CN-121990870-A - Synthesis method of 1,2, 3-pentafluoropropane and 2,3, 3, 3-tetrafluoropropene

CN121990870ACN 121990870 ACN121990870 ACN 121990870ACN-121990870-A

Abstract

The invention belongs to the fields of refrigerants, fire protection, new materials for fluoride industry, foaming agents and chemical synthesis, and particularly relates to a synthesis method of 1,2, 3-pentafluoropropane and 2, 3-tetrafluoropropene. The synthesis method of the 1,2, 3-pentafluoropropane comprises the step of carrying out a first reaction of 3, 3-trifluoropropene, a first catalyst, an HF source and a selective fluorine reagent in a first solvent to obtain the 1,2, 3-pentafluoropropane. The synthetic method of the 2, 3-tetrafluoropropene comprises the following steps: and carrying out a second reaction on the obtained 1,2, 3-pentafluoropropane in the presence of a second catalyst to obtain 2, 3-tetrafluoropropene. The synthesis method of the 1,2, 3-pentafluoropropane has the advantages of simple operation, short time consumption, mild reaction, simple reagents required by the reaction, high substrate conversion rate, high selectivity of target products and the like, and is beneficial to industrialized production. The preparation method of the 2, 3-tetrafluoropropene provided by the invention has the advantages of safety, environmental protection, simple operation, mild reaction, high yield, high selectivity of target products, high reaction speed and the like, and is beneficial to industrial production.

Inventors

BAI JUNCHUAN
NING ZHICHAO
Zhang Dongdu
TANG HUOQIANG
XU SHENG
LIU QUNFANG
Dai Yinhao
YANG HENG
LIU GUANGWEN
Ma Zhuofan

Assignees

东莞东阳光科研发有限公司

Dates

Publication Date: 20260508
Application Date: 20260228

Claims (10)

1. A method for synthesizing 1,2, 3-pentafluoropropane, comprising: , performing a first reaction of 3, 3-trifluoropropene, a first catalyst, an HF source and a selective fluorine reagent in a first solvent to obtain 1,2, 3-pentafluoropropane; wherein the selective fluorine reagent comprises 1-chloromethyl-4-fluoro-1, 4-diazotized bicyclo [2.2.2] octane bis (tetrafluoroborate).
2. The synthesis method according to claim 1, wherein the HF source comprises at least one of Et 3 N xHF, pyr yHF, wherein x and y are each independently selected from integers of 1 to 10, and/or The HF source comprises at least one of Et 3 N.3HF, pyr.HF, preferably a mixture of Et 3 N.3HF and pyr.HF; Optionally, the molar ratio of Et 3 N.3HF to pyr.HF in the mixture of Et 3 N.3HF and pyr.HF is 1:1 to 1:10, preferably 1:1 to 1:8, more preferably 1:4; Preferably, the first catalyst comprises at least one of 4-iodotoluene, 1-iodo-4-methoxybenzene, ethyl 4-iodobenzoate, 2-iodo-1, 3-dimethoxybenzene, 2- (2-iodophenyl) -2-propanol or 2-iodobenzoic acid, more preferably, the first catalyst comprises at least one of 4-iodotoluene, 1-iodo-4-methoxybenzene, 2-iodo-1, 3-dimethoxybenzene, and most preferably, the first catalyst comprises at least one of 4-iodotoluene, 1-iodo-4-methoxybenzene.
3. The synthesis method according to any one of claims 1 to 2, wherein the reaction temperature of the first reaction is 20 ℃ to 50 ℃, preferably selected from 20 ℃ to 40 ℃, more preferably 30 ℃, and/or The reaction time of the first reaction is 14 hours or more, and/or The first solvent comprises at least one of acetonitrile, dichloromethane, chloroform, carbon tetrachloride, 1-dichloroethane, preferably 1, 1-dichloroethane, and/or The molar ratio of the 3, 3-trifluoropropene to the first catalyst is 1:1-10:1, or 3:1-5:1, and/or The molar ratio of the 3, 3-trifluoropropene to the selective fluorine reagent is 1:1-10:1, or 7:1-8:1, and/or The molar ratio of the 3, 3-trifluoropropene to the F element in the HF source is 1:2 or less, preferably 1:2-1:10, and/or Optionally, 0.1 mol-10 mol of 3, 3-trifluoropropene is added per 1L of the first solvent, and/or Preferably, the first reaction is carried out under nitrogen atmosphere or inert gas atmosphere; optionally, the inert gas in the first reaction comprises at least one of helium, neon, argon, krypton, xenon.
4. A method for synthesizing 2, 3-tetrafluoropropene, comprising: , The synthesis method of 1,2, 3-pentafluoropropane according to any one of claims 1 to 3, and then carrying out a second reaction on the obtained 1,2, 3-pentafluoropropane in the presence of a second catalyst to obtain 2, 3-tetrafluoropropene.
5. The synthetic method according to claim 4, wherein the reaction temperature of the second reaction is 200 ℃ to 400 ℃; Optionally, the second reaction is carried out in a continuous reactor filled with the second catalyst.
6. The synthesis method according to claim 4 to 6, The 1,2, 3-pentafluoropropane is mixed with carrier gas and then introduced into a continuous reactor for reaction, and/or The volume space velocity of the 1,2, 3-pentafluoropropane and the carrier gas in the second reaction is 100h -1 ~1000h -1 , and/or The carrier gas comprising an inert gas and/or nitrogen, and/or The inert gas in the carrier gas in the second reaction comprises at least one of helium, neon, argon, krypton and xenon, and/or The molar ratio of the 1,2, 3-pentafluoropropane to the carrier gas is 1:5-1:20, or 1:10.
7. The synthesis method according to any one of claims 4 to 6, wherein the second catalyst comprises any one of (1) to (4): (1) A procatalyst, or (2) A procatalyst and a cocatalyst, or (3) A main catalyst, a cocatalyst and a forming aid, or (4) A main catalyst and a forming aid; optionally, the main catalyst in the groups (1) - (4) comprises an oxide of a first metal element and/or Optionally, the first metal element in the oxide of the first metal element in the groups (1) - (4) independently comprises at least one of Cr, mn, fe, zn, ni, cu, co, al, mg, ga, in, Y, zr, ti, nb, preferably at least one of Cr, al, fe, mg, more preferably at least one of Cr, al and Fe; Optionally, the cocatalysts in the groups (2) - (3) independently comprise oxides of a second metal element; Optionally, the second metal elements in the oxides of the second metal elements in the groups (2) - (3) independently comprise at least one of rare earth elements, main group metal elements and transition metal elements; optionally, the rare earth elements in the groups (2) - (3) independently comprise at least one of lanthanum and yttrium; optionally, the main group metal elements in the groups (2) - (3) independently comprise at least one of aluminum and magnesium; optionally, the transition metal elements in the groups (2) - (3) independently comprise at least one of zinc and nickel; Preferably, in the group (2) or (3), the cocatalysts independently comprise at least one of Cr 2 O 3 、Al 2 O 3 、Fe 2 O 3 ; preferably, in the groups (2) - (3), the main catalyst comprises at least one of Cr 2 O 3 、Al 2 O 3 , and the cocatalyst comprises at least one of lanthanum oxide, yttrium oxide and zinc oxide.
8. The synthetic method according to claim 7, wherein the preparation method of the catalyst of group (2) comprises method 1 or method 2; The method 1 comprises the steps of mixing a main catalyst and a cocatalyst to obtain a second catalyst; mixing a salt of a first metal element or a hydrate of the salt with a salt of a second metal element or a hydrate of the salt in water, adding alkali to mix to form a precipitate, filtering, drying and filtering the obtained precipitate, roasting in nitrogen or inert gas atmosphere, and crushing to obtain a second catalyst; the preparation method of the catalyst of the (3) group comprises a method 3 or a method 4; Mixing a main catalyst, a cocatalyst and a forming auxiliary agent, and tabletting and forming to obtain the second catalyst; Mixing a salt of a first metal element or a hydrate of the salt with a salt of a second metal element or a hydrate of the salt in water, adding alkali, mixing to form a precipitate, filtering, drying and filtering the obtained precipitate, roasting in nitrogen or inert gas atmosphere, crushing to obtain a mixture of a main catalyst and a cocatalyst, mixing the obtained mixture with a forming auxiliary agent, tabletting and forming to obtain the second catalyst; Optionally, the roasting of the method 2 or the method 4 independently comprises roasting at 200-300 ℃ or 250 ℃ for 5-10 hours in nitrogen or inert gas atmosphere, and then roasting at 300-400 ℃ or 350 ℃ for 5-10 hours in nitrogen or inert gas atmosphere; Optionally, the salts of the first metal element of method 2 or method 4 each independently comprise chromium chloride; optionally, the hydrates of the salts of the first metallic element of either method 2 or method 4 each independently comprise chromium chloride hexahydrate; optionally, the salts of the second metal element of method 2 or method 4 independently comprise a nitrate salt of the second metal element or a chloride salt of the second metal element, respectively; Optionally, the inert gases of method 2 and method 4 each independently comprise at least one of helium, neon, argon, krypton, xenon; Optionally, the hydrates of the salts of the second metal elements of method 2 or method 4 each independently include a hydrate of a nitrate salt of the second metal element or a hydrate of a chloride salt of the second metal element; Optionally, the preparation method of the catalyst in the (4) group comprises the steps of mixing a main catalyst with a forming auxiliary agent, tabletting and forming to obtain the second catalyst; Optionally, in the method 1, the main catalyst and the cocatalyst are crushed before mixing; Optionally, in the method 3, the main catalyst, the cocatalyst and the forming aid are crushed before mixing; optionally, in the method 5, the main catalyst and the cocatalyst are crushed before mixing; optionally, the forming aids in the groups (2) - (3) respectively and independently comprise graphite; optionally, the molar ratio of the first metal element to the second metal element in the (2) or (3) group is independently selected from 1:0.01-1:0.1; optionally, the ratio of the total mass of the main catalyst and the cocatalyst to the mass of the molding aid in the group (3) is 100:0.1-100:10, or 100:5; optionally, the mass ratio of the main catalyst to the molding auxiliary agent in the group (4) is 100:0.1-100:10, or 100:5.
9. A catalyst comprising the second catalyst of the group (2) or the group (3) in the synthesis method according to any one of claims 7 to 8.
10. Use of the catalyst of claim 9 in a reaction to catalyze 1,2, 3-pentafluoropropane to produce 2, 3-tetrafluoropropene.

Description

Synthesis method of 1,2, 3-pentafluoropropane and 2,3, 3, 3-tetrafluoropropene Technical Field The invention relates to the fields of refrigerants, fire protection, new materials for fluoride industry, foaming agents and chemical synthesis, in particular to a synthesis method of 1,2, 3-pentafluoropropane and 2,3,3, 3-tetrafluoropropene. Background 2,3, 3, 3-Tetrafluoropropene, chemical name 2,3, 3, 3-tetrafluoro-1-propene, trade name HFO-1234yf or R-1234yf, is a Hydrofluoroolefin (HFO) type compound. 2,3, 3, 3-tetrafluoropropene has excellent environmental protection characteristics of odp=0, gwp=4 and an atmospheric lifetime of only 11 days, and the thermodynamic performance is highly similar to that of HFC-134a, so that the 2,3, 3-tetrafluoropropene can be directly used for the existing R134a system without great improvement, and is recognized as an ideal substitute in the fields of automobile air conditioning and the like. The Chinese patent application CN105367378A discloses a preparation process of 2, 3, 3, 3-tetrafluoropropene, but the preparation process has the problems of needing to use fluorine gas, alkali liquor, expensive solvent, ultralow temperature, special treatment of a reaction container and the like, wherein the fluorine gas is dangerous and extremely toxic, safety protection is needed during use, the operation is complex, the cost of three wastes of the alkali liquor is high, and the operation is complex and the cost is high due to the use of the expensive solvent, ultralow temperature and special treatment of the reaction container. The Chinese patent application CN101979364B discloses a preparation process of 2,3, 3, 3-tetrafluoropropene and an intermediate thereof, but the preparation process has the problems of long steps, complex operation, ultralow temperature, ultraviolet lamp irradiation, chlorine use and the like, wherein the long process steps, ultralow temperature and ultraviolet lamp irradiation lead to high cost and complex operation, the chlorine use is dangerous and extremely toxic, and the safety protection is needed during the use and the operation is complex. 1,2, 3-Pentafluoropropane, the common name HFC-245eb, belongs to Hydrofluorocarbon (HFCs) fluorine-containing fine chemicals, is an environment-friendly fluorine-containing solvent/foaming agent/refrigerant with low ozone depletion potential value and low global warming potential value, is also an important intermediate for fluorine-containing fine chemical synthesis, and is widely applied to the fields of fine chemical synthesis, electronic cleaning, foaming materials, low-temperature refrigeration and the like. Chinese patent application CN101921169A discloses a preparation method of 1,2, 3-pentafluoropropane, but the method has the problems of high reaction temperature, low selectivity of target products and the like because of the need of a catalyst containing noble metals. Therefore, there is still a need for a safe, environment-friendly, simple process, mild reaction, high yield of 2,3, 3, 3-tetrafluoropropene preparation method and a1, 2, 3-pentafluoropropane synthesis method which are simple to operate, short in time consumption, mild in reaction, simple in reagents required for the reaction, high in substrate conversion rate and high in target product selectivity. Disclosure of Invention In order to solve the technical problems, the invention provides the following technical scheme. In a first aspect, the present invention provides a method of synthesizing 1,2, 3-pentafluoropropane. A method for synthesizing 1,2, 3-pentafluoropropane, comprising: , performing a first reaction of 3, 3-trifluoropropene, a first catalyst, an HF source and a selective fluorine reagent in a first solvent to obtain 1,2, 3-pentafluoropropane; wherein the selective fluorine reagent comprises 1-chloromethyl-4-fluoro-1, 4-diazotized bicyclo [2.2.2] octane bis (tetrafluoroborate). In some embodiments, the HF source comprises at least one of Et3N xHF, pyr yHF, where x and y are each independently selected from integers of 1-10. In some embodiments, x and y are each independently selected from 1,2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments, the HF source comprises at least one of Et 3 N.3HF, pyr.HF, which is useful for increasing substrate conversion and selectivity to the desired product 1,2, 3-pentafluoropropane. In some preferred embodiments, the HF source is a mixture of Et 3 N.3 HF and pyr.HF, which is advantageous for increasing the substrate conversion and the selectivity to the desired product 1,2, 3-pentafluoropropane. In some embodiments, the molar ratio of Et 3 N.3HF to pyr.HF in the mixture of Et 3 N.3HF and pyr.HF is 1:1 to 1:10. In some embodiments, the molar ratio of Et 3 n.3 HF to pyr.hf in the mixture of Et 3 n.3 HF and pyr.hf is 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or any value in the range between any two of these values. In some preferred embodiments, the molar ratio of Et 3 N.3HF to pyr.HF in th