CN107721845A - A kind of method for synthesizing fluorine neoprene diacid - Google Patents
A kind of method for synthesizing fluorine neoprene diacid Download PDFInfo
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- CN107721845A CN107721845A CN201711081511.0A CN201711081511A CN107721845A CN 107721845 A CN107721845 A CN 107721845A CN 201711081511 A CN201711081511 A CN 201711081511A CN 107721845 A CN107721845 A CN 107721845A
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- cyclobutane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
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Abstract
The present invention relates to " one kind synthesis fluorine neoprene diacid ", belong to organic chemical synthesis field.The method of this synthesis fluorine neoprene diacid：Hexachlorobutadiene (molecular formula CCl2=CCl CCl=CCl2) under the effect of ring fluorination catalyst, generate fluorine chlorine cyclobutane (molecular formula Cyclo C2FxClyCCl=CCl, wherein x+y=4), then, fluorine neoprene diacid (molecular formula HOOC C are generated in the presence of oxidant2FxCly‑COOH)。CCl2=CCl CCl=CCl2→Cyclo‑C2FxClyCCl=CCl → HOOC C2FxClyCOOH the inventive method raw materials are cheap, source facility；Product separating-purifying is simple；It is easy to industrialized production；Three industrial wastes are few.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, more particularly to a kind of method for synthesizing fluorine neoprene diacid.
Background technology
Fluorine neoprene diacid has very high industrial value, is a kind of widely used raw material of industry, and product can use downstream
In five heterocyclic compound alkyd resins of production, agricultural chemical insecticide etc., while in fluoride-containing PMMAs such as fluorine-containing medicines intermediates
Also there is higher application value in terms of synthesis.It is reported that fluorine neoprene diacid has been widely used for the corrosion resistance green wood such as resin
The synthesis of material.
At present, the study on the synthesis about fluorine neoprene diacid, relevant report are less.One is reported in patent (US2438485)
Kind synthesis tetrafluoro succinic acid method, this method is by aoxidizing hexafluoro cyclobutane reaction generation tetrafluoro succinic acid.This method raw material is difficult
In preparation, industrialized production is limited.A kind of synthesizing succinic acid method is reported in patent (US2426224), this method passes through
Acetic acid dimerization is generated into succinic acid.This method expensive raw material price, reactions steps length, reaction yield are low.
It can be seen from more than when preparing fluorine neoprene diacid, there is route length, condition is harsh, and raw material is not easy to prepare
The shortcomings that, these all limit the industrialized production of fluorine neoprene diacid.
The content of the invention
In order to solve the above problems, it is an object of the invention to provide a kind of method for synthesizing fluorine neoprene diacid.
In order to achieve the above object, the method for synthesis fluorine neoprene diacid provided by the invention is following including carrying out in order
Step：
(1) with hexachlorobutadiene (CCl2=CCl-CCl=CCl2) and hydrogen fluoride as raw material, make in ring fluorination catalyst
Gas phase ring fluorination reaction, generation fluorine chlorine cyclobutane (Cyclo-C are carried out under2FxCly- CCl=CCl-, wherein x+y=4)；
(2) fluorine chlorine cyclobutane (Cyclo-C2FxCly- CCl=CCl-, wherein x+y=4) oxidant effect under carry out oxygen
Change reaction generation fluorine neoprene diacid (HOOC-C2FxCly-COOH)。
In step (1), described ring fluorination catalyst is selected from Cr, Ni, Cu, Zn, Mg, the one or more in Co, In
Compounding ingredients catalyst.
In step (1), the temperature of described gas phase ring fluorination reaction is 100-600 DEG C.
In step (1), the time of described gas phase ring fluorination reaction is 0.1-20s.
In step (1), the mol ratio of described hexachlorobutadiene and hydrogen fluoride is 1/4-1/16.
In step (2), described oxidant is selected from KMnO4、KCr2O7、KClO3、MnO2Any of.
In step (2), the temperature of described oxidation reaction is -20-100 DEG C.
In step (2), the time of described oxidation reaction is 1-20h.
The method of synthesis fluorine neoprene diacid provided by the invention has the beneficial effect that：
1. raw material of the present invention is cheap, source facility.
2. three industrial wastes are less.
3. product yield is high, product separating-purifying is simple.
4. building-up process is safe, it is suitable for industrialized production.
Embodiment
Below by way of the description of embodiment, the invention will be further described, but this is not the limit to the present invention
System, those skilled in the art according to the present invention basic thought, various modifications may be made or improve, but without departing from this
The basic thought of invention, within the scope of the present invention.
Embodiment 1
(1) preparation of ring fluorination catalyst：Using coprecipitation, step is as follows, by CrCl3、Cu(NO3)2、Zn(NO3)2It is molten
The ammoniacal liquor for accounting for the weight of mixed liquor 30%, into mixed liquor, is then added drop-wise to above-mentioned mixed liquor by liquid with 85: 10: 5 mixed in molar ratio
In, the pH value of mixed liquor is adjusted to 9.0, by precipitation aging in 24 hours, precipitation filtering, is washed with deionized, dries, compacting
Shaping, so as to obtain Cr-Cu-Zn catalyst.
The drying process of Cr-Cu-Zn catalyst：20ml Cr-Cu-Zn catalyst is loaded into fixed bed reactors, Ran Houyong
Open-type pipe heats stove heat fixed bed reactors.Make Cr-Cu-Zn catalyst under the protection of 50ml/min nitrogen, first with 10
DEG C/min speed rises to 400 DEG C of temperature and dries 10 hours, then, temperature is reduced to 200 DEG C, thus complete Cr-Cu-Zn and urge
The drying process of agent.
The activation process of Cr-Cu-Zn catalyst：Fixed bed reactors are heated to 200 DEG C, first with 100ml/min
Nitrogen carries out activating catalytic 4 hours with 20ml/min hydrogen fluoride；Then entered using 100ml/min nitrogen and 50ml/min hydrogen fluoride
Row activating catalytic 4 hours；Afterwards activating catalytic is carried out using 50ml/min nitrogen and 100ml/min hydrogen fluoride 4 hours；Recycle
The pure hydrogen fluoride of 100ml/min carries out activating catalytic 4 hours；Temperature is raised to 400 DEG C, finally utilizes the pure hydrogen fluoride of 100ml/min
Carry out activating catalytic 4 hours, thus complete the activation process of Cr-Cu-Zn catalyst.
Above-mentioned ring fluorination catalyst participates in course of reaction：Fixed bed reactors are heated to 350 DEG C, make the six of 0.1g/min
Chlorobutadiene is well mixed together with 34.4ml/min hydrogen fluoride into hybrid chamber.Afterwards, by fixed bed reactors until slow
Rush bottle, washing bottle, concentrated base absorber, cooling collector, should during the time of contact of gas phase and catalyst in reactor be
12.1s.After experiment terminates, product is mainly distributed in cooling collector.Collect the product in cooling collector and carry out GC and divide
Analysis.GC results are shown, are collected in product and are contained 40% tetrafluoro dichloro cyclobutane (Cyclo-CF2-CF2- CCl=CCl-), 30% 3
Fluorine trichlorine cyclobutane (Cyclo-CF2- CFCl-CCl=CCl-), 10% difluoro dichloro cyclobutane (Cyclo-CFCl-CFCl-CCl
=CCl-), 18% hexachlorobutadiene.By collecting and separating rectifying, 300g products are finally collected into.The component distribution of the product
For：51% tetrafluoro dichloro cyclobutane (Cyclo-CF2-CF2- CCl=CCl-), 37% trifluoro trichlorine cyclobutane (Cyclo-CF2-
CFCl-CCl=CCl-), 8% difluoro dichloro cyclobutane (Cyclo-CFCl-CFCl-CCl=CCl-).
(2) in 150ml three-necked flasks, 42g KMnO is added4, ethanol nitrogen mixture controlling reaction temperature is used as 5
DEG C or so, the rotating speed of flask is 30r/min.After reaction 4 hours, a small amount of white solid is taken to be dissolved using acetone.GC is analyzed
As a result show, wherein 48% tetrafluoro dichloro succinic acid (HOOC-CF2-CF2- COOH), 32% trifluoro trichlorine succinic acid (HOOC-
CF2- CFCl-COOH), 5% difluoro dichloro succinic acid (HOOC-CFCl-CFCl-COOH).
Embodiment 2
(1) preparation of ring fluorination catalyst：Using coprecipitation, step is as follows, by CrCl3、Ni(NO3)3、In(NO3)3It is molten
The ammoniacal liquor for accounting for the weight of mixed liquor 30%, into mixed liquor, is then added drop-wise to above-mentioned mixed liquor by liquid with 85: 10: 5 mixed in molar ratio
In, the pH value of mixed liquor is adjusted to 9.0, by precipitation aging in 24 hours, precipitation filtering, is washed with deionized, dries, compacting
Shaping, so as to obtain Cr-Ni-In catalyst.
The drying process of Cr-Ni-In catalyst：20ml Cr-Ni-In catalyst is loaded into fixed bed reactors, Ran Houyong
Open-type pipe heats stove heat fixed bed reactors.Make Cr-Ni-In catalyst under the protection of 50m/minl nitrogen, first with 10
DEG C/min speed rises to 400 DEG C of temperature and dries 10 hours, then, temperature is reduced to 200 DEG C, thus complete Cr-Ni-In and urge
The drying process of agent.
The activation process of Cr-Ni-In catalyst：Fixed bed reactors are heated to 200 DEG C, first with 100ml/min
Nitrogen carries out activating catalytic 4 hours with 20ml/min hydrogen fluoride；Then entered using 100ml/min nitrogen and 50ml/min hydrogen fluoride
Row activating catalytic 4 hours；Afterwards activating catalytic is carried out using 50ml/min nitrogen and 100ml/min hydrogen fluoride 4 hours；Recycle
The pure hydrogen fluoride of 100ml/min carries out activating catalytic 4 hours；Temperature is raised to 400 DEG C, finally utilizes the pure hydrogen fluoride of 100ml/min
Carry out activating catalytic 4 hours, thus complete the activation process of Cr-Ni-In catalyst.
Above-mentioned ring fluorination catalyst participates in course of reaction：Fixed bed reactors are heated to 340 DEG C, make the six of 0.1g/min
Chlorobutadiene is well mixed together with 86ml/min hydrogen fluoride into hybrid chamber.Afterwards, by fixed bed reactors until buffering
Bottle, washing bottle, concentrated base absorber, cooling collector, the time of contact of gas phase and catalyst in reactor is 5.5s during being somebody's turn to do.
After experiment terminates, product is mainly distributed in cooling collector.Collect the product in cooling collector and carry out GC analyses.GC is tied
Fruit shows, collects in product and contains 31% tetrafluoro dichloro cyclobutane (Cyclo-CF2-CF2- CCl=CCl-), 21% trifluoro trichlorine
Cyclobutane (Cyclo-CF2- CFCl-CCl=CCl-), 5% difluoro dichloro cyclobutane (Cyclo-CFCl-CFCl-CCl=
CCl-), 40% hexachlorobutadiene.By collecting and separating rectifying, 223g products are finally collected into.The component distribution of the product
For：48% tetrafluoro dichloro cyclobutane (Cyclo-CF2-CF2- CCl=CCl-), 36% trifluoro trichlorine cyclobutane (Cyclo-CF2-
CFCl-CCl=CCl-), 5% difluoro dichloro cyclobutane (Cyclo-CFCl-CFCl-CCl=CCl-).
(2) in 150ml three-necked flasks, 59g KCr is added2O7, ethanol nitrogen mixture controlling reaction temperature is used as 5
DEG C or so, the rotating speed of flask is 30r/min.After reaction 2 hours, a small amount of white solid is taken to be dissolved using acetone.GC is analyzed
As a result show, wherein 45% tetrafluoro dichloro succinic acid (HOOC-CF2-CF2- COOH), 32% trifluoro trichlorine succinic acid (HOOC-
CF2- CFCl-COOH), 3% difluoro dichloro succinic acid (HOOC-CFCl-CFCl-COOH).
Claims (8)
- A kind of 1. method for synthesizing fluorine neoprene diacid, it is characterised in that：Hexachlorobutadiene (molecular formula CCl2=CCl-CCl= CCl2) and hydrogen fluoride as raw material, carry out gas phase ring fluorination reaction under the effect of ring fluorination catalyst, generate fluorine chlorine cyclobutane (molecular formula Cyclo-C2FxCly- CCl=CCl-, wherein x+y=4)；Then, fluorine neoprene diacid is generated in the presence of oxidant (molecular formula HOOC-C2FxCly-COOH)。
- 2. according to the method for claim 1, it is characterised in that：Hexachlorobutadiene gas phase fluorine under the effect of ring fluorination catalyst Metaplasia is into fluorine chlorine cyclobutane, and the ring fluorination catalyst is Cr, Ni, Cu, Zn, Mg, one or more compounding ingredients in Co, In Catalyst.
- 3. according to the method for claim 1, it is characterised in that：Hexachlorobutadiene gas phase fluorine under the effect of ring fluorination catalyst For metaplasia into fluorine chlorine cyclobutane, the gas phase reaction temperature is 100-600 DEG C.
- 4. according to the method for claim 1, it is characterised in that：Hexachlorobutadiene gas phase fluorine under the effect of ring fluorination catalyst Metaplasia is into fluorine chlorine cyclobutane, the time of contact of the gas phase reaction：0.1—20s.
- 5. according to the method for claim 1, it is characterised in that：The mol ratio of hexachlorobutadiene and hydrogen fluoride is 1/4-1/ 16。
- 6. according to the method for claim 1, it is characterised in that：Fluorine chlorine cyclobutane generates fluorine chlorine in the presence of oxidant Succinic acid, the oxidant are KMnO4,KCr2O7,KClO3,MnO2In a kind of oxidant.
- 7. according to the method for claim 1, it is characterised in that：Fluorine chlorine cyclobutane generates fluorine chlorine in the presence of oxidant Succinic acid, the reaction temperature are -20-100 DEG C.
- 8. according to the method for claim 1, it is characterised in that：Fluorine chlorine cyclobutane generates fluorine chlorine in the presence of oxidant Succinic acid, the reaction time is：1—20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981688A (en) * | 2019-10-31 | 2020-04-10 | 中国矿业大学(北京) | Method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis |
| CN110981689A (en) * | 2019-10-31 | 2020-04-10 | 中国矿业大学(北京) | Method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis |
| CN111039746A (en) * | 2019-10-31 | 2020-04-21 | 中国矿业大学(北京) | Method for synthesizing 4, 4-difluorocyclobutene by gas phase catalysis |
| CN114591154A (en) * | 2022-03-17 | 2022-06-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutenyl dimethyl ether |
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| US2438485A (en) * | 1946-10-04 | 1948-03-23 | Univ Ohio State Res Found | Fluorinated dibasic acids and method of preparing same |
| CN105348034A (en) * | 2015-12-07 | 2016-02-24 | 天津医科大学 | Hexafluoropropylene-2-butyne synthesizing method |
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2017
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|---|---|---|---|---|
| US2438485A (en) * | 1946-10-04 | 1948-03-23 | Univ Ohio State Res Found | Fluorinated dibasic acids and method of preparing same |
| CN105348034A (en) * | 2015-12-07 | 2016-02-24 | 天津医科大学 | Hexafluoropropylene-2-butyne synthesizing method |
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| R.N. HASZELDINE ET AL.: "Fluoro-olefins. Part III. Some rearrangement reactions of polyhalogeno-olefins, and routes to butadienes", 《JOURNAL OF THE CHEMICAL SOCIETY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981688A (en) * | 2019-10-31 | 2020-04-10 | 中国矿业大学(北京) | Method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis |
| CN110981689A (en) * | 2019-10-31 | 2020-04-10 | 中国矿业大学(北京) | Method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis |
| CN111039746A (en) * | 2019-10-31 | 2020-04-21 | 中国矿业大学(北京) | Method for synthesizing 4, 4-difluorocyclobutene by gas phase catalysis |
| CN110981689B (en) * | 2019-10-31 | 2021-03-23 | 中国矿业大学(北京) | Method for synthesizing 3, 4-difluorocyclobutene by gas phase catalysis |
| CN110981688B (en) * | 2019-10-31 | 2021-03-23 | 中国矿业大学(北京) | Method for synthesizing 3,4, 4-trifluoro cyclobutene by gas phase catalysis |
| CN111039746B (en) * | 2019-10-31 | 2021-03-23 | 中国矿业大学(北京) | Method for synthesizing 4, 4-difluorocyclobutene by gas phase catalysis |
| CN114591154A (en) * | 2022-03-17 | 2022-06-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutenyl dimethyl ether |
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