops situation, tower reactor is supplemented raw material and is got final product successive reaction, and wherein raw material comprises one or more and ring-type hydro fluoroalkanes of above-mentioned catalyzer.The method technique is simple, low production cost, and selectivity is high, no coupling product, can suitability for industrialized production, meets the 12 planning policies of China and the guilding principle of long-range energy-saving and emission-reduction.
The cycloalkyl hydroperoxide fluoroolefin selectivity that the inventive method prepares is high; Reaction efficiency is high; Purify easy and can serialization be realized, being applicable to the industrial method preparing cycloalkyl hydroperoxide fluoroolefin.
Accompanying drawing explanation
Fig. 1 is process flow sheet.
Embodiment
Below by embodiment and accompanying drawing, the present invention is described in further detail.
Fig. 1 is process flow sheet.
Icon annotates: Z
ffor input concentration (7FA and Lewis alkali mol ratio), X
dfor distillate concentration, X
bfor tower bottoms concentration (7FA and Lewis alkali mol ratio), L
bfor rectifying tower liquid level, L
dfor gas-liquid separator liquid level, F is feed rate, and V is rectifying steam flow, and L is withdrawing fluid flow, and D is distillate flow, and B is still flow quantity.
Rectifying tower is because of health material, tower height 4m, tower diameter 1m, and filler type selecting is metal Raschig ring.
Gas-liquid separator is stainless steel, tower height 2m, tower diameter 1m.
As shown in Figure 1, continuous rectificating technique flow process is:
1. opening fresh feed pump, is that the mixture of 1 to 2 is 20m with F by 7FA and Lewis alkali mol ratio
3/ h squeezes into rectifying tower, as rectifying tower liquid level L
bduring to 80cm, get through rectifying tower top reflux process.
2. get through rectifying tower reboiler heating procedure, open steam regulating valve and rectifying tower is boosted.By regulating reboiler steam and overhead condenser recirculated water, rectifying tower is made to rise to 1.150MPa in 8h internal pressure.In fill process, when rectifying tower liquid level is to 140cm, close rectifying tower charging variable valve, rectifying tower stops charging.Regulate reboiler steam and condenser recirculated water, keep Rectification column pressure to maintain 1.150MPa, liquid level 70-130cm and stable quantity of reflux, rectifying tower carries out single tower operation.
3.L
dduring for 1m, open reflux pump, L is 10m3/h, makes L
dreduce to 0.5m
4. Analysis of X
d, when 6FE purity is 99.9%, extraction product.
5. if rectifying tower drops, Analysis of X
b, open fresh feed pump, supplement material, maintain X
bbe between 1.5 to 2.
Embodiment 1
7FA (0.02mmol, 3.92g) and nitrogen is added, nitrogen dimethyl formamide (0.1mol in 50ml stainless steel steel cylinder, 7.3g), under air-tight state, be heated to 150 DEG C, after reaction 20h, pressure itself is 0.380Mpa, stopped reaction, Temperature fall, carefully opens steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilizes the composition of chromatographic organic product, the results are shown in table 1.
7FA transformation efficiency=(7FA that reaction consumes measures/adds the amount of 7FA) * 100%
6FE selectivity=(summation of 6FE growing amount/growing amount) * 100%
Reaction equation is as follows:
Embodiment 2
7FA (2mol, 392g) and nitrogen is added, nitrogen dimethyl formamide (4mol in 1L stainless steel steel cylinder, 292g), 150 DEG C are heated under dimethyl sulfoxide (DMSO) (2mol, 156g) air tight condition, after reaction 1h, steel cylinder pressure itself is 0.556Mpa, stopped reaction, Temperature fall, carefully open steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilize the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as follows:
Embodiment 3
7FA (2mol, 392g) and nitrogen is added, nitrogen dimethyl formamide (4mol in 50mL stainless steel steel cylinder, 292g), under air tight condition, be heated to 150 DEG C, after reaction 24h, steel cylinder pressure itself is 0.392Mpa, stopped reaction, Temperature fall, carefully opens steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilizes the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as shown in case study on implementation 1
Embodiment 4
7FA (0.02mol, 3.92g) and nitrogen is added, nitrogen N,N-DIMETHYLACETAMIDE (0.06mol in 50mL stainless steel steel cylinder, 5.22g), under air tight condition, be heated to 170 DEG C, after reaction 10h, steel cylinder pressure itself is 0.374Mpa, stopped reaction, Temperature fall, carefully opens steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilizes the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as follows:
Embodiment 5
7FA (20mmol, 3.92g) and dimethyl sulfoxide (DMSO) (60mmol, 4.68g) is added in 50mL stainless steel steel cylinder, 170 DEG C are heated under air tight condition, after reaction 18h, stopped reaction, steel cylinder pressure itself is 0.316Mpa, Temperature fall, carefully open steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilize the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as follows:
Embodiment 6
7FA (20mmol, 3.92g) and quinoline (60mmol, 7.74g) is added in 50mL stainless steel steel cylinder, 150 DEG C are heated under air tight condition, after reaction 30h, stopped reaction, steel cylinder pressure itself is 0.333Mpa, Temperature fall, carefully open steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilize the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as follows:
Embodiment 7
7FA (20mmol, 3.92g) and triethylamine (60mmol, 6.06g) is added in 50mL stainless steel steel cylinder, 100 DEG C are heated under air tight condition, after reaction 10h, stopped reaction, steel cylinder pressure itself is 0.316Mpa, Temperature fall, carefully open steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilize the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as follows:
Embodiment 8
7FA (20mmol, 3.92g) and DIPEA (60mmol is added in 50mL stainless steel steel cylinder, 7.74g), under air tight condition, be heated to 130 DEG C, after reaction 20h, stopped reaction, steel cylinder pressure itself is 0.305Mpa, Temperature fall, carefully opens steel cylinder upper end valve, after non-condensable gas use water is absorbed, collection liquid product, utilizes the organic composition of chromatographic, the results are shown in table 1.
Reaction equation is as follows:
The reaction result of each embodiment of table 1.
| Case | Temperature of reaction (DEG C) | 7FA transformation efficiency (%) | 6FE selectivity (%) |
| Embodiment 1 | 150 | 100 | 99.16 |
| Embodiment 2 | 150 | 53.40 | 99.14 |
| Embodiment 3 | 150 | 100 | 99.35 |
| Embodiment 4 | 170 | 100 | 99.18 |
| Embodiment 5 | 170 | 100 | 99.21 |
| Embodiment 6 | 150 | 100 | 99.16 |
| Embodiment 7 | 100 | 100 | 99.17 |
| Embodiment 8 | 130 | 100 | 99.32 |
Claims (9)
1. a method for synthesis of cyclic HF hydrocarbon, with ring-type hydro fluoroalkanes for raw material, with Lewis alkali for solvent, reacts, sloughs a part hydrogen fluoride and obtain hydrogen fluorine list hydrocarbon hydrocarbon at temperature 150 DEG C-300 DEG C;
The structure of described ring-type hydro fluoroalkanes is such as formula I, and wherein n is 0-3, and the structural formula of described cycloalkyl hydroperoxide fluoroolefin is such as formula II.
2. method according to claim 1, described Lewis alkali is nitrogen-nitrogen dimethyl formamide, nitrogen-nitrogen N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), triethylamine, one or more in DIPEA.
3. method according to claim 2, the mol ratio of described cycloalkyl hydroperoxide fluoroolefin and Lewis alkali is 1:1-5.
4. method according to claim 3, the mol ratio of described cycloalkyl hydroperoxide fluoroolefin and Lewis alkali is 1:1-3.
5. method according to claim 4, the mol ratio of described cycloalkyl hydroperoxide fluoroolefin and Lewis alkali is 1:1-2.
6. method according to claim 1, described temperature of reaction is 150-170 DEG C, and the reaction times is 20-40 hour.
7. method according to claim 1, described reaction, at rectifying tower, is carried out in steel cylinder or reactor.
8. method according to claim 7, described reaction is carried out in rectifying tower, utilizes rectifying tower to realize successive reaction, and tower top gathers cycloalkyl hydroperoxide fluoroolefin.
9. method according to claim 7, described rectifying tower, the material of steel cylinder or reactor is nickelalloy, and breathe out formula alloy, Monel metal, because of Kang Hejin or stainless steel.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365244A (en) * | 2017-08-03 | 2017-11-21 | 北京宇极科技发展有限公司 | Organic solvent provides hydrogen source and the method that hydrogen halogen exchange reaction prepares 1H perhalogeno cycloolefins occurs |
| JP2019127466A (en) * | 2018-01-25 | 2019-08-01 | 日本ゼオン株式会社 | Method for producing 1h,2h-perfluorocycloalkene |
| JP2019127465A (en) * | 2018-01-25 | 2019-08-01 | 日本ゼオン株式会社 | Method for producing 1h,2h-perfluorocycloalkene |
| JP2020100595A (en) * | 2018-12-25 | 2020-07-02 | ダイキン工業株式会社 | Production method of cyclobutene |
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| WO2008081804A1 (en) * | 2006-12-28 | 2008-07-10 | National Institute Of Advanced Industrial Science And Technology | Cleaning agent containing fluorinated cyclic unsaturated hydrocarbon and cleaning method |
| CN101637732A (en) * | 2009-08-14 | 2010-02-03 | 西安近代化学研究所 | Dehydrofluorination catalyst |
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2015
- 2015-10-22 CN CN201510689891.0A patent/CN105330513B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008081804A1 (en) * | 2006-12-28 | 2008-07-10 | National Institute Of Advanced Industrial Science And Technology | Cleaning agent containing fluorinated cyclic unsaturated hydrocarbon and cleaning method |
| CN101637732A (en) * | 2009-08-14 | 2010-02-03 | 西安近代化学研究所 | Dehydrofluorination catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365244A (en) * | 2017-08-03 | 2017-11-21 | 北京宇极科技发展有限公司 | Organic solvent provides hydrogen source and the method that hydrogen halogen exchange reaction prepares 1H perhalogeno cycloolefins occurs |
| JP2019127466A (en) * | 2018-01-25 | 2019-08-01 | 日本ゼオン株式会社 | Method for producing 1h,2h-perfluorocycloalkene |
| JP2019127465A (en) * | 2018-01-25 | 2019-08-01 | 日本ゼオン株式会社 | Method for producing 1h,2h-perfluorocycloalkene |
| JP2020100595A (en) * | 2018-12-25 | 2020-07-02 | ダイキン工業株式会社 | Production method of cyclobutene |
| WO2020137824A1 (en) * | 2018-12-25 | 2020-07-02 | ダイキン工業株式会社 | Cyclobutene production method |
| CN113227025A (en) * | 2018-12-25 | 2021-08-06 | 大金工业株式会社 | Process for producing cyclobutene |
| JP7166911B2 (en) | 2018-12-25 | 2022-11-08 | ダイキン工業株式会社 | Method for producing cyclobutene |
| TWI787567B (en) * | 2018-12-25 | 2022-12-21 | 日商大金工業股份有限公司 | The production method of cyclobutene |
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