CN104496823B - Preparation method of fluorine-containing carbonic ester - Google Patents
Preparation method of fluorine-containing carbonic ester Download PDFInfo
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- CN104496823B CN104496823B CN201410805377.4A CN201410805377A CN104496823B CN 104496823 B CN104496823 B CN 104496823B CN 201410805377 A CN201410805377 A CN 201410805377A CN 104496823 B CN104496823 B CN 104496823B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
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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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Abstract
The invention discloses a preparation method of a fluorine-containing carbonic ester. According to the method, a carbonic ester and a fluorine-containing olefin are taken as starting raw materials and telomerization is performed on the starting raw materials to directly obtain the desired fluorine-containing carbonic ester. The raw materials adopted in the method are cheap and easily available, and the method has relatively high reaction conversion rate and selectivity. The results of a plurality of tests indicate that the selectivity of the fluorine-containing carbonic ester is between 75% and 90%, the molecular weight distribution of the telomerization product is bias to low carbon number components (link number=1 to 4), and a few high carbon number components can be generated.
Description
Technical field
The present invention relates to chemical preparation process, particularly to a kind of preparation method of fluorine-containing carbonic ester.
Background technology
In recent years, with increasingly sharpening the problems such as the day by day exhausted of traditional energy and global warming, novel lithium from
Sub- secondary cell has obtained widely applying in the field such as electric motor car and new-energy automobile, simultaneously also to as lithium ion secondary electricity
The material property of pond electrolyte is put forward higher requirement.
The electrolyte of early stage lithium ion battery adopts the carbonats compound such as ethylene carbonate, dimethyl carbonate as molten
Agent.But, the flash-point of such solvent is relatively low, so being easily caused combustion explosion in the case of the superheated that overcharges, and
And its viscosity is higher, conductivity at low temperature is relatively low.
A kind of linear carbonate containing fluoroalkyl of the patent report of Application No. CN200680004963.2 as lithium from
The electrolyte of sub- battery.This electrolyte is in the compatibility of anti-flammability, the dissolubility of electrolytic salt and varsol, low-temperature characteristics
All very excellent with aspects such as proof voltages.In this patented technology, the method that the preparation of this electrolyte employs traditional ester exchange,
Using fluorinated alcohols as raw material, obtain with alkyl carbonate or phosgene reaction under acid catalyst or base catalyst effect, the method
Raw materials used fluorinated alcohols are general all costly, relatively costly.
The United States Patent (USP) of Application No. US20090086408 reports a kind of fluorine-containing carbonic ester of ring-type as lithium ion battery
The application of electrolyte.This electrolyte has the cryogenic property of brilliance, and has higher flash-point, is conducive to improving lithium-ion electric
The safety in pond.This patented technology adopts a kind of epoxide of fluorine-containing side chain as raw material, with CO under LiBr catalysis2Send out
Raw ring expansion obtains the fluorine-containing carbonic ester of ring-type, the epoxide of the raw materials used fluorine-containing side chain of the method also costly, work
Industry production cost is too high.
Content of the invention
The technical problem to be solved in the present invention is that a kind of reaction raw materials of offer are cheap and easy to get, process route is simple, reaction
Conversion ratio and selectivity all compare the preparation method of high fluorine-containing carbonic ester.
For solving above-mentioned technical problem, the present invention provides a kind of preparation method of fluorine-containing carbonic ester, prepares following formula 1 or formula 2
Shown fluorine-containing carbonic ester：
Wherein, Rf1And Rf2It is containing fluoroalkyl, formula is:
Wherein：Chain number n is positive integer, and q is nonnegative integer, R1、R2、R3、R4、R5、R6For H, F or CF3, m is non-negative
Integer, R is H or hydrocarbon chain group.
Wherein, during fluorine-containing carbonic ester shown in formula 1, the linear carbonate shown in formula 3 is as initiation material：
Reaction condition is：In a kettle., add 0.02 part -0.04 part（The ratio of molal quantity）Containing iodine catalyst and
0.07 part -0.12 part（The ratio of molal quantity）Initiator, 2 parts of linear carbonate, rear reactor is hunted leak evacuation, addition portion
Divide Fluorine containing olefine, be heated to more than the boiling point of raw material, when pressure rises to 1.5MPa-3MPa, add again and contain for one or more
Fluoroolefins, to Fluorine containing olefine total amount be 0.1 part -2 parts（The ratio of molal quantity）, obtain fluorine-containing shown in formula 1 through telomerisation
Carbonic ester, rectification obtains final products.
Wherein, during fluorine-containing carbonic ester shown in formula 2, the cyclic carbonate shown in formula 4 is as initiation material：
Reaction condition is：In a kettle., add 0.02 part -0.04 part（The ratio of molal quantity）Containing iodine catalyst and
0.07 part -0.12 part（The ratio of molal quantity）Initiator, 2 parts of cyclic carbonate, rear reactor is hunted leak evacuation, addition portion
Point Fluorine containing olefine, is heated to more than the boiling point of raw material, when pressure rises to 1.5MPa-3MPa, adds Fluorine containing olefine again, to containing
The total amount of fluoroolefins is 0.1～2 part（The ratio of molal quantity）, obtain the fluorine-containing carbonic ester shown in formula 2, rectification through telomerisation
Obtain final products.
Preferably：Described Fluorine containing olefine adds again.
Preferably：Described is KI containing iodine catalyst, NaI, I2, NaIO3,Bu4NI, Me4NI or Me3Any one in BuNI
Or it is several.
Preferably：Described initiator can be dibenzoyl peroxide, tert-butyl hydroperoxide, azodiisobutyronitrile or two
Any one or several in tert-butyl peroxide.
Preferably：Described Fluorine containing olefine can be tetrafluoroethene, hexafluoropropene, vinylidene, 3,3,3- trifluoropropyl
Any one or several in alkene, 2,3,3,3- tetrafluoropropene or 1,3,3,3- tetrafluoropropene.
The present invention compared with prior art has the following advantages：
The present invention with carbonic ester and Fluorine containing olefine as initiation material, under acting on containing iodine catalyst and initiator, through toning
Poly- reaction directly obtains required fluorine-containing carbonic ester.Compared with preparing the method for fluorine-containing carbonic ester with existing other, the method institute
Using raw material more cheap and easy to get, and there is higher reaction conversion ratio and selectivity.Show through test of many times result, adopt
This technical scheme, between 75-90%, the molecular weight distribution of telomerization product is partial to low carbon number component to the selectivity of fluorine-containing carbonic ester
（Chain number n=1～4）, produce the component of seldom high carbon number.
Specific embodiment
Embodiment 1
To in 1L rustless steel vertical response kettle, add Bu410 grams of NI catalyst, 8 grams of tert-Butanol peroxide, dimethyl carbonate
180 grams.Reactor nitrogen leak test, evacuation.Add 30 grams of TFE, be warming up to 130 DEG C, when pressure is down to 2.0MPa, supplement
TFE, is repeated several times, until dimethyl carbonate is equal to 2 with the mol ratio of TFE:1, pressure no longer declines, cooling, reclaims unreacted
Dimethyl carbonate, obtain telomerization product CH3OCO2CH2(CF2CF2)nTotally 142 grams of H.Distillation, gas chromatographic analysiss, each component
Ratio is shown in Table 1.
Table 1：
Embodiment 2
To in 1L rustless steel vertical response kettle, add Bu410 grams of NI catalyst, 8 grams of tert-Butanol peroxide, diethyl carbonate
236 grams.Reactor nitrogen leak test, evacuation.Add 30 grams of TFE, be warming up to 140 DEG C, when pressure is down to 2.0MPa, supplement
TFE, is repeated several times, until diethyl carbonate is equal to 2 with the mol ratio of TFE:1, pressure no longer declines, cooling, reclaims unreacted
Diethyl carbonate, obtain telomerization product CH3CH2OCO2CHCH3(CF2CF2)nTotally 159 grams of H.Distillation, gas chromatographic analysiss, respectively
The ratio of component is shown in Table 2.
Table 2：
Embodiment 3
To in 1L rustless steel vertical response kettle, sequentially add 176 grams of the cyclic carbonate shown in following formula 5, Bu4NI catalyst
10 grams, 6 grams of tert-Butanol peroxide.Reactor nitrogen leak test, evacuation.Add 30 grams of TFE, be warming up to 140 DEG C, treat that pressure is down to
During 2.0MPa, supplement TFE, be repeated several times, until cyclic carbonate is equal to 2 with the mol ratio of TFE:1, pressure no longer declines, cold
But, reclaim unreacted cyclic carbonate, obtain totally 131 grams of the telomerization product shown in following formula 6.Distillation, gas chromatographic analysiss, respectively
The ratio of component is shown in Table 3.
Table 3：
Embodiment 4
To in 1L rustless steel vertical response kettle, add 180 grams of dimethyl carbonate, Bu410 grams of NI catalyst, di-t-butyl mistake
10 grams of oxide.Reactor nitrogen leak test, evacuation.Add 30 grams of TFE, be warming up to 130 DEG C, treat that pressure is down to 2.0MPa
When, supplement TFE, be repeated several times, until dimethyl carbonate is equal to 2 with the mol ratio of TFE:1, pressure no longer declines, cooling, reclaims
Unreacted dimethyl carbonate, obtains telomerization product CH3OCO2CH2(CF2CF2)nTotally 138 grams of H.Distillation, gas chromatographic analysiss, respectively
The ratio of component is shown in Table 4.
Table 4：
Embodiment 5
To in 1L rustless steel vertical response kettle, add 180 grams of dimethyl carbonate, Bu410 grams of NI catalyst, di-t-butyl mistake
10 grams of oxide.Reactor nitrogen leak test, evacuation.Add 10 grams of TFE, 30 grams of hexafluoropropenes, be warming up to 130 DEG C, wait to press
When power is down to 2.0MPa, supplements TFE and hexafluoropropene, be repeated several times, until mol ratio of dimethyl carbonate and tetrafluoroethene etc.
In 2:1, dimethyl carbonate and Fluorine containing olefine mol ratio be less than 2:2, pressure no longer declines, cooling, reclaims unreacted containing
Fluoroolefins and dimethyl carbonate, obtain telomerization product CH3OCO2CH2(CF2CF2)n(CFCF3CF2)qTotally 192 grams of H.Distillation, gas phase
Chromatography, the ratio of each component is shown in Table 5.
Table 5：
Claims (3)
1. a kind of preparation method of fluorine-containing carbonic ester, described fluorine-containing carbonic ester is as shown in following formula 1：
Wherein, Rf 1It is containing fluoroalkyl, formula is:
Wherein：Chain number n is positive integer, and q is nonnegative integer, R1、R2、R3、R4、R5、R6For H, F or CF3, R is hydrogen or hydrocarbon chain base
Group it is characterised in that：
Linear carbonate shown in following formula 3 as initiation material,
Reaction condition is：In a kettle., add 0.02 part -0.04 part of the initiation containing iodine catalyst and 0.07 part -0.12 part
Agent, described is Bu containing iodine catalyst4NI, Me4NI or Me3Any one or several in BuNI, described initiator can be peroxide
Change dibenzoyl, tert-butyl hydroperoxide, any one or several in azodiisobutyronitrile or di-tert-butyl peroxide, 2 parts
Linear carbonate, rear reactor is hunted leak evacuation, adds part Fluorine containing olefine, is heated to more than the boiling point of raw material, works as pressure
When rising to 1.5MPa-3MPa, add one or more Fluorine containing olefine again, be 0.1 part～2 parts to Fluorine containing olefine total amount, pass through
Telomerisation obtains the fluorine-containing carbonic ester shown in formula 1, and rectification obtains final products, is directed to the ratio that number is all molal quantity
Example.
2. a kind of preparation method of fluorine-containing carbonic ester, described fluorine-containing carbonic ester is as shown in following formula 2：
Wherein, Rf 2It is containing fluoroalkyl, formula is:
Wherein：Chain number n is positive integer, and q is nonnegative integer, R1、R2、R3、R4、R5、R6For H, F or CF3,
M in formula 2 is nonnegative integer, R be hydrogen or hydrocarbon chain group it is characterised in that：
Cyclic carbonate shown in following formula 4 is initiation material：
Reaction condition is：In a kettle., add 0.02 part -0.04 part of the initiation containing iodine catalyst and 0.07 part -0.12 part
Agent, described is Bu containing iodine catalyst4NI, Me4NI or Me3Any one or several in BuNI, described initiator can be peroxide
Change dibenzoyl, tert-butyl hydroperoxide, any one or several in azodiisobutyronitrile or di-tert-butyl peroxide, 2 parts
Cyclic carbonate, rear reactor is hunted leak evacuation, adds part Fluorine containing olefine, is heated to more than the boiling point of raw material, works as pressure
When rising to 1.5MPa-3MPa, add Fluorine containing olefine again, be 0.1～2 part to Fluorine containing olefine total amount, obtain through telomerisation
Fluorine-containing carbonic ester shown in formula 2, rectification obtains final products, is directed to the ratio that number is all molal quantity.
3. a kind of fluorine-containing carbonic ester according to claim 1 and 2 preparation method it is characterised in that：Described fluorine-containing alkene
Hydrocarbon can be tetrafluoroethene, hexafluoropropene, vinylidene, 3,3,3- trifluoro propenes, 2,3,3,3- tetrafluoropropenes or 1,3,3,3-
Any one or several in tetrafluoropropene.
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