A liquid phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene and application thereof
By using a liquid-phase method to carry out the dehydrofluorination reaction of polyethylene glycol and inorganic alkaline aqueous solution in two series high-pressure reactors, the problems of easy catalyst deactivation, low yield and excessive solvent in the synthesis of cis-1-chloro-2,3,3-trifluoropropylene in the prior art are solved. This achieves an efficient and green synthesis route, and improves selectivity and yield.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JUHUA GROUP TECH CENT
- Filing Date
- 2026-02-04
- Publication Date
- 2026-05-29
AI Technical Summary
In the existing technology, the synthesis method of cis-1-chloro-2,3,3-trifluoropropene has problems such as easy deactivation of catalyst, low yield, safety hazards, complex process and large amount of organic solvent used, making it difficult to achieve efficient and green synthesis.
A liquid-phase method was adopted, using polyethylene glycol as a phase transfer catalyst and an inorganic alkaline aqueous solution to carry out the dehydrofluorination reaction in two high-pressure reactors connected in series. Through the Lewis basicity of polyethylene glycol and the synergistic effect of ether oxygen atoms, the efficient synthesis of cis-1-chloro-2,3,3-trifluoropropylene was achieved, avoiding metal residue and separation problems.
The synthesis of cis-1-chloro-2,3,3-trifluoropropene with high selectivity and high yield was achieved, reducing the amount of organic solvent used, lowering costs, improving reaction efficiency and safety, and realizing the continuous reaction process.
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Figure CN122102833A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a liquid-phase synthesis method for cis-1-chloro-2,3,3-trifluoropropylene and its application. Background Technology
[0002] Cis-1-chloro-2,3,3-trifluoropropene, abbreviated as HCFO-1233yd(Z), is a fifth-generation ozone-depleting substance (ODS) substitute with "zero ODP, low GWP, and zero TFA degradation". It also has a high KB value (butanol value of pine resin), a suitable boiling point, high density, and low surface tension. It does not belong to the category of perfluorinated and polyfluoroalkyl substances (PFAS) and is an ideal substitute for AK-225 (1,2-dichloro-1,1,3,3,3-pentafluoropropane). It is widely used in industrial cleaning, foam fire extinguishing, refrigeration, pharmaceutical and pesticide synthesis and other fields.
[0003] The development of an efficient synthetic method for cis-1-chloro-2,3,3-trifluoropropene has significant academic and industrial importance. Theoretically, this molecule contains a cis stereoconfiguration with carbon-carbon double bonds and polyfluorinated substituents. Achieving its highly selective synthesis involves optimizing stereochemical control and fluorine atom introduction strategies. This provides an important research model for organofluorine chemistry and stereoselective catalysis, deepening our understanding of reaction mechanisms and structure-property relationships. In terms of applications, this compound is a key component of potential next-generation refrigerants or blowing agents with extremely low GWP and negligible ODP. Developing an economical and green synthetic route will help promote sustainable refrigeration technology and alleviate climate change pressures. Simultaneously, the active chlorine and trifluoromethyl functional groups in its molecule make it a valuable intermediate for the synthesis of fluorinated pharmaceuticals, pesticides, and functional materials. The establishment of a controllable synthetic method for cis-1-chloro-2,3,3-trifluoropropene will improve the accessibility of fluorinated fine chemicals and promote research and development in related fields. Therefore, the synthesis of this compound is not only a technical challenge in the field of fluorine chemistry, but also a key foundation for the development of advanced materials and environmental science.
[0004] A series of methods for synthesizing cis-1-chloro-2,3,3-trifluoropropene have been reported in the prior art, as detailed below: Patent document CN107250088A discloses a method for manufacturing 1-chloro-2,3,3-trifluoropropene, specifically including a step of dehydrofluorinating 3-chloro-1,1,2,2-tetrafluoropropane (244ca). The dehydrofluorination process is carried out in the gas phase with a contact time of 1 to 100 seconds, and the product is continuously taken out. When the dehydrofluorination reaction is carried out in the gas phase, the catalyst can be alumina, chromium oxide, tin oxide, ferric chloride, aluminum fluoride, aluminum fluoride, chromium fluoride, magnesium oxide, magnesium fluoride, magnesium fluoride, lanthanum oxide, lanthanum oxyfluoride, lanthanum fluoride, nickel, nickel oxide, or a catalyst composed of two or more of them. Patent document CN115803308A discloses a method for producing 1-chloro-2,3,3-trifluoropropene. This method involves reacting 3-chloro-1,1,2,2-tetrafluoropropane 244ca with hydrogen fluoride in the gas phase in the presence of a catalyst to produce 1-chloro-2,3,3-trifluoropropene. The catalyst used is a metal compound catalyst activated in the gas phase with a fluorine compound (hydrogen fluoride, trifluoromethane, or difluoromethane) that does not contain chlorine atoms. However, the gas-phase method suffers from the problem of easy catalyst deactivation and low yield.
[0005] Patent document CN117396453A discloses a method for manufacturing 1-chloro-2,3,3-trifluoropropene. In this method, 1,3-dichloro-2,3,3-trifluoropropene is contacted with a metal salt and a zero-valent metal, followed by contact with an acid to produce 1-chloro-2,3,3-trifluoropropene. The metal salt contains copper, iron, cobalt, or nickel atoms, and the zero-valent metal is zinc, magnesium, iron, cobalt, or nickel. The above-mentioned reduction and dechlorination process may lack selectivity, and the zero-valent metal is highly reactive, potentially generating hydrogen gas upon contact with acid, posing a safety hazard.
[0006] Patent document CN120208750A discloses a method for preparing 1-chloro-2,3,3-trifluoropropene, comprising: (1) an addition step: trifluorochloroethylene and methanol are reacted by an addition process under the action of a free radical initiator to obtain 2-chloro-2,3,3-trifluoropropanol; (2) a chlorination step: 2-chloro-2,3,3-trifluoropropanol is reacted by a chlorination reaction under the combined action of a chlorinating agent and a catalyst to obtain 1,2-dichloro-2,3,3-trifluoropropane; (3) a dehydrochlorination step: 1,2-dichloro-2,3,3-trifluoropropane is dehydrochlorinated in the gas phase to obtain 1-chloro-2,3,3-trifluoropropene. The process of this invention is relatively complex and the separation and purification costs are high.
[0007] The commonly used liquid-phase method also suffers from the problem of high organic solvent consumption. Therefore, it is of great significance to develop a method for synthesizing cis-1-chloro-2,3,3-trifluoropropene with low organic solvent consumption, high conversion rate and selectivity. Summary of the Invention
[0008] To address the shortcomings of the existing technology, this invention provides a method for synthesizing cis-1-chloro-2,3,3-trifluoropropene. This method employs a liquid-phase approach, which offers high selectivity and avoids metal residue and separation issues. The phase transfer catalyst is polyethylene glycol, which is easily recyclable. The synthesis of cis-1-chloro-2,3,3-trifluoropropene can be achieved without the addition of external organic solvents.
[0009] The specific technical solution adopted is as follows: A liquid-phase synthesis method for cis-1-chloro-2,3,3-trifluoropropene, comprising: Cis-1-chloro-2,3,3-trifluoropropene was prepared by dehydrofluorination of 3-chloro-1,1,2,2-tetrafluoropropane in the presence of polyethylene glycol and an aqueous inorganic alkali solution.
[0010] This invention introduces polyethylene glycol as a phase transfer catalyst in the dehydrofluorination reaction of 3-chloro-1,1,2,2-tetrafluoropropane. Multiple ether oxygen atoms on its molecular chain possess lone pairs of electrons and can act as Lewis bases. These oxygen atoms, through synergistic action, can complex cations (such as K+) in the aqueous phase. + Na + This exposes the paired aqueous anions, which then enter the organic phase along with the polyethylene glycol, thereby reacting in the organic phase.
[0011] Preferably, the molecular weight of the polyethylene glycol is 200-600 g / mol. Low molecular weight polyethylene glycol has good solubility and flowability, can be uniformly dispersed in the reaction system, improves mass transfer efficiency, has good thermal stability, and avoids the problem of nitrogen impurity residue that may be caused by quaternary ammonium salts. In addition, the ether oxygen atoms in the PEG molecular chain have binding interactions with different alkali metal ions, which helps to further improve the reaction efficiency.
[0012] Specifically, the polyethylene glycol is hydroxyl-terminated polyethylene glycol or alkoxy-terminated polyethylene glycol, and the alkoxy group is further methoxy or ethoxy.
[0013] The polyethylene glycol is preferably hydroxyl-terminated polyethylene glycol, which has better phase transfer catalytic performance and also has proton donation capability, resulting in superior performance.
[0014] Preferably, the inorganic base is an alkali metal hydroxide, including but not limited to potassium hydroxide, sodium hydroxide, cesium hydroxide, etc. More preferably, it is potassium hydroxide, low molecular weight polyethylene glycol, and K. + It has a stronger ability to combine.
[0015] Preferably, the mass ratio of 3-chloro-1,1,2,2-tetrafluoropropane to polyethylene glycol is 100:0.5~5, the molar ratio of 3-chloro-1,1,2,2-tetrafluoropropane to inorganic base is 1:1~3, and the mass concentration range of the inorganic base aqueous solution is 20-40wt%.
[0016] Preferably, the temperature for the defluorination reaction is 80~120 ℃ and the reaction time is 0.5~2 h.
[0017] Furthermore, the defluorination reaction is carried out in high-pressure reactors A and B connected in series. Preferably, the rotation speed in both high-pressure reactors A and B is set to 600~1000 rpm, and the materials of high-pressure reactors A and B are Hastelloy or nickel alloy.
[0018] Using two high-pressure reactors in series can greatly enhance mass transfer and mixing, significantly shorten reaction time, suppress side reactions, improve selectivity, and achieve continuous reaction process.
[0019] Furthermore, the specific steps of the defluorination reaction are as follows: (1) 3-chloro-1,1,2,2-tetrafluoropropane is introduced into high-pressure reactor A by feed pump 1, polyethylene glycol is introduced into high-pressure reactor A by feed pump 2, and an inorganic alkaline aqueous solution is introduced into high-pressure reactor A by feed pump 3. The temperature is raised to react (temperature 80~120 ℃, reaction residence time is 0.5-1.5h). (2) After the reaction in high pressure reactor A has been going on for a certain period of time, the material in it is pumped into high pressure reactor B by feed pump 4. At the same time, inorganic alkali solution is introduced into high pressure reactor B by feed pump 5, and the temperature is raised to react (temperature 80~120 ℃, reaction residence time is 0.5-1.5h).
[0020] Preferably, the mass ratio of the inorganic alkaline aqueous solution added to high-pressure reactor A and high-pressure reactor B is 1:0.01~1. The secondary addition of inorganic alkaline aqueous solution can further enhance the defluorination reaction, improve selectivity and yield, and polyethylene glycol is added continuously only in high-pressure reactor A.
[0021] The 3-chloro-1,1,2,2-tetrafluoropropane is prepared from 2,2,3,3-tetrafluoropropanol and thionyl chloride through chlorination and thermal decomposition reactions.
[0022] 2,2,3,3-Tetrafluoropropanol was mixed with N,N-dimethylformamide and added dropwise to a container containing thionyl chloride for chlorination. After the reaction was completed, the resulting reaction solution was heated to 80-115°C for thermal decomposition distillation. The distillate was collected and washed with ice water and alkali to obtain 3-chloro-1,1,2,2-tetrafluoropropane.
[0023] Preferably, in the chlorination reaction, the molar ratio of 2,2,3,3-tetrafluoropropanol to thionyl chloride is 1:1 to 1.5, and the amount of N,N-dimethylformamide is 1 to 20% of the mass of 2,2,3,3-tetrafluoropropanol.
[0024] More preferably, the chlorination reaction temperature is 0~40℃ and the chlorination reaction time is 1~5 h.
[0025] The method of this invention has high selectivity for cis-1-chloro-2,3,3-trifluoropropene, few side reactions, and can synthesize cis-1-chloro-2,3,3-trifluoropropene in ≥90% yield.
[0026] The present invention also provides the application of the liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropylene in the preparation of cleaning agents, refrigerants, foaming agents or fire extinguishing agents.
[0027] This invention also provides the application of the liquid-phase synthesis method for cis-1-chloro-2,3,3-trifluoropropene in the field of organic synthesis.
[0028] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The method of the present invention utilizes the dehydrofluorination reaction of 3-chloro-1,1,2,2-tetrafluoropropane in the presence of polyethylene glycol and inorganic alkaline aqueous solution, which realizes the efficient synthesis of cis-1-chloro-2,3,3-trifluoropropene. It is green, environmentally friendly and efficient, with a short synthesis route and high conversion rate and selectivity.
[0029] (2) The phase transfer catalyst polyethylene glycol used in this invention has the advantages of easy recovery and low cost compared with traditional quaternary ammonium salts, crown ethers and other catalysts.
[0030] (3) The method of the present invention utilizes polyethylene glycol as a phase transfer catalyst and an inorganic alkaline aqueous solution as a catalyst. Multiple ether oxygen atoms on the polyethylene glycol molecular chain carry lone pairs of electrons and can act as Lewis bases. These oxygen atoms, through synergistic action, can complex cations (such as K+) in the aqueous phase. + Na + This exposes the paired aqueous anions, which then enter the organic phase along with the polyethylene glycol, thus facilitating the reaction within the organic phase. Polyethylene glycol is non-toxic, possesses good solubility and flowability, is low in cost, and can be uniformly dispersed in the reaction system, improving mass transfer efficiency.
[0031] (4) In the reaction process, the present invention uses two high-pressure reactors connected in series and adds alkali solution in batches to greatly enhance mass transfer and mixing at high speed, significantly shorten the reaction time, suppress side reactions, improve selectivity, and realize the continuous reaction process.
[0032] (5) The method of the present invention does not require the use of traditional organic solvents. Compared with the prior art that uses aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane and octane, and ether organic solvents such as diethyl ether and tetrahydrofuran, the route of the present invention is green, environmentally friendly and efficient.
[0033] (6) The method of the present invention sets up a specific reaction system and combines two reactors in series, while controlling the process parameters. In the end, the system does not reduce the conversion rate and selectivity without adding traditional organic solvents such as toluene. The method of the present invention has a selectivity of ≥90% for cis-1-chloro-2,3,3-trifluoropropene and a yield of ≥80% for cis-1-chloro-2,3,3-trifluoropropene. Attached Figure Description
[0034] Figure 1 The high-performance liquid chromatogram of 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) is shown.
[0035] Figure 2 This is a high-performance liquid chromatogram of the product obtained from the defluorination reaction.
[0036] Figure 3 This is a simplified schematic diagram of a two-vessel high-pressure reactor connected in series. Detailed Implementation
[0037] To make the objectives, features, and advantages of this invention more apparent and understandable, a detailed description is provided below through specific embodiments. Many specific details are set forth in the following description to provide a thorough understanding of the invention. However, the invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below. Technical features in various embodiments of the invention can be combined appropriately without mutual conflict.
[0038] Unless otherwise specified, the operating methods in the following examples are generally performed under conventional conditions or as recommended by the manufacturer. Contents not described in detail in this specification are prior art known to those skilled in the art. Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.
[0039] All scopes disclosed herein include endpoints, and endpoints can be combined independently of each other.
[0040] Unless otherwise stated herein or clearly contradicted by the context, the terms “an”, “a”, and “the” do not imply a limitation of quantity and should be interpreted to cover both the singular and the plural.
[0041] This invention provides a liquid-phase synthesis method for cis-1-chloro-2,3,3-trifluoropropene, comprising: subjecting 3-chloro-1,1,2,2-tetrafluoropropane to a dehydrofluorination reaction in the presence of polyethylene glycol and an inorganic alkaline aqueous solution to prepare cis-1-chloro-2,3,3-trifluoropropene. A representative high-performance liquid chromatography (HPLC) chromatogram of the product is shown below. Figure 2 As shown.
[0042] In some preferred embodiments, the molecular weight of polyethylene glycol is 200-600 g / mol.
[0043] In some preferred embodiments, the polyethylene glycol is hydroxyl-terminated polyethylene glycol.
[0044] In some preferred embodiments, the polyethylene glycol is alkoxy-terminated polyethylene glycol, and the alkoxy group is methoxy or ethoxy.
[0045] In some preferred embodiments, the inorganic base is an alkali metal hydroxide, including potassium hydroxide, sodium hydroxide, or cesium hydroxide.
[0046] In some preferred embodiments, the mass ratio of 3-chloro-1,1,2,2-tetrafluoropropane to polyethylene glycol is 100:0.5~5, the molar ratio of 3-chloro-1,1,2,2-tetrafluoropropane to inorganic base is 1:1~3, and the mass concentration range of the inorganic base aqueous solution is 20-40wt%.
[0047] In some preferred embodiments, the temperature of the defluorination reaction is 80~120 °C and the reaction time is 0.5~2 h.
[0048] In some preferred embodiments, the provided liquid-phase synthesis method for cis-1-chloro-2,3,3-trifluoropropene is carried out in a two-reactor series high-pressure reactor, as shown in the schematic diagram below. Figure 3 As shown.
[0049] In some preferred embodiments, the specific steps of the defluorination reaction are as follows: (1) 3-chloro-1,1,2,2-tetrafluoropropane is introduced into high-pressure reactor A by feed pump 1, polyethylene glycol is introduced into high-pressure reactor A by feed pump 2, and an inorganic alkaline aqueous solution is introduced into high-pressure reactor A by feed pump 3, and the temperature is raised to react. (2) After the reaction in high pressure reactor A has been going on for a certain period of time, the material in it is pumped into high pressure reactor B by feed pump 4, and at the same time, inorganic alkali solution is introduced into high pressure reactor B by feed pump 5 to raise the temperature and react. In both high-pressure reactor A and high-pressure reactor B, the rotation speed is set to 600~1000 rpm.
[0050] In some preferred embodiments, the 3-chloro-1,1,2,2-tetrafluoropropane is prepared from 2,2,3,3-tetrafluoropropanol and thionyl chloride via a chlorination and thermal decomposition reaction; the specific preparation steps include: 2,2,3,3-Tetrafluoropropanol and N,N-dimethylformamide were mixed and added dropwise to a container containing thionyl chloride for chlorination. The chlorination reaction was carried out at 0–40 °C for 1–5 h, with a molar ratio of 2,2,3,3-tetrafluoropropanol to thionyl chloride of 1:1–1.5. The amount of N,N-dimethylformamide was 1–20% of the mass of 2,2,3,3-tetrafluoropropanol. After the reaction, the resulting reaction solution was heated to 80–115 °C for thermal decomposition distillation. The distillate was collected and washed with ice water and alkali to obtain 3-chloro-1,1,2,2-tetrafluoropropane. A representative high-performance liquid chromatogram of 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) is shown below. Figure 1 As shown.
[0051] Example 1 2,2,3,3-Tetrafluoropropanol (132.06 g) and N,N-dimethylformamide (13.2 g) were mixed and added dropwise to a three-necked flask containing thionyl chloride (130.87 g) for chlorination. The molar ratio of 2,2,3,3-tetrafluoropropanol to thionyl chloride was 1:1.1. The amount of N,N-dimethylformamide was 10% of the mass of 2,2,3,3-tetrafluoropropanol. The reaction temperature was 20 °C. After the addition was complete, the reaction continued for 1 h. After the reaction was completed, the reaction solution was heated to 90-115 °C for thermal decomposition distillation. The distillate was collected and washed with ice water and alkali to obtain 3-chloro-1,1,2,2-tetrafluoropropane with a yield of 85.2%.
[0052] Liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene was carried out in two series-connected high-pressure reactors: In both reactors A and B, the rotation speed was set to 700 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, hydroxyl-terminated polyethylene glycol (molecular weight 400 g / mol) was pumped in by feed pump 2 at a rate of 0.75 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 187 g / min. The reaction was carried out at 100℃ with a residence time of 1 h. Feed pump 4 continued to pump the material from reactor A into reactor B at a rate of 338 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH aqueous solution at a rate of 187 g / min. The temperature of reactor B was maintained at 100℃, and the residence time was 1 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.3% and a yield of 90.2%.
[0053] Example 2 2,2,3,3-Tetrafluoropropanol (132.06 g) and N,N-dimethylformamide (26.4 g) were mixed and added dropwise to a three-necked flask containing thionyl chloride (118.97 g) for chlorination. The molar ratio of 2,2,3,3-tetrafluoropropanol to thionyl chloride was 1:1. The amount of N,N-dimethylformamide was 20% of the mass of 2,2,3,3-tetrafluoropropanol. The reaction temperature was 10 °C. After the addition was complete, the reaction continued for 2 h. After the reaction was completed, the reaction solution was heated to 90-115 °C for thermal decomposition distillation. The distillate was collected and washed with ice water and alkali to obtain 3-chloro-1,1,2,2-tetrafluoropropane with a yield of 86.0%.
[0054] Liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene was carried out in two series-connected high-pressure reactors: In both reactors A and B, the rotation speed was set to 600 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 75.3 g / min, hydroxyl-terminated polyethylene glycol (molecular weight 300 g / mol) was pumped in by feed pump 2 at a rate of 0.75 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 140.3 g / min. The reaction was carried out at 110 °C with a residence time of 1 h. Feed pump 4 continued to pump the material from reactor A into reactor B at a rate of 216 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH aqueous solution at a rate of 47.0 g / min. The temperature of reactor B was maintained at 110 °C, and the residence time was 0.5 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.0% and a yield of 90.5%.
[0055] Example 3 2,2,3,3-Tetrafluoropropanol (132.06 g) and N,N-dimethylformamide (19.8 g) were mixed and added dropwise to a three-necked flask containing thionyl chloride (142.80 g) for chlorination. The molar ratio of 2,2,3,3-tetrafluoropropanol to thionyl chloride was 1:1.2, and the amount of N,N-dimethylformamide was 15% of the mass of 2,2,3,3-tetrafluoropropanol. The reaction temperature was 10 °C, and the reaction continued for 2 h after the addition was complete. After the reaction was completed, the reaction solution was heated to 90-115 °C for thermal decomposition distillation. The distillate was collected and washed with ice water and alkali to obtain 3-chloro-1,1,2,2-tetrafluoropropane with a yield of 85.9%.
[0056] Liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene was carried out in two series-connected high-pressure reactors: In both reactors A and B, the rotation speed was set to 800 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in at a rate of 150.5 g / min by feed pump 1, hydroxyl-terminated polyethylene glycol (molecular weight 300 g / mol) was pumped in at a rate of 1.5 g / min by feed pump 2, and 30 wt% KOH aqueous solution was pumped in at a rate of 280.5 g / min by feed pump 3. The reaction was carried out at 105 °C with a residence time of 1 h. Feed pump 4 continued to pump the material from reactor A into reactor B at a rate of 446 g / min, while feed pump 5 simultaneously pumped 30 wt% KOH aqueous solution at a rate of 93.5 g / min. The temperature of reactor B was maintained at 105 °C, and the residence time was 0.5 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.8% and a yield of 90.5%.
[0057] Example 4 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 1 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene: In both high-pressure reactors A and B, the rotation speed was set to 900 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 300.1 g / min, hydroxyl-terminated polyethylene glycol (molecular weight 600 g / mol) was pumped in by feed pump 2 at a rate of 3.0 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 561 g / min. The reaction was carried out at 90°C, with a reaction residence time of 0.5 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 864 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH aqueous solution at a rate of 187 g / min. The temperature of high-pressure reactor B was controlled at 90°C, and the reaction residence time was 1 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.6% and a yield of 90.2%.
[0058] Example 5 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 2 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene: In both high-pressure reactors A and B, the rotation speed was set to 1000 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, feed pump 2 pumped in hydroxyl-terminated polyethylene glycol (molecular weight 200 g / mol) at a rate of 0.75 g / min, and feed pump 3 pumped in a 20 wt% NaOH aqueous solution at a rate of 200 g / min. The reaction was carried out at 80°C, with a reaction residence time of 1 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 351 g / min, while feed pump 5 simultaneously pumped in a 20 wt% NaOH aqueous solution at a rate of 133 g / min. The temperature of high-pressure reactor B was controlled at 110°C, and the reaction residence time was 1 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.0% and a yield of 88.2%.
[0059] Example 6 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 1 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene. In both high-pressure reactors A and B, the rotation speed was set to 600 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, methoxy-terminated polyethylene glycol (molecular weight 300 g / mol) was pumped in by feed pump 2 at a rate of 1.5 g / min, and 40 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 336.6 g / min. The reaction was carried out at 100°C, with a reaction residence time of 1.5 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 488 g / min, while feed pump 5 simultaneously pumped in 40 wt% KOH aqueous solution at a rate of 84.1 g / min. The temperature of high-pressure reactor B was controlled at 100°C, and the reaction residence time was 0.5 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 90.5% and a yield of 86.2%.
[0060] Example 7 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 3 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene. In both high-pressure reactors A and B, the rotation speed was set to 700 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, methoxy-terminated polyethylene glycol (molecular weight 300 g / mol) was pumped in by feed pump 2 at a rate of 3.0 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 168.0 g / min. The reaction was carried out at 105°C, with a reaction residence time of 1 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 321 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH solution at a rate of 168.0 g / min. The temperature of high-pressure reactor B was controlled at 105°C, and the reaction residence time was 0.5 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 91.3% and a yield of 80.2%.
[0061] Example 8 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 2 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene. In both high-pressure reactors A and B, the rotation speed was set to 800 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, hydroxyl-terminated polyethylene glycol (molecular weight 400 g / mol) was pumped in by feed pump 2 at a rate of 4.5 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 140.0 g / min. The reaction was carried out at 105°C, with a reaction residence time of 1 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 295 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH aqueous solution at a rate of 140.0 g / min. The temperature of high-pressure reactor B was controlled at 105°C, and the reaction residence time was 0.5 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 91.5% and a yield of 90.2%.
[0062] Example 9 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 1 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene: In both high-pressure reactors A and B, the rotation speed was set to 900 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, hydroxyl-terminated polyethylene glycol (molecular weight 600 g / mol) was pumped in by feed pump 2 at a rate of 6.0 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 250.0 g / min. The reaction was carried out at 105°C, with a reaction residence time of 1 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 406 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH aqueous solution at a rate of 124.0 g / min. The temperature of high-pressure reactor B was controlled at 105°C, and the reaction residence time was 1 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.5% and a yield of 91.6%.
[0063] Example 10 In this embodiment, cis-1-chloro-1,1,2,2-tetrafluoropropane prepared in Example 3 was used for the liquid-phase synthesis of cis-1-chloro-2,3,3-trifluoropropene: In both high-pressure reactors A and B, the rotation speed was set to 1000 rpm. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, hydroxyl-terminated polyethylene glycol (molecular weight 500 g / mol) was pumped in by feed pump 2 at a rate of 7.5 g / min, and 30 wt% KOH aqueous solution was pumped in by feed pump 3 at a rate of 207.0 g / min. The reaction was carried out at 100°C, with a reaction residence time of 1 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 365 g / min, while feed pump 5 simultaneously pumped in 30 wt% KOH aqueous solution at a rate of 166.0 g / min. The temperature of high-pressure reactor B was controlled at 100°C, and the reaction residence time was 1 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.8% and a yield of 91.0%.
[0064] Comparative Example 1 In this comparative example, cis-1-chloro-2,3,3-trifluoropropane prepared in Example 1 was used for liquid-phase synthesis: the reactor was changed from a two-vessel series high-pressure reactor to a single reactor.
[0065] In a single-reactor autoclave, under stirring at 700 rpm, 3-chloro-1,1,2,2-tetrafluoropropane was pumped in at a rate of 150.5 g / min by feed pump 1, hydroxyl-terminated polyethylene glycol (molecular weight 400 g / mol) was pumped in at a rate of 0.75 g / min by feed pump 2, and 30 wt% KOH aqueous solution was pumped in at a rate of 375 g / min by feed pump 3. The reaction was carried out at 100 °C, and the reaction residence time was controlled at 2 h. After centrifugation and other post-treatment, crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer was obtained. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 90.6% and a yield of 70.3%.
[0066] Comparative Example 2 In this comparative example, cis-1-chloro-2,3,3-trifluoropropane prepared in Example 1 was used for liquid-phase synthesis: in both high-pressure reactor A and high-pressure reactor B, the rotation speed was set to 700 rpm, and the hydroxyl-terminated polyethylene glycol catalyst was replaced with the solid phase transfer catalyst tetrabutylammonium bromide. The solid phase transfer catalyst tetrabutylammonium bromide was pre-dissolved in a 30wt% KOH alkaline solution, with a molar ratio of tetrabutylammonium bromide to solid alkali of 0.0012:1. 3-chloro-1,1,2,2-tetrafluoropropane was pumped in by feed pump 1 at a rate of 150.5 g / min, and the mixed solution of KOH and tetrabutylammonium bromide was pumped in by feed pump 2 at a rate of 285 g / min. The reaction was carried out at 100℃, with a reaction residence time of 1 h. Feed pump 4 continued to pump the material from high-pressure reactor A into high-pressure reactor B at a rate of 435 g / min, while feed pump 5 simultaneously pumped in a 30wt% KOH aqueous solution at a rate of 93.5 g / min. The temperature of high-pressure reactor B was controlled at 100℃, and the reaction residence time was 1 h. h. After centrifugation and separation, the reaction solution was processed to obtain crude cis-1-chloro-2,3,3-trifluoropropene with an organic layer. The crude product was then distilled to obtain cis-1-chloro-2,3,3-trifluoropropene with a selectivity of 92.5% and a yield of 60.3%.
[0067] The embodiments described above provide a detailed explanation of the technical solutions of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, or similar substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A liquid-phase synthesis method for cis-1-chloro-2,3,3-trifluoropropene, characterized in that, include: Cis-1-chloro-2,3,3-trifluoropropene was prepared by dehydrofluorination of 3-chloro-1,1,2,2-tetrafluoropropane in the presence of polyethylene glycol and an aqueous inorganic alkali solution.
2. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 1, characterized in that, The molecular weight of the polyethylene glycol is 200~600 g / mol.
3. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 1, characterized in that, The polyethylene glycol mentioned is hydroxyl-terminated polyethylene glycol.
4. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 3, characterized in that, The polyethylene glycol mentioned is alkoxy-terminated polyethylene glycol, and in alkoxy-terminated polyethylene glycol, the alkoxy group is methoxy or ethoxy.
5. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropylene according to claim 1, characterized in that, The inorganic base is an alkali metal hydroxide, including potassium hydroxide, sodium hydroxide, or cesium hydroxide.
6. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 1, characterized in that, The mass ratio of 3-chloro-1,1,2,2-tetrafluoropropane to polyethylene glycol is 100:0.5~5, the molar ratio of 3-chloro-1,1,2,2-tetrafluoropropane to inorganic base is 1:1~3, and the mass concentration range of the inorganic base aqueous solution is 20-40wt%.
7. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 1, characterized in that, The temperature for the defluorination reaction is 80~120 ℃, and the reaction time is 0.5~2 h.
8. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 1, characterized in that, The defluorination reaction is carried out in high-pressure reactors A and B connected in series.
9. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 8, characterized in that, In both high-pressure reactor A and high-pressure reactor B, the rotation speed is set to 600~1000 rpm.
10. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 8, characterized in that, The specific steps of the dehydrofluorination reaction are as follows: (1) 3-chloro-1,1,2,2-tetrafluoropropane, polyethylene glycol and inorganic alkali aqueous solution were introduced into high-pressure reactor A and the temperature was raised to react; (2) After the reaction in high-pressure reactor A has been going on for a certain period of time, the material in it is pumped into high-pressure reactor B, and an inorganic alkaline aqueous solution is introduced into high-pressure reactor B to raise the temperature for reaction.
11. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 1, characterized in that, The 3-chloro-1,1,2,2-tetrafluoropropane is prepared from 2,2,3,3-tetrafluoropropanol and thionyl chloride through chlorination and thermal decomposition reactions.
12. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 11, characterized in that, 2,2,3,3-Tetrafluoropropanol was mixed with N,N-dimethylformamide and added dropwise to a container containing thionyl chloride for chlorination. After the reaction was completed, the resulting reaction solution was heated to 80-115°C for thermal decomposition distillation. The distillate was collected and washed with ice water and alkali to obtain 3-chloro-1,1,2,2-tetrafluoropropane.
13. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 11, characterized in that, In the chlorination reaction, the molar ratio of 2,2,3,3-tetrafluoropropanol to thionyl chloride is 1:1 to 1.5, and the amount of N,N-dimethylformamide used is 1 to 20% of the mass of 2,2,3,3-tetrafluoropropanol.
14. The liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to claim 11, characterized in that, The chlorination reaction temperature is 0~40℃, and the chlorination reaction time is 1~5 h.
15. The application of the liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropene according to any one of claims 1-14 in the field of organic synthesis.
16. The application of the liquid-phase synthesis method of cis-1-chloro-2,3,3-trifluoropropylene according to any one of claims 1-14 in the preparation of cleaning agents, refrigerants, foaming agents or fire extinguishing agents.