CN108033942A - The preparation method of the fluoro- 1,2- propane diols of coproduction 3,3,3- tri- and 4- trifluoromethyl ethylene carbonates - Google Patents
The preparation method of the fluoro- 1,2- propane diols of coproduction 3,3,3- tri- and 4- trifluoromethyl ethylene carbonates Download PDFInfo
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- CN108033942A CN108033942A CN201711378674.5A CN201711378674A CN108033942A CN 108033942 A CN108033942 A CN 108033942A CN 201711378674 A CN201711378674 A CN 201711378674A CN 108033942 A CN108033942 A CN 108033942A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
- C07C29/103—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 of cyclic ethers
Abstract
The invention discloses the preparation method of a kind of 3,3,3 trifluoro of coproduction, 1,2 propane diols and 4 trifluoromethyl ethylene carbonates, comprise the following steps：In the presence of hydrogen halide solution, organic base, 3,3,3 trifluoro-epoxy propanes are reacted with carbon dioxide, 180 DEG C of reaction temperature 70 DEG C, reaction pressure 0.1MPa 5MPa, reaction finishes, obtain 3,3,3 trifluoros 1,2 propane diols and 4 trifluoromethyl ethylene carbonate crude products, through separating, being refining to obtain 3,3,3 trifluoro 1 of target product, 2 propane diols and 4 trifluoromethyl ethylene carbonates, wherein, hydrogen halides dosage is 3,3,0.5% the 20% of 3 trifluoro-epoxy propane moles, the dosage of organic base is 0.5% the 20% of 3,3,3 trifluoro-epoxy propane moles.The present invention has the characteristics that gentle reaction condition, easy to operate, reaction of atomic good economy performance, product distribution is adjustable, is mainly used for coproduction and prepares 3,3,3 trifluoro, 1,2 propane diols and 4 trifluoromethyl ethylene carbonates.
Description
Technical field
The present invention relates to the preparation method of a kind of fluorine-containing alcohol and fluorine-containing five-membered cyclic carbonate ester, more particularly to a kind of coproduction 3,
The fluoro- 1,2- propane diols (TFPG) of 3,3- tri- and the preparation method of 4- trifluoromethyls ethylene carbonate (TFPC).
Background technology
Trifluoromethyl is incorporated into the acidity that compound can be significantly changed in organic compound, dipole moment, polarity, lipophilic
Property and its chemistry and metabolic stability, the compound containing trifluoromethyl is in national defense industry, new high-tech industry and life science
In play an increasingly important role.The one kind of 3,3,3- tri- fluoro- 1,2-PDs (TFPG) as fluorine-containing alcohol, in structure at the same time
Containing trifluoromethyl and two hydroxyls, unique structure, excellent performance, has a extensive future；3,3,3- trifluoro propene carbonic esters
(TFPC) be it is a kind of it is important contain trifluoromethyl compound, electrolyte co-solvents or additive application can be used as in lithium-ion electric
Pond, is alternatively arranged as polymer precursor, reaction dissolvent is applied to pharmaceutical synthesis and field of fine chemical.
Japan Patent JP2008230970 discloses one kind with 1,1- bis- chloro- 3, and 3,3- trifluoroacetones are starting material, warp
The method that three steps synthesize TFPG, is to hydrolyze to obtain 2- hydroxyls -3,3 in alkaline conditions first, 3- trifluoroacetic acids, then anti-through being esterified
2- hydroxyls -3,3 should be obtained, 3- trifluoropropyl acid esters, finally reduction obtains TFPG under sodium borohydride/ethanol system again, but this
There are raw material to be not easy to obtain for method, the deficiency that reactions steps are more, yield is low.
Document Electrochem.Commun., 2010,12 (3):386-389 reports one kind with trifluoroacetone acetoacetic ester
For raw material, in lithium aluminium hydride reduction (LiAlH4) method for preparing TFPG under effect through reduction reaction, although this method yield is higher,
Substantial amounts of anhydrous tetrahydro furan, ether equal solvent are needed, it is unfriendly to environment, also relate to meet wet inflammable LiAlH4,
Security is poor, seriously restricts its industrial applications.
J.Am.Chem.Soc.,1952,74(12):3022-3023 reports a kind of acid condition hydrolysis and prepares TFPG's
Method, the aqueous sulfuric acid reaction 12h of 3,3,3- trifluoro-epoxy propanes and mass fraction 1%, reaction is finished to be extracted through ether
To target product, yield 26.2%；To improve reaction yield, document J.Org.Chem., 1995,60 (1):41-46 is by 3,3,3-
Trifluoro-epoxy propane and 1% aqueous sulfuric acid are placed in sealing device, react 2h at 100 DEG C, yield is up to 80%；The U.S. is special
Sharp US6010806 discloses the method that a kind of hydrolysis of alkaline condition prepares TFPG, be 3% sodium bicarbonate aqueous solution effect
Under, TFPO is converted into TFPG, 40 DEG C, reaction time 48h of reaction temperature, yield 71%；Chinese patent CN102372689 is also public
A kind of method that alkaline condition hydrolysis prepares TFPG is opened, this method is with 2- bromo- 3, and 3,3- trifluoropropanols are raw material, 20%
In aqueous sodium carbonate, 6h, yield 78%-83%, product purity 94%-96% are reacted at 70 DEG C.These three above-mentioned hydrolysis
Method is both needed to use substantial amounts of water, but the dissolubility due to target product in water is preferable, and product should not separate, and loss is more.
United States Patent (USP) US4210733 discloses a kind of method that 3,3,3- trifluoro propenes oxidation prepares TFPG, and this method is
With K2CO3/K2OsO2(OH)2/K3Fe(CN)6/C5H5N is catalyst, and in water and the tert-butyl alcohol, oxidation obtains target product.Although
Reactions steps are short, but are related to four kinds of catalyst, two kinds of reaction dissolvents, the deficiencies such as reaction system is complicated, reaction selectivity is low.
At present, 3,3,3- trifluoro 1,2-PD (TFPG) methods can be divided into by the difference of raw material on preparing the report of TFPC
With 3,3,3- trifluoro-epoxy propanes (TFPO) method.The report of TFPG methods is relatively more, document
Electrochem.Commun.2010,3:386-389, Chinese patent CN104761529 and CN102807549 using TFPG with
Phosgene or triphosgene reaction prepare TFPC, this is related to severe toxicity, severe corrosive phosgene or triphosgene and uses, dangerous big, unfavorable
In large-scale production；Patent CN102659747 reacts generation TFPC using TFPG and urea under the catalysis of metal oxide, but
Reaction temperature is higher (150 DEG C -190 DEG C), and reaction yield is relatively low (29.5%-69%), and ammonia gas as byproduct, and currently increasingly severe
Environmental requirement be not inconsistent；Chinese patent CN102372689 and United States Patent (USP) US6010806 is using TFPG with dimethyl carbonate through ester
Exchange reaction prepare TFPC, such reaction condition is gentle, but it is longer there is the reaction time, it is necessary to large excess of ester and
The problem of yield is low.TFPO methods have 100% Atom economy, while can be to greenhouse gases CO2Recycling, is not
Come the direction of research and development.
Japan Patent JP2008230970 discloses a kind of method for preparing TFPC, under the effect of 3mol% lithium bromides,
TFPO and CO2In 1-methyl-2-pyrrolidinone, 100 DEG C, under 1.2MPa pressure conditions, cycloaddition reaction generation TFPC occurs,.But
This method reaction yield is low, is 49%, while also need to use expensive solvent.
Chinese patent 201510734534.1 discloses a kind of method for preparing TFPC, the i.e. catalysis in tungsten compound
Under, TFPO is changed into TFPC, 30-70 DEG C of reaction temperature, reaction pressure 0.5-3MPa.This method is among autoclave
Have a rest progress, reaction efficiency is low, and there are tungsten to remain risk for product, and the high-quality requirement with LITHIUM BATTERY reagent is not inconsistent.
Although having been disclosed for some reports on TFPG or TFPC at present, also not on coproduction TFPG with
There are such as severe reaction conditions, safety in various degree on these above-mentioned methods in the open report of TFPC, what is more important
Poor performance；Reaction of atomic is less economical, and yield is not high；Reactions steps are more, reaction system is complicated；It is related to hypertoxic harmful substance, it is right
Environment is unfriendly；Metal residual, the deficiencies such as product quality is low, it is gentle, easy to operate that assistant officer need to develop a kind of reaction condition, atom warp
Ji property is good, the preparation side of the adjustable fluoro- 1,2- propane diols of coproduction 3,3,3- tri- of product distribution and 4- trifluoromethyl ethylene carbonates
Method.
The content of the invention
It is insufficient present in background technology it is an object of the invention to overcome, there is provided a kind of reaction condition is gentle, operation letter
Just, Atom economy is good, product is distributed the adjustable fluoro- 1,2- propane diols (TFPG) of coproduction 3,3,3- tri- and 4- trifluoromethyl carbonic acid
The preparation method of vinyl acetate (TFPC).
In order to achieve the object of the present invention, the preparation method of coproduction TFPG and TFPC provided by the invention, including following step
Suddenly：With 3,3,3- trifluoro-epoxy propanes for raw material, in the presence of hydrogen halide solution, organic base, reacted with carbon dioxide,
70 DEG C -180 DEG C of reaction temperature, reaction pressure 0.1MPa-5MPa, reaction finishes, 3 obtained, 3,3- tri- fluoro- 1,2-PDs with
4- trifluoromethyl ethylene carbonate crude products, target product 3,3,3- tri- fluoro- 1,2-PD and 4- are obtained through separation, process for refining
Trifluoromethyl ethylene carbonate；Wherein, hydrogen halides dosage is the 0.5%-20% of 3,3,3- trifluoro-epoxy propane moles；It is organic
Alkali is dialkylamine, trialkylamine, N, and N- dimethylformamides or nitrogen-containing heterocycle compound, the dosage of organic base is 3,3,3- trifluoros
The 0.5%-20% of propylene oxide mole.
The hydrogen halide solution is commercially available the hydroiodic acid of mass percent 55%-58%, mass percent 48%
Hydrobromic acid, the hydrochloric acid of mass percent 36%-38%, the one or more of hydrofluoric acid of mass percent 40% combine.
The machine alkali is selected from trialkylamine, DMAC N,N' dimethyl acetamide, imidazoles, alkyl imidazole, pyridine, 4- dimethylaminos
Pyridine, 11 carbon -7- alkene of 1,8- diazabicylos, 1,5- diazabicyclos [4.3.0] -5- nonenes, tri- azabicyclics of 1,5,7-
[4.4.0] decyl- 5- alkene, 7- methyl isophthalic acids, tri- azabicyclics of 5,7- [4.4.0] decyl- 5- alkene or triethylene diamine.
The hydrogen halides dosage is the 3%-15% of 3,3,3- trifluoro-epoxy propane moles, and organic base amount is 3,3,
The 3%-15% of 3- trifluoro-epoxy propane moles.
The hydrogen halides dosage is the 5%-10% of 3,3,3- trifluoro-epoxy propane moles, and organic base amount is 3,3,
The 5%-10% of 3- trifluoro-epoxy propane moles.
The reaction temperature is 100 DEG C -150 DEG C, reaction pressure 0.5MPa-2MPa.
The preparation method comprises the following steps：With 3,3,3- trifluoro-epoxy propanes for raw material, in hydrogen fluoride solution, three
In the presence of ethamine, at 120 DEG C, reacted under 0.5MPa with carbon dioxide, 3 obtained, 3,3- tri- fluoro- 1,2-PDs and 4-
Trifluoromethyl ethylene carbonate crude product, 3,3,3- tri- fluoro- 1,2-PD of target product and 4- tri- are obtained through separation, process for refining
Methyl fluoride ethylene carbonate；Wherein, hydrogen fluoride dosage is the 10% of 3,3,3- trifluoro-epoxy propane moles；Water consumption is trifluoro
The 50% of propylene oxide molal weight；Triethylamine dosage is the 10% of 3,3,3- trifluoro-epoxy propane moles.
Compared with prior art, the advantage of the invention is that：Provide a kind of effective coproduction and prepare TFPG's and TFPC
Method, while also have the characteristics that (1) present invention realizes that reaction process is joined without metal under the action of organic molecule
With without any reaction dissolvent is added, reaction condition is gentle, easy to operate；(2) reaction process of the invention be related to two
Carbonoxide, water can be participated in reaction, and without the generation of other accessory substances, Atom economy is good, and step is few, reaction yield
Height, documents, which generally require Duo Walk reactions, to be completed, and Atom economy is poor, and accessory substance is more；(3) product TFPG with
TFPC distributions are controllable, and documents either only generate TFPG or only generate TFPC, it is impossible to while realize that both is adjustable
The synthesis of control property.
Embodiment
The preparation method of coproduction TFPG and TFPC provided by the invention, comprises the following steps：With 3,3,3- trifluoros epoxy third
Alkane is raw material, in the presence of hydrogen halide solution, organic base, is reacted with carbon dioxide, 70 DEG C -180 DEG C of reaction temperature, instead
Pressure 0.1MPa-5MPa is answered, reaction finishes, 3 obtained, 3,3- tri- fluoro- 1,2-PDs and 4- trifluoromethyl ethylene carbonates
Crude product, target product TFPG and TFPC are obtained through separation, process for refining.
Hydrogen halide solution in the present invention is iodate hydrogen solution, hydrogen bromide solution, hydrogen chloride solution or hydrogen fluoride solution
One or more combination, the hydroiodic acid of preferably commercially available mass percent 55%-58%, the hydrobromic acid of mass percent 48%,
One or more combinations of the hydrochloric acid of mass percent 36-38%, the hydrofluoric acid of mass percent 40%；Hydrogen halides in the present invention
Dosage is the 0.5%-20% of 3,3,3- trifluoro-epoxy propane moles, more preferably preferably 3%-15%, 5%-10%；The present invention
The molar ratio of middle hydrogen halides and organic base is 0.9-1.2:1；Water content is also to influence to react important in reaction solution in the present invention
Factor, is advisable with the water content less than 3,3,3- trifluoro-epoxy propane quality 13.8%.
Wider range of organic base selection in the present invention, including the alkylamine such as primary amine such as methylamine, ethamine, butylamine, dioxane
The base amine such as secondary amine such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutyl amine, trialkylamine such as trimethylamine, triethylamine, 3 third
The tertiary amines such as amine, N, N- dimethylformamides or nitrogen-containing heterocycle compound for example morpholine, indoles, quinoline, pteridine, acridine, thiazole, pyrazine,
Pyrimidine, pyridazine, triazine, triazole, and its their derivative, preferably trialkylamine, n,N-dimethylacetamide (DMAC), imidazoles
(IMD), alkyl imidazole, pyridine (Py), 4-dimethylaminopyridine (DMAP), 11 carbon -7- alkene (DBU) of 1,8- diazabicylos,
1,5- diazabicyclos [4.3.0] -5- nonenes (DBN), tri- azabicyclics of 1,5,7- [4.4.0] decyl- 5- alkene (TBD), 7- methyl -
Tri- azabicyclics of 1,5,7- [4.4.0] decyl- 5- alkene (MTBD) or triethylene diamine (DABCO).Certainly suitable organic base also wraps
Include hydroxyl substituent of guanidine, trialkylamine etc.；The dosage of organic base is 3,3,3- trifluoro-epoxy propane moles in the present invention
0.5%-20%, preferably 3%-15%, more preferably 5%-10%.
Reactive mode, the type of reactor of the present invention is not crucial, can use still reaction intermittently operated, can also adopt
Operation is carried out continuously with shell and tube reactor, corresponding preferably reaction temperature, reaction pressure when simply selecting different reactors
Power, hydrogen halide solution and organic base amount are different.
Beneficial effects of the present invention：
(1) present invention realizes under the action of organic molecule, and reaction process is participated in without metal, appoints without addition
What reaction dissolvent, reaction condition is gentle, easy to operate；
(2) carbon dioxide, the water that reaction process of the invention is related to can be participated in reaction, and without other by-products
The generation of thing, Atom economy is good, and step is few, and reaction yield is high,
(3) product of the invention distribution is controllable.
The present invention is described in further detail below by specific embodiment
Embodiment 1：
3,3,3- trifluoro-epoxy propanes (0.3mol), 48% are sequentially added in the 50mL stainless steel autoclaves equipped with stirring
HBr solution (15mmol), triethylamine (15mmol), CO is used after sealing2To reaction kettle displacement twice, open and stir and heat
To 100 DEG C, CO is continuously passed through2Reaction pressure is kept to react 4h, postcooling to room temperature, it is unnecessary to slowly release in 0.5MPa
CO2Gas, obtains 3,3,3- tri- fluoro- 1,2-PDs and 4- trifluoromethyl ethylene carbonate crude products, gas chromatographic analysis product
Distribution, wherein TFPG, TFPC content are respectively 21.2%, 78.4%, are isolated to 3,3,3- tri- fluoro- 1,2- third of target product
Glycol and 4- trifluoromethyl ethylene carbonate 44.3g, calculated yield 98.7%, reaction result is as shown in table 1.
Analytical conditions for gas chromatography：7820 type gas-chromatography of Agilent, flame ionization ditector, DB-5 capillary colors
Column (30m × 0.320mm × 0.25 μm) is composed, 250 DEG C of injector temperature and detector temperature are 280 DEG C, post case temperature programming：Rise
Beginning temperature 50 C, keeps 3min, 10 DEG C/min to be warming up to 200 DEG C, retains 5min；0.06 μ L of sample size, using area normalization
Method carries out analysis calculating.
Embodiment 2-11：
Embodiment 2~11 is reacted according to method identical in embodiment 1, its used hydrogen halide solution, organic
The conditions such as alkali, reaction temperature, reaction pressure, reaction time and corresponding reaction result, product distribution are as shown in table 1.
Table 1
Embodiment 12：
React A：Sequentially added in the 50mL stainless steel autoclaves equipped with stirring 3,3,3- trifluoro-epoxy propanes (33.6g,
0.3mol), the HI solution (15mmol) of 55%-58%, triethylamine (15mmol), use CO after sealing2To reaction kettle displacement two
Secondary, unlatching is stirred and heated to 100 DEG C, is continuously passed through CO2Keep reaction pressure slow in 2MPa, reaction 4h, postcooling to room temperature
Slow release releases unnecessary CO2Gas, obtains 3,3,3- tri- fluoro- 1,2-PDs and 4- trifluoromethyl ethylene carbonate crude products, leads to
Cross gas-chromatography and carry out distribution of reaction products analysis, wherein TFPG, TFPC content is respectively 23.5%, 76.1%, through separation, essence
Technique processed obtains 3,3,3- tri- fluoro- 1,2-PD of target product and the 4- common 43.5g of trifluoromethyl ethylene carbonate, yield
98.5%.
React B：Added in the 50mL stainless steel autoclaves equipped with stirring 3,3,3- trifluoro-epoxy propanes (33.6g,
0.3mol), the reaction residual that A isolates the fluoro- 1,2- propane diols of 3,3,3- tri- and 4- trifluoromethyl ethylene carbonates will be reacted again
Liquid all adds, and CO is used after sealing2To reaction kettle displacement twice, unlatching is stirred and heated to 100 DEG C, is continuously passed through CO2Keep
Reaction pressure reacts 4h, postcooling to room temperature, slowly releases unnecessary CO in 0.5MPa2Gas, it is fluoro- to obtain 3,3,3- tri-
1,2-PD and 4- trifluoromethyl ethylene carbonate crude products, wherein TFPG, TFPC content is respectively 0.5%, 99.0%, through dividing
3,3,3- tri- fluoro- 1,2-PD of target product and the 4- common 45.2g of trifluoromethyl ethylene carbonate are obtained from, process for refining, is received
Rate 97.1%.
React C：Added in the 50mL stainless steel autoclaves equipped with stirring 3,3,3- trifluoro-epoxy propanes (33.6g,
0.3mol), water 0.3g is added, then reaction A is isolated into 3,3,3- tri- fluoro- 1,2-PDs and 4- trifluoromethyl ethylene carbonates
Reaction Liquid Residue all add, CO is used after sealing2To reaction kettle displacement twice, unlatching is stirred and heated to 100 DEG C, continuously
It is passed through CO2Reaction pressure is kept to react 4h, postcooling to room temperature, slowly releases unnecessary CO in 0.5MPa2Gas, then add
The water of 3,3,3- trifluoro-epoxy propane molal weights 30%, be further continued for reaction 12h, obtain 3,3,3- tri- fluoro- 1,2-PDs with
4- trifluoromethyl ethylene carbonate crude products, distribution of reaction products analysis, wherein TFPG, TFPC content point are carried out by gas-chromatography
Not Wei 25.7%, 73.8%, through separation, process for refining obtain 3,3,3- tri- fluoro- 1,2-PD of target product and 4- fluoroforms
The common 42.2g of base ethylene carbonate, yield 95.3%.
Embodiment 13~16：
Embodiment 13~16 is reacted according to method identical in embodiment 1, except that the halogenation in embodiment 1
Hydrogen solution be 48% HBr solution (5mol%), and in embodiment 12~15 hydrogen halide solution be followed successively by 40% hydrofluoric acid/
55%-58% hydroiodic acids (1mo%/4mol%), 48% hydrobromic acid/36%-38% hydrochloric acid (4mo%/1mol%), 30% hydrogen bromine
Sour (5mo%), 20% hydroiodic acid (3mo%), reaction result is as shown in table 2.
Table 2
Embodiment 17：
Sequentially added in the 50mL stainless steel autoclaves equipped with stirring 3,3,3- trifluoro-epoxy propanes (33.6g,
0.3mol), water (0.15mol), triethylamine (30mmol), then hydrogen fluoride (30mmol) is passed through, CO is used after sealing2To reaction
Kettle is replaced twice, and unlatching is stirred and heated to 120 DEG C, is continuously passed through CO2Reaction pressure is kept in 0.5MPa, reacts 24h, it is rear cold
But to room temperature, unnecessary CO is slowly released2Gas, obtains 3,3,3- tri- fluoro- 1,2-PDs and 4- trifluoromethyl ethylenes
Enester crude product, distribution of reaction products analysis is carried out by gas-chromatography, wherein TFPG, TFPC content be respectively 44.6%,
55.0%, obtain 3,3,3- tri- fluoro- 1,2-PD of target product and 4- trifluoromethyl ethylene carbonates through separation, process for refining
Common 42.3g, yield 98.6%.
Embodiment 18：
Embodiment 18 is reacted according to method identical in embodiment 17, except that the hydrogen halides in embodiment 17
Solution is passed through aqueous reaction liquid by HF and is formed, and embodiment 18 is passed through aqueous reaction liquid using HCl and is formed, as a result table
TFPG, TFPC content are respectively 43.9%, 55.4% in bright reaction solution, yield 88.3%.
Embodiment 19：
Commercially available hydrobromic acid (content 48%), mole matter of its molal weight 10% are added into 3,3,3- trifluoro-epoxy propanes
Amount 10% N- methylimidazoles, after mixing, by metering pump be delivered to preheater preheating, 70 DEG C of preheating temperature, then with CO2
Micro-mixer mix (200 μm of channel size), 160 DEG C of micro-mixer temperature, after mixing again through shell and tube reactor 180 DEG C,
(volume 300ml) is reacted under 1MPa, reaction contact time 1h, reacting product stream enters knockout drum, and top group is divided into dioxy
Change carbon, into carbon dioxide recovery system, in accordance, recycle；Bottoms material enters first rectifying column and carries out 3,3,3- trifluoros epoxy third
Alkane separates, and tower top obtains 3,3,3- trifluoro-epoxy propanes, returns to preheater and recycles, tower reactor obtains 3,3,3- tri- fluoro- 1,2-
Propane diols and 4- trifluoromethyl ethylene carbonate crude products, distribution of reaction products analysis is carried out by gas-chromatography, wherein TFPG,
TFPC contents are respectively 43.5%, 56.2%, then obtain the 3 of purity 99%, 3,3- tri- fluoro- 1,2- third through separation, process for refining
Glycol and 99.9% 4- trifluoromethyl ethylene carbonates, yield 98.2%.
(1) first product, purity 99.0%, warp1H-NMR、13C-NMR、19F-NMR characterizations are accredited 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)：δ 125.42 (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 products, purity 99.9%, warp1H-NMR、13C-NMR、19F-NMR characterizations are accredited as TFPC.
1H-NMR(500MHz,CDCl3)：δ4.98(m,1H),4.67(t,1H),4.57(q,1H)；13C-NMR(500MHz,
CDCl3)：δ 152.55 (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, is only the section Example of the present invention, and limitation in any form is not done to the present invention, all
It is any simple modification made according to the technical spirit of the present invention to above-described embodiment, equivalent variations and modification, belongs to this
In the range of inventive technique scheme.
Claims (7)
1. the preparation method of a kind of 3,3,3- tri- fluoro- 1,2-PD of coproduction and 4- trifluoromethyl ethylene carbonates, its feature exist
, for raw material, in the presence of hydrogen halide solution, organic base, reacted in 3,3,3- trifluoro-epoxy propanes with carbon dioxide,
70 DEG C -180 DEG C of reaction temperature, reaction pressure 0.1MPa-5MPa, reaction finishes, 3 obtained, 3,3- tri- fluoro- 1,2-PDs with
4- trifluoromethyl ethylene carbonate crude products, target product 3,3,3- tri- fluoro- 1,2-PD and 4- are obtained through separation, process for refining
Trifluoromethyl ethylene carbonate；Wherein, hydrogen halides dosage is the 0.5%-20% of 3,3,3- trifluoro-epoxy propane moles；It is organic
Alkali is dialkylamine, trialkylamine, N, and N- dimethylformamides or nitrogen-containing heterocycle compound, the dosage of organic base is 3,3,3- trifluoros
The 0.5%-20% of propylene oxide mole.
2. the fluoro- 1,2- propane diols of a kind of coproduction 3,3,3- tri- according to claim 1 and 4- trifluoromethyl ethylene carbonates
Preparation method, it is characterised in that the hydrogen halide solution is commercially available the hydroiodic acid of mass percent 55%-58%, quality
The hydrobromic acid of percentage 48%, the hydrochloric acid of mass percent 36%-38%, mass percent 40% hydrofluoric acid one kind or more
Kind combination.
3. the fluoro- 1,2- propane diols of a kind of coproduction 3,3,3- tri- according to claim 1 and 4- trifluoromethyl ethylene carbonates
Preparation method, it is characterised in that the machine alkali be selected from trialkylamine, n,N-dimethylacetamide, imidazoles, alkyl imidazole, pyrrole
Pyridine, 4-dimethylaminopyridine, 11 carbon -7- alkene of 1,8- diazabicylos, 1,5- diazabicyclos [4.3.0] -5- nonenes, 1,5,
Tri- azabicyclics of 7- [4.4.0] decyl- 5- alkene, 7- methyl isophthalic acids, tri- azabicyclics of 5,7- [4.4.0] decyl- 5- alkene or triethylene diamine.
4. the fluoro- 1,2- propane diols of a kind of coproduction 3,3,3- tri- according to claim 1 and 4- trifluoromethyl ethylene carbonates
Preparation method, it is characterised in that the hydrogen halides dosage be 3,3,3- trifluoro-epoxy propane moles 3%-15%, have
Machine base amount is the 3%-15% of 3,3,3- trifluoro-epoxy propane moles.
5. the fluoro- 1,2- propane diols of a kind of coproduction 3,3,3- tri- according to claim 1 and 4- trifluoromethyl ethylene carbonates
Preparation method, it is characterised in that the hydrogen halides dosage be 3,3,3- trifluoro-epoxy propane moles 5%-10%, have
Machine base amount is the 5%-10% of 3,3,3- trifluoro-epoxy propane moles.
6. the fluoro- 1,2- propane diols of a kind of coproduction 3,3,3- tri- according to claim 1 and 4- trifluoromethyl ethylene carbonates
Preparation method, it is characterised in that the reaction temperature be 100 DEG C -150 DEG C, reaction pressure 0.5MPa-2MPa.
7. the fluoro- 1,2- propane diols of a kind of coproduction 3,3,3- tri- according to claim 1 and 4- trifluoromethyl ethylene carbonates
Preparation method, it is characterised in that with 3,3,3- trifluoro-epoxy propanes for raw material, in the presence of hydrogen fluoride solution, triethylamine,
120 DEG C, reacted under 0.5MPa with carbon dioxide, 3 obtained, 3,3- tri- fluoro- 1,2-PDs and 4- trifluoromethyl carbonic acid
Vinyl acetate crude product, 3,3,3- tri- fluoro- 1,2-PD of target product and 4- trifluoromethyl ethylenes are obtained through separation, process for refining
Enester；Wherein, hydrogen fluoride dosage is the 10% of 3,3,3- trifluoro-epoxy propane moles；Water consumption is trifluoro-epoxy propane mole
The 50% of quality；Triethylamine dosage is the 10% of 3,3,3- trifluoro-epoxy propane moles.
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| CN115819662A (en) * | 2022-12-18 | 2023-03-21 | 四川轻化工大学 | Novel fluorine-containing epoxy resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115819662A (en) * | 2022-12-18 | 2023-03-21 | 四川轻化工大学 | Novel fluorine-containing epoxy resin and preparation method thereof |
| CN115819662B (en) * | 2022-12-18 | 2023-09-12 | 四川轻化工大学 | Fluorine-containing epoxy resin and preparation method thereof |
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