CN110283043A - A method of preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- - Google Patents

A method of preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- Download PDF

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CN110283043A
CN110283043A CN201910682819.3A CN201910682819A CN110283043A CN 110283043 A CN110283043 A CN 110283043A CN 201910682819 A CN201910682819 A CN 201910682819A CN 110283043 A CN110283043 A CN 110283043A
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chloro
butylene
hexafluoro
nitrae
isosorbide
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CN110283043B (en
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韩升
吕剑
赵波
曾纪珺
张伟
杨志强
唐晓博
郝志军
亢建平
李凤仙
淡保松
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

2- chloro- 1 is prepared the invention discloses a kind of, 1, 1, 4, 4, the method of 4- hexafluoro -2- butylene, this method is in the presence of liquid phase composite catalyst, hydrogen fluoride and 1, 1, 1, 3, 3- five chloro- 4, 4, 4- trifluorobutane liquid-phase fluorination prepares 2- chloro- 1, 1, 1, 4, 4, 4- hexafluoro -2- butylene, HF and 1, 1, 1, 3, 3- five chloro- 4, 4, the molar ratio of 4- trifluorobutane is 3~50:1, 1, 1, 1, 3, 3- five chloro- 4, 4, the molar ratio of 4- trifluorobutane and liquid phase composite catalyst is 0.1~3:1, reaction temperature is 50 DEG C~150 DEG C, reaction time is 0.5h~10h, wherein liquid phase composite catalyst is made of metal fluoride and compounding agent, metal fluoride is TaF5、NbF5、TiF4Or SnF4, compounding agent is organic amine or quaternary ammonium salt, and the molar ratio of compounding agent and metal fluoride is 0~2:1.Present invention is mainly used for the preparation chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2-.

Description

A method of preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2-
Technical field
2- chloro- 1,1 is prepared the present invention relates to a kind of, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, more particularly to 1,1,1, The chloro- 4,4,4- trifluorobutane of 3,3- five is the side that raw material prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- through liquid-phase fluorination Method.
Background technique
Cis- 1,1,1,4,4,4- hexafluoro -2- butylene (Z-HFO-1336mzz) foaming, heat-insulated, thermal insulation property and tradition foam Agent is suitable, and ozone-depleting value (ODP) of diving is zero, and the latent value (GWP) of greenhouse effects is 9, and effect on environment very little is considered as new one For environmentally protective foaming agent.As the important intermediate of synthesis Z-HFO-1336mzz, 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- fourths The extensive synthesis of alkene is one of the key technology for realizing that Z-HFO-1336mzz is industrially prepared.
Chinese patent CN 104072333B is reported under Antimony pentachloride catalytic action, and reaction temperature is 100 DEG C, chlordene Butadiene synthesizes 2- chloro- 1,1 with anhydrous hydrogen fluoride liquid-phase fluorination, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, under this condition Antimony pentachloride The disadvantages of there are valence states to reduce inactivation, thermal stability is poor, the service life is extremely short, it is difficult to realize extensive synthesis；Chinese patent It is chloro- by hydrogenation-dechlorination reaction synthesis 2- that CN106536462A reports the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2,3- bis- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, but due to the problems such as hydrogenation reaction is difficult to control, and the technique is poor there are selectivity of product.
Summary of the invention
It is an object of the invention to overcome deficiency present in background technique, provide that a kind of selectivity of product is high, catalyst The preparation method of the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- of service life length.
In order to achieve the object of the present invention, present invention introduces compounding agents and metal fluoride to form liquid phase composite catalyst, The acidity of the selected adjustable metal fluoride of compounding agent, catalytic fluorination 1 with high selectivity, 1,1,3,3- five chloro- 4,4, 4- trifluorobutane prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2-.
The present invention prepares 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, comprising the following steps: compound in liquid phase In the presence of catalyst, hydrogen fluoride and 1,1,1,3,3- five chloro- 4,4,4- trifluorobutane liquid-phase fluorinations preparation 2- chloro- 1,1, Isosorbide-5-Nitrae, 4, 4- hexafluoro -2- butylene, HF and 1,1,1,3,3- five chloro- 4, the molar ratios of 4,4- trifluorobutanes is 3~50:1,1,1,1,3,3- five Chloro- 4, the molar ratio of 4,4- trifluorobutanes and liquid phase composite catalyst is 0.1~3:1, and reaction temperature is 50 DEG C~150 DEG C, instead It is 0.5h~10h between seasonable, wherein liquid phase composite catalyst is made of metal fluoride and compounding agent, and metal fluoride is TaF5、NbF5、TiF4Or SnF4, compounding agent is organic amine or quaternary ammonium salt, and the molar ratio of compounding agent and metal fluoride is 0~2: 1。
In the present invention can direct commodity in use metal fluoride, can also be before the reaction with HF by metal fluoride Precursor, such as TaCl5、NbCl5、TiCl4Or SnCl4Equal fluorinations are corresponding metal fluoride, and the reaction effect of the two is basic Quite.
Preferred metal fluoride is TaF in the present invention5Or TiF4, further preferably TiF4。
Preferred organic amine is n-propylamine, n-octyl amine, triethylamine, ethylenediamine, triethylene diamine, pyrroles, miaow in the present invention Azoles, piperidines, pyridine or pyrazine, further preferably n-propylamine, triethylamine, ethylenediamine, imidazoles or piperidines；Preferably quaternary ammonium salt is The fluorination of tetramethyl ammonium chloride, etamon chloride, Methanaminium, N,N,N-trimethyl-, fluoride or tetraethyl ammonium fluoride, further preferably tetramethyl Ammonium.
Present invention introduces compounding agents, form liquid phase composite catalyst, the adjustable metal fluorine of compounding agent with metal fluoride The acidity of compound, to obtain and react the catalytic activity to match, the molar ratio of suitable compounding agent and metal fluoride is 0~ 1:1, further preferred molar ratio are 0.2~0.5:1.
The method for preparing the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- of the invention can be carried out intermittently or serially.? In method of having a rest, HF and 1,1,1,3,3- five chloro- 4,4,4- trifluorobutanes are added at one time to reactor, rise to corresponding reaction temperature Degree, preferred reaction condition are HF and 1,1,1,3,3- five chloro- 4, the molar ratios of 4,4- trifluorobutanes is 5~20:1, and 1,1,1, 3,3- five chloro- 4, the molar ratio of 4,4- trifluorobutanes and liquid phase composite catalyst is 0.2~1:1, and reaction temperature is 90 DEG C~120 DEG C, the reaction time is 1h~5h, and reaction pressure is 1.0MPa~2.5MPa；In a continuous process, HF and 1,1,1,3,3- five is chloro- 4,4,4- trifluorobutanes continuously enter reactor, preferred reaction condition are as follows: HF and 1,1,1,3,3- five chloro- 4, and 4,4- trifluoro fourths The molar ratio of alkane is 5~10:1,1,1,1,3,3- five chloro- 4, the inventory of 4,4- trifluorobutanes and rubbing for liquid phase composite catalyst You are than being 0.2~0.5:1, and reaction temperature is 100 DEG C~110 DEG C, and reaction pressure is 1.1MPa~1.5MPa.
Compared with prior art, the present invention includes following beneficial effect:
(1) reaction selectivity is high, and present invention introduces the acidity that compounding agent adjusts metal fluoride, improves reaction selectivity, The chloro- 1,1,1,4,4,4- hexafluoro -2- butylene selectivity of 2- is 95.0% or more；
(2) catalyst life is long, continuous operation 300h, and 1,1,1,3,3- five chloro- 4,4,4- trifluorobutane conversion ratios are close 100%, 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene selectivity are 95.0% or more.
Specific embodiment
It is following that explanation is described in further detail to the present invention in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment 1
Liquid phase fluorination reaction prepares 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, in the 250mL stainless steel height with stirring It is carried out in pressure kettle.12.4g TiF is successively put into reaction kettle4, 5.1g triethylamine, 12g HF and 5.96g 1,1,1,3,3- five Chloro- 4,4,4- trifluorobutanes, reaction temperature is 120 DEG C, reacts 5h.The gas-chromatography point after washing deacidification is sampled after reaction Analysis, the results showed that 1,1,1,3,3- five chloro- 4, the conversion ratios of 4,4- trifluorobutanes is 100%, 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- six The selectivity of fluoro- 2- butylene is 96.5%.
Embodiment 2~14
2~14 liquid phase fluorination reaction of embodiment prepares 2- chloro- 1,1, and Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene are same as Example 1, Except that it is as shown in table 1 to change liquid phase composite catalyst component, reaction temperature and reaction time, reaction result.
Table 1
Embodiment 15
In reaction kettle same as Example 1.19.0g TiCl is successively put into reaction kettle4, add 60g HF Fluorination treatment is carried out, treatment process excludes the HCl generated by gas phase mouth, controls pressure within 0.20MPa.It is warming up to 90 DEG C, constant temperature 2h, treatment process terminates.5.96g 1,1,1,3,3- five chloro- 4,4,4- trifluorobutanes, reaction are added into reaction kettle Temperature is 120 DEG C, is cooled down after reacting 2h.Sampling gas chromatographic analysis after washing deacidification, 1,1,1,3,3- five chloro- 4,4,4- tri- The conversion ratio of fluorine butane is 100%, 2- chloro- 1,1, and Isosorbide-5-Nitrae, the selectivity of 4,4- hexafluoro -2- butylene is 98.0%.
Embodiment 16~21
16~21 liquid phase fluorination reaction of embodiment prepares the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- and 1 phase of embodiment Together, except that adjusting liquid phase composite catalyst component ratio, HF and 1,1,1,3,3- five chloro- 4,4,4- trifluorobutanes rub , than the inventory with 1,1,1,3,3- five chloro- 4,4,4- trifluorobutanes, reaction result is as shown in table 2 for you.
Table 2
Embodiment 22
Continuous Liquid Phase fluorination carries out in 2L stainless steel autoclave, and the top of autoclave is equipped with destilling tower and reflux condensation mode Device, bottom are heated using oil cauldron, and tower top material is collected in -20 DEG C of cold baths after washing alkalinity deacidification.Into reaction kettle Successively put into 285g TiCl4, 75.9g triethylamine, 500g HF, the HCl generated by gas phase mouth exclusion, control system pressure is not More than 0.20MPa, 90 DEG C are warming up to, constant temperature 2h.Then by metering pump continuously by the chloro- 4,4,4- trifluoro fourth of 1,1,1,3,3- five Alkane and HF are squeezed into reactor, and 1,1,1,3,3- five chloro- 4, the feed rate of 4,4- trifluorobutanes is 128g/h, the charging of HF Rate is 72g/h, 1,1,1,3,3- five chloro- 4,4,4- trifluorobutanes and HF molar ratio are 1:8, and reaction temperature is 105 DEG C~110 DEG C, reaction pressure is 1.2~1.4MPa.The composition of top gaseous phase material is analyzed, reaction result is shown in Table 3.As shown in Table 3, continuously It running in 300h, 1,1,1,3,3- five chloro- 4,4,4- trifluorobutane conversion ratios are close to 100%, 2- chloro- 1,1, Isosorbide-5-Nitrae, and 4,4- six Fluoro- 2- butylene selectivity catalyst in 95.0% or more, reaction process keeps good stability.
Table 3

Claims (7)

1. a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, it is characterised in that the following steps are included: in liquid In the presence of phase composite catalyst, hydrogen fluoride and 1,1,1,3,3- five chloro- 4,4,4- trifluorobutane liquid-phase fluorinations prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, HF and 1,1,1,3,3- five chloro- 4, the molar ratios of 4,4- trifluorobutanes is 3~50:1,1,1,1, 3,3- five chloro- 4, the molar ratio of 4,4- trifluorobutanes and liquid phase composite catalyst is 0.1~3:1, and reaction temperature is 50 DEG C~150 DEG C, the reaction time is 0.5h~10h, and wherein liquid phase composite catalyst is made of metal fluoride and compounding agent, metal fluoride For TaF5、NbF5、TiF4Or SnF4, compounding agent is organic amine or quaternary ammonium salt, the molar ratio of compounding agent and metal fluoride is 0~ 2:1。
2. it is according to claim 1 it is a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, feature exists In the metal fluoride be TaF5Or TiF4。
3. it is according to claim 2 it is a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, feature exists In the metal fluoride be TiF4。
4. it is according to claim 1 it is a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, feature exists In the organic amine be n-propylamine, n-octyl amine, triethylamine, ethylenediamine, triethylene diamine, pyrroles, imidazoles, piperidines, pyridine or Pyrazine, the quaternary ammonium salt are tetramethyl ammonium chloride, etamon chloride, Methanaminium, N,N,N-trimethyl-, fluoride or tetraethyl ammonium fluoride.
5. it is according to claim 4 it is a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, feature exists It is n-propylamine, triethylamine, ethylenediamine, imidazoles or piperidines in the organic amine, the quaternary ammonium salt is Methanaminium, N,N,N-trimethyl-, fluoride.
6. it is according to claim 1 it is a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, feature exists In the compounding agent and metal fluoride molar ratio be 0.2~0.5:1.
7. it is according to claim 1 it is a kind of prepare 2- chloro- 1,1, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, feature exists In the HF and 1,1,1,3,3- five chloro- 4, the molar ratio of 4,4- trifluorobutanes is 5~20:1,1,1,1,3,3- five chloro- 4, The molar ratio of 4,4- trifluorobutanes and liquid phase composite catalyst is 0.2~1:1, and reaction temperature is 90 DEG C~120 DEG C, the reaction time For 1h~5h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112159301A (en) * 2020-09-29 2021-01-01 西安近代化学研究所 Synthetic method of 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene
CN112552141A (en) * 2020-12-18 2021-03-26 西安近代化学研究所 Preparation method of 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene

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Publication number Priority date Publication date Assignee Title
CN103508844A (en) * 2013-09-28 2014-01-15 西安近代化学研究所 Liquid-phase fluorination preparation method for 1, 2-dichloro-3, 3, 3-trifluoropropene
CN104072333A (en) * 2014-05-21 2014-10-01 巨化集团技术中心 Preparation method for 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene
CN107652160A (en) * 2017-10-25 2018-02-02 西安近代化学研究所 A kind of method for preparing the trans trifluoro propene of 1 chlorine 3,3,3

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103508844A (en) * 2013-09-28 2014-01-15 西安近代化学研究所 Liquid-phase fluorination preparation method for 1, 2-dichloro-3, 3, 3-trifluoropropene
CN104072333A (en) * 2014-05-21 2014-10-01 巨化集团技术中心 Preparation method for 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene
CN107652160A (en) * 2017-10-25 2018-02-02 西安近代化学研究所 A kind of method for preparing the trans trifluoro propene of 1 chlorine 3,3,3

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112159301A (en) * 2020-09-29 2021-01-01 西安近代化学研究所 Synthetic method of 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene
CN112159301B (en) * 2020-09-29 2022-12-13 西安近代化学研究所 Synthesis method of 2-chloro-1, 4-hexafluoro-2-butene
CN112552141A (en) * 2020-12-18 2021-03-26 西安近代化学研究所 Preparation method of 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene

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