CN108033942B - Preparation method for co-producing 3,3, 3-trifluoro-1, 2-propylene glycol and 4-trifluoromethyl ethylene carbonate - Google Patents
Preparation method for co-producing 3,3, 3-trifluoro-1, 2-propylene glycol and 4-trifluoromethyl ethylene carbonate Download PDFInfo
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- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
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Abstract
The invention discloses a preparation method for co-producing 3,3, 3-trifluoro-1, 2-propylene glycol and 4-trifluoromethyl ethylene carbonate, which comprises the following steps: in the presence of a hydrogen halide solution and an organic base, 3,3, 3-trifluoro propylene oxide reacts with carbon dioxide at the temperature of 70-180 ℃ and the reaction pressure of 0.1-5 MPa to obtain crude products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate after the reaction is finished, and the target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate are obtained after separation and refining, wherein the dosage of the hydrogen halide is 0.5-20 percent of the molar weight of the 3,3, 3-trifluoro propylene oxide, and the dosage of the organic base is 0.5-20 percent of the molar weight of the 3,3, 3-trifluoro propylene oxide. The method has the characteristics of mild reaction conditions, simple and convenient operation, good economy of reaction atoms and adjustable product distribution, and is mainly used for coproducing and preparing the 3,3, 3-trifluoro-1, 2-propanediol and the 4-trifluoromethyl ethylene carbonate.
Description
Technical Field
The invention relates to a preparation method of fluorine-containing alcohol and fluorine-containing five-membered cyclic carbonate, in particular to a preparation method for co-producing 3,3, 3-trifluoro-1, 2-propanediol (TFPG) and 4-trifluoromethyl ethylene carbonate (TFPC).
Background
The introduction of trifluoromethyl into organic compounds can significantly alter the acidity, dipole moment, polarity, lipophilicity and chemical and metabolic stability of the compounds, and trifluoromethyl-containing compounds play an increasingly important role in defense industry, high and new technology industry and life sciences. 3,3, 3-trifluoro-1, 2-propanediol (TFPG) is used as one of the fluorine-containing alcohols, the structure contains trifluoromethyl and two hydroxyl groups at the same time, the structure is unique, the performance is excellent, and the application prospect is wide; 3,3, 3-trifluoropropene carbonate (TFPC) is an important trifluoromethyl-containing compound, can be used as an electrolyte cosolvent or an additive to be applied to a lithium ion battery, and can also be used as a polymer precursor and a reaction solvent to be applied to the fields of drug synthesis and fine chemical engineering.
Japanese patent JP2008230970 discloses a method for synthesizing TFPG in three steps by using 1, 1-dichloro-3, 3, 3-trifluoroacetone as a starting material, firstly hydrolyzing under an alkaline condition to obtain 2-hydroxy-3, 3, 3-trifluoropropionic acid, then performing esterification to obtain 2-hydroxy-3, 3, 3-trifluoropropionate, and finally performing reduction under a sodium borohydride/ethanol system to obtain TFPG.
The document electrochem, Commun, 2010,12(3):386-389 reports that ethyl trifluoropyruvate is used as a raw material and lithium aluminum hydride (LiAlH)4) The method for preparing TFPG through reduction reaction under the action has high yield, but needs a large amount of solvents such as anhydrous tetrahydrofuran, diethyl ether and the like, is not environment-friendly, and also relates to LiAlH which is inflammable when meeting moisture4The safety is poor, and the industrial application of the product is severely restricted.
J.am.chem.Soc.,1952,74(12):3022-3023 reported a method for preparing TFPG by hydrolysis under acidic conditions, 3,3, 3-trifluoro-propylene oxide reacted with 1% by weight of sulfuric acid aqueous solution for 12 hours, after the reaction, the target product was obtained by ether extraction with a yield of 26.2%; in order to increase the reaction yield, the document J.org.chem.,1995,60(1):41-46 puts 3,3, 3-trifluoro-epoxypropane and 1% sulfuric acid water solution into a sealing device to react for 2h at 100 ℃, and the yield can reach 80%; US patent US6010806 discloses a method for preparing TFPG by hydrolysis under alkaline conditions, which is to convert TFPO into TFPG under the action of 3% sodium bicarbonate water solution, the reaction temperature is 40 ℃, the reaction time is 48h, and the yield is 71%; chinese patent CN102372689 also discloses a method for preparing TFPG by alkaline hydrolysis, which takes 2-bromine-3, 3, 3-trifluoropropanol as raw material to react for 6 hours in 20% sodium carbonate aqueous solution at 70 ℃, the yield is 78% -83%, and the product purity is 94% -96%. The three hydrolysis methods all need to use a large amount of water, but the target product has better solubility in water, so the product is not easy to separate and has more loss.
US4210733 discloses a process for preparing TFPG by oxidizing 3,3, 3-trifluoropropene, which process uses K2CO3/K2OsO2(OH)2/K3Fe(CN)6/C5H5And N is a catalyst, and is oxidized in water and tert-butyl alcohol to obtain a target product. Although the reaction steps are short, four catalysts and two reaction solvents are involved, the reaction system is complex, the reaction selectivity is low and the like.
Currently, reports on the preparation of TFPC are classified into a 3,3, 3-trifluoro 1, 2-propanediol (TFPG) method and a 3,3, 3-trifluoro propylene oxide (TFPO) method according to the raw materials. The reports of the TFPG method are relatively more, and documents of electrochem, Commun, 2010,3:386-389, Chinese patents CN104761529 and CN102807549 adopt TFPG and phosgene or triphosgene to react to prepare TFPC, which relates to the use of virulent and strong corrosive phosgene or triphosgene, has large danger and is not beneficial to large-scale production; patent CN102659747 adopts TFPG and urea to react under the catalysis of metal oxide to generate TFPC, but the reaction temperature is higher (150 ℃ -190 ℃), the reaction yield is lower (29.5% -69%), and the by-product ammonia gas is inconsistent with the current increasingly strict environmental protection requirement; chinese patent CN102372689 and US6010806 adopt TFPG and dimethyl carbonate to prepare TFPC through ester exchange reaction, the reaction conditions are mild, but the reaction time is long, and the reaction needs to be greatly exceededEster content and low yield. The TFPO method has 100% atom economy and can simultaneously treat greenhouse gas CO2Resource utilization is the direction of future research and development.
Japanese patent JP2008230970 discloses a process for preparing TFPC by reacting TFPO with CO under the action of 3 mol% lithium bromide2In N-methyl pyrrolidone, the TFPC is generated by cycloaddition reaction under the conditions of 100 ℃ and 1.2MPa pressure. However, this method has a low reaction yield of 49%, and requires the use of an expensive solvent.
Chinese patent 201510734534.1 discloses a method for preparing TFPC, namely converting TFPO into TFPC under the catalysis of metal tungsten compound, wherein the reaction temperature is 30-70 ℃, and the reaction pressure is 0.5-3 MPa. The method is carried out intermittently in a high-pressure reaction kettle, the reaction efficiency is low, and the product has the risk of metal tungsten residue and is not in accordance with the high-quality requirement of the battery-grade reagent.
Although some reports on TFPG or TFPC have been disclosed, no report on the co-production of TFPG and TFPC is disclosed, and more importantly, the methods have the defects of harsh reaction conditions and poor safety performance; the reaction atom has poor economy and low yield; the reaction steps are multiple, and the reaction system is complex; the method relates to highly toxic and harmful substances, and is not environment-friendly; metal residue, low product quality and the like, and needs to develop a preparation method for coproducing 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate, which has mild reaction conditions, simple and convenient operation, good atom economy and adjustable product distribution.
Disclosure of Invention
The invention aims to overcome the defects in the background technology and provide a preparation method for coproducing 3,3, 3-trifluoro-1, 2-propanediol (TFPG) and 4-trifluoromethyl ethylene carbonate (TFPC), which has the advantages of mild reaction conditions, simple and convenient operation, good atom economy and adjustable product distribution.
In order to realize the purpose of the invention, the preparation method of the co-produced TFPG and TFPC provided by the invention comprises the following steps: 3,3, 3-trifluoro propylene oxide is used as a raw material and reacts with carbon dioxide in the presence of a hydrogen halide solution and organic alkali, the reaction temperature is 70-180 ℃, the reaction pressure is 0.1-5 MPa, and after the reaction is finished, the obtained 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate crude products are separated and refined to obtain the target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate; wherein, the dosage of the hydrogen halide is 0.5 to 20 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane; the organic base is dialkyl amine, trialkyl amine, N-dimethyl amide or a nitrogen-containing heterocyclic compound, and the amount of the organic base is 0.5 to 20 percent of the molar amount of the 3,3, 3-trifluoro propylene oxide.
The hydrogen halide solution is one or more of 55-58% by mass of hydroiodic acid, 48% by mass of hydrobromic acid, 36-38% by mass of hydrochloric acid and 40% by mass of hydrofluoric acid which are sold in the market.
The organic base is selected from trialkylamine, N-dimethylacetamide, imidazole, alkylimidazole, pyridine, 4-dimethylaminopyridine, 1, 8-diazabicycloundecen-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene or triethylenediamine.
The dosage of the hydrogen halide is 3 to 15 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane, and the dosage of the organic base is 3 to 15 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane.
The dosage of the hydrogen halide is 5 to 10 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane, and the dosage of the organic base is 5 to 10 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane.
The reaction temperature is 100-150 ℃, and the reaction pressure is 0.5-2 MPa.
The preparation method comprises the following steps: 3,3, 3-trifluoro propylene oxide is used as a raw material and reacts with carbon dioxide at 120 ℃ and 0.5MPa in the presence of hydrogen fluoride solution and triethylamine to obtain 3,3, 3-trifluoro-1, 2-propanediol and a 4-trifluoromethyl ethylene carbonate crude product, and the target products of the 3,3, 3-trifluoro-1, 2-propanediol and the 4-trifluoromethyl ethylene carbonate are obtained through separation and refining processes; wherein, the usage amount of the hydrogen fluoride is 10 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane; the water consumption is 50 percent of the molar mass of the trifluoro epoxypropane; the dosage of triethylamine is 10 percent of the molar weight of 3,3, 3-trifluoro epoxypropane.
Compared with the prior art, the invention has the advantages that: the invention provides an effective method for preparing TFPG and TFPC by co-production, and has the following characteristics of (1) realization under the action of organic micromolecules, no metal participation in the reaction process, no addition of any reaction solvent, mild reaction conditions and simple and convenient operation; (2) the carbon dioxide and water involved in the reaction process can participate in the reaction, no other byproducts are generated, the atomic economy is good, the steps are few, the reaction yield is high, the comparison files are often completed by multi-step reactions, the atomic economy is poor, and the number of byproducts is large; (3) the product TFPG and TFPC are controllable in distribution, and a comparison file only generates TFPG or only generates TFPC, so that the controllable synthesis of the product TFPG and the TFPC cannot be realized at the same time.
Detailed Description
The preparation method of the co-produced TFPG and TFPC provided by the invention comprises the following steps: 3,3, 3-trifluoro epoxypropane is used as a raw material and reacts with carbon dioxide in the presence of a hydrogen halide solution and organic alkali at the temperature of 70-180 ℃ and the reaction pressure of 0.1-5 MPa, and after the reaction is finished, the obtained 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate crude product are separated and refined to obtain target products TFPG and TFPC.
The hydrogen halide solution in the invention is one or more combinations of hydrogen iodide solution, hydrogen bromide solution, hydrogen chloride solution or hydrogen fluoride solution, preferably one or more combinations of 55-58% by mass of hydroiodic acid, 48% by mass of hydrobromic acid, 36-38% by mass of hydrochloric acid and 40% by mass of hydrofluoric acid which are commercially available; in the invention, the amount of the hydrogen halide is 0.5 to 20 percent, preferably 3 to 15 percent, and more preferably 5 to 10 percent of the molar amount of the 3,3, 3-trifluoro propylene oxide; the molar ratio of the hydrogen halide to the organic base is 0.9-1.2: 1; in the invention, the water content in the reaction liquid is also an important factor influencing the reaction, and the water content is preferably less than 13.8 percent of the mass of the 3,3, 3-trifluoro propylene oxide.
The organic base in the present invention is selected from a wide range of organic bases including primary amines such as methylamine, ethylamine, butylamine, etc., secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, etc., tertiary amines such as trimethylamine, triethylamine, tripropylamine, etc., N, N-dimethylamide or nitrogen-containing heterocyclic compounds such as morpholine, indole, quinoline, pteridine, acridine, thiazole, pyrazine, pyrimidine, pyridazine, triazine, triazole, and derivatives thereof, preferably trialkylamine, N, N-Dimethylacetamide (DMAC), Imidazole (IMD), alkylimidazole, pyridine (Py), 4-Dimethylaminopyridine (DMAP), 1, 8-diazabicycloundecen-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] -5-nonene (DBN), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene (MTBD) or triethylenediamine (DABCO). Suitable organic bases include, of course, guanidine, hydroxy-substituted trialkylamines, and the like; the organic base is used in the present invention in an amount of 0.5 to 20%, preferably 3 to 15%, more preferably 5 to 10% based on the molar amount of 3,3, 3-trifluoropropene oxide.
The reaction mode and the type of the reactor are not critical, the batch operation of the kettle type reaction can be used, the continuous operation of the tubular reactor can also be adopted, and only the corresponding optimal reaction temperature, reaction pressure, hydrogen halide solution and organic base dosage are different when different reactors are selected.
The invention has the beneficial effects that:
(1) the method is realized under the action of organic micromolecules, no metal participates in the reaction process, no reaction solvent is added, the reaction condition is mild, and the operation is simple and convenient;
(2) the carbon dioxide and water involved in the reaction process of the invention can participate in the reaction, and no other by-products are generated, the atom economy is good, the steps are few, the reaction yield is high,
(3) the product distribution of the invention can be regulated.
The present invention will be described in further detail with reference to the following examples
Example 1:
3,3, 3-trifluoro propylene oxide (0.3mol), 48% HBr solution (15mmol) and the like are sequentially added into a 50mL stainless steel autoclave with stirring,Triethylamine (15mmol), sealed and then charged with CO2Replacing the reaction kettle twice, starting stirring and heating to 100 ℃, and continuously introducing CO2Keeping the reaction pressure at 0.5MPa, reacting for 4h, cooling to normal temperature, and slowly releasing excessive CO2Obtaining crude products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate, analyzing the distribution of products by gas chromatography, wherein the contents of TFPG and TFPC are respectively 21.2 percent and 78.4 percent, separating to obtain target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate 44.3g, calculating the yield to be 98.7 percent, and the reaction result is shown in table 1.
Gas chromatography conditions: agilent 7820 gas chromatography, hydrogen flame ionization detector, DB-5 capillary chromatography column (30m × 0.320mm × 0.25 μm), injector temperature 250 ℃ and detector temperature 280 ℃, column box programmed temperature: the initial temperature is 50 ℃, the temperature is kept for 3min, the temperature is raised to 200 ℃ at the speed of 10 ℃/min, and the temperature is kept for 5 min; the sample amount is 0.06 mu L, and the analysis and calculation are carried out by adopting an area normalization method.
Examples 2 to 11:
examples 2 to 11 reactions were carried out in the same manner as in example 1, and the conditions such as the hydrogen halide solution, the organic base, the reaction temperature, the reaction pressure, the reaction time, and the like, and the corresponding reaction results and product distributions were as shown in table 1.
TABLE 1
Example 12:
reaction A: adding 3,3, 3-trifluoro propylene oxide (33.6g, 0.3mol), 55% -58% HI solution (15mmol) and triethylamine (15mmol) in turn into a stirred 50mL stainless steel autoclave, sealing, and adding CO2Replacing the reaction kettle twice, starting stirring and heating to 100 ℃, and continuously introducing CO2Keeping the reaction pressure at 2MPa, reacting for 4h, cooling to normal temperature, and slowly releasing redundant CO2Gas is generated to obtain 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate crude product, and the reaction product is distributed and divided by gas chromatographyAnd (3) separating and refining, wherein the TFPG content and the TFPC content are respectively 23.5 percent and 76.1 percent, so that the total yield of the target product, namely 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate, is 43.5g, and is 98.5 percent.
Reaction B: a50 mL stainless steel autoclave equipped with stirring was charged with 3,3, 3-trifluoroepoxypropane (33.6g, 0.3mol), and the reaction residue obtained by separating 3,3, 3-trifluoro-1, 2-propanediol from reaction A and 4-trifluoromethylethylene carbonate was completely charged, followed by sealing with CO2Replacing the reaction kettle twice, starting stirring and heating to 100 ℃, and continuously introducing CO2Keeping the reaction pressure at 0.5MPa, reacting for 4h, cooling to normal temperature, and slowly releasing excessive CO2And (3) obtaining crude products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate, wherein the contents of TFPG and TFPC are respectively 0.5 percent and 99.0 percent, and obtaining 45.2g of the target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate through separation and refining processes, wherein the yield is 97.1 percent.
Reaction C: adding 3,3, 3-trifluoro propylene oxide (33.6g, 0.3mol) into a 50mL stainless steel autoclave with stirring, supplementing 0.3g of water, completely adding reaction residual liquid of 3,3, 3-trifluoro-1, 2-propanediol separated from the reaction A and 4-trifluoromethyl ethylene carbonate, sealing, and then adopting CO2Replacing the reaction kettle twice, starting stirring and heating to 100 ℃, and continuously introducing CO2Keeping the reaction pressure at 0.5MPa, reacting for 4h, cooling to normal temperature, and slowly releasing excessive CO2And supplementing water accounting for 30% of the molar mass of the 3,3, 3-trifluoro propylene oxide into the gas, continuing to react for 12 hours to obtain a crude product of the 3,3, 3-trifluoro-1, 2-propanediol and the 4-trifluoromethyl ethylene carbonate, performing distribution analysis on reaction products by gas chromatography, wherein the contents of TFPG and TFPC are respectively 25.7% and 73.8%, and obtaining 42.2g of the target product of the 3,3, 3-trifluoro-1, 2-propanediol and the 4-trifluoromethyl ethylene carbonate by separation and refining processes, wherein the yield is 95.3%.
Examples 13 to 16:
examples 13 to 16 reactions were carried out in the same manner as in example 1, except that the hydrogen halide solution in example 1 was a 48% HBr solution (5 mol%), and the hydrogen halide solutions in examples 12 to 15 were 40% hydrofluoric acid/55% to 58% hydroiodic acid (1 mo%/4 mol%), 48% hydrobromic acid/36% to 38% hydrochloric acid (4 mo%/1 mol%), 30% hydrobromic acid (5 mo%), and 20% hydroiodic acid (3 mo%), and the reaction results are shown in Table 2.
TABLE 2
Example 17:
a50 mL stainless steel autoclave equipped with stirring was charged with 3,3, 3-trifluoroepoxypropane (33.6g, 0.3mol), water (0.15mol), and triethylamine (30mmol) in this order, and hydrogen fluoride (30mmol) was introduced, followed by sealing with CO2Replacing the reaction kettle twice, starting stirring and heating to 120 ℃, and continuously introducing CO2Keeping the reaction pressure at 0.5MPa, reacting for 24h, cooling to normal temperature, and slowly releasing excessive CO2And (3) obtaining crude products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate, analyzing the distribution of reaction products by gas chromatography, wherein the contents of TFPG and TFPC are respectively 44.6% and 55.0%, and obtaining 42.3g of the target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate by separation and refining processes, wherein the yield is 98.6%.
Example 18:
example 18 the reaction was carried out in the same manner as in example 17 except that the hydrogen halide solution in example 17 was formed by passing HF through the aqueous reaction solution, whereas example 18 was formed by passing HCl through the aqueous reaction solution, and the results showed that the TFPG and TFPC contents in the reaction solutions were 43.9% and 55.4%, respectively, and the yield was 88.3%.
Example 19:
adding commercial hydrobromic acid (content 48%) with molar mass of 10% and N-methylimidazole with molar mass of 10% into 3,3, 3-trifluoro-epoxypropane, uniformly mixing, conveying to a preheater by a metering pump for preheating, and preheatingHot temperature 70 deg.C, then mixing with CO2Mixing in a micro mixer (with channel size of 200 μm), reacting at 160 deg.C and 1MPa in a tubular reactor (volume of 300ml) for 1h, introducing the reaction product stream into a gas-liquid separation tank, introducing the top component of carbon dioxide into a carbon dioxide recovery system, and recycling; the bottom material enters a first rectifying tower to separate 3,3, 3-trifluoro epoxypropane, the 3,3, 3-trifluoro epoxypropane is obtained at the tower top and returns to a preheater for recycling, the tower bottom obtains crude products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate, the distribution analysis of reaction products is carried out by gas chromatography, wherein the contents of TFPG and TFPC are respectively 43.5 percent and 56.2 percent, and the 3,3, 3-trifluoro-1, 2-propanediol with the purity of 99 percent and the 4-trifluoromethyl ethylene carbonate with the purity of 99.9 percent are obtained by separation and refining processes, and the yield is 98.2 percent.
(1) First product, 99.0% pure, via1H-NMR、13C-NMR、19F-NMR characterization was identified as TFPG.
1H-NMR(500MHz,DMSO-d6)：δ6.19(d,6.5Hz,1H),4.98(t,6Hz,1H),3.91(m,1Hz,1H),3.58(m,6Hz,1H),3.47(m,6Hz,1H)；13C-NMR(500MHz,DMSO-d6)：δ125.42(q,JC-F＝1128.5Hz,1C),70.02(q,JC-F＝110.5Hz,1C),60.2(s,1C)；19F-NMR(500MHz,DMSO-d6)：δ-76.48(s,3F)。
(2) Second product, 99.9% pure, via1H-NMR、13C-NMR、19F-NMR characterization was identified as TFPC.
1H-NMR(500MHz,CDCl3)：δ4.98(m,1H),4.67(t,1H),4.57(q,1H)；13C-NMR(500MHz,CDCl3)：δ152.55(s,1C),122.15(q,JC-F＝1114.5Hz,1C),71.79(q,JC-F＝143.5Hz,1C),63.69(s,1C)；19F-NMR(500MHz,CDCl3)：δ-80.07(s,3F)。
The above description is only a part of the embodiments of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (5)
1. A preparation method for co-producing 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate is characterized in that 3,3, 3-trifluoro-propylene oxide is used as a raw material to react with carbon dioxide in the presence of a hydrogen halide solution and organic alkali, the reaction temperature is 70-180 ℃, the reaction pressure is 0.1-5 MPa, and after the reaction is finished, the obtained 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate crude products are separated and refined to obtain target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate; wherein, the dosage of the hydrogen halide is 0.5 to 20 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane; the dosage of the organic alkali is 0.5 to 20 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane;
the hydrogen halide solution is one or more of a combination of 55-58% by mass of hydroiodic acid, 48% by mass of hydrobromic acid, 36-38% by mass of hydrochloric acid and 40% by mass of hydrofluoric acid which are sold in the market;
the organic base is selected from the group consisting of trialkylamines, N-dimethylacetamide, imidazole, alkylimidazoles, pyridine, 4-dimethylaminopyridine, 1, 8-diazabicycloundecen-7-ene, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, and triethylenediamine.
2. The preparation method for the co-production of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate according to claim 1, characterized in that the amount of the hydrogen halide is 3% -15% of the molar amount of 3,3, 3-trifluoro propylene oxide, and the amount of the organic base is 3% -15% of the molar amount of 3,3, 3-trifluoro propylene oxide.
3. The preparation method for the co-production of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate according to claim 2, characterized in that the amount of the hydrogen halide is 5% -10% of the molar amount of 3,3, 3-trifluoro propylene oxide, and the amount of the organic base is 5% -10% of the molar amount of 3,3, 3-trifluoro propylene oxide.
4. The preparation method for the co-production of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate according to claim 1, characterized in that the reaction temperature is 100-150 ℃, and the reaction pressure is 0.5-2 MPa.
5. The preparation method of co-production of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate according to claim 1, characterized in that 3,3, 3-trifluoro-propylene oxide is used as raw material, and reacts with carbon dioxide at 120 ℃ and 0.5MPa in the presence of hydrogen fluoride solution and triethylamine to obtain 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate crude product, and the target products of 3,3, 3-trifluoro-1, 2-propanediol and 4-trifluoromethyl ethylene carbonate are obtained through separation and refining processes; wherein, the usage amount of the hydrogen fluoride is 10 percent of the molar weight of the 3,3, 3-trifluoro epoxypropane; the dosage of triethylamine is 10 percent of the molar weight of 3,3, 3-trifluoro epoxypropane.
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| CN1995032A (en) * | 2006-12-27 | 2007-07-11 | 中国科学院过程工程研究所 | Process for preparing annular carbonate |
| CN106966862A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | It is a kind of while preparing the method for propane diols and propene carbonate |
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| CN1995032A (en) * | 2006-12-27 | 2007-07-11 | 中国科学院过程工程研究所 | Process for preparing annular carbonate |
| CN106966862A (en) * | 2016-01-14 | 2017-07-21 | 中国石油化工股份有限公司 | It is a kind of while preparing the method for propane diols and propene carbonate |
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