CN106893090B - A kind of preparation method and products therefrom of perfluoro polyether oil - Google Patents
A kind of preparation method and products therefrom of perfluoro polyether oil Download PDFInfo
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- CN106893090B CN106893090B CN201510955756.6A CN201510955756A CN106893090B CN 106893090 B CN106893090 B CN 106893090B CN 201510955756 A CN201510955756 A CN 201510955756A CN 106893090 B CN106893090 B CN 106893090B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
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Abstract
The present invention provides a kind of preparation method of perfluoro polyether oil, comprising steps of 1) being placed in gas-liquid reaction equipment through unsaturated fluorine ether polymer obtained by photocatalysis as raw material using hexafluoropropene and/or tetrafluoroethene；2) it is passed through the gaseous mixture of fluorine gas and nitrogen into gas-liquid reaction equipment, the ratio of fluorine gas and nitrogen is 1/4~1/1；3) it was reacted by 6~12 hours, stops ventilation, material in gas-liquid reaction equipment is released, filtering, washing obtain product.The present invention is using the carboxyl and carbonyl in the direct fluorination treatment perfluor organic matter of higher concentration fluorine gas, the concentration of fluorine being strict in control fluorination process, avoid because concentration of fluorine it is too low do not react or it is excessively high and generate CF4And CF2O is obtained and is fluorinated substantially complete effect.
Description
Technical field
The invention belongs to organic chemistry fileds, and in particular to a kind of preparation method of perfluoropolyether object.
Background technique
Perfluoropolyether (being abbreviated as PFPE) is colourless, tasteless, transparency liquid at normal temperature, because there is saturation end group and a large amount of
Fluoro group, has heat-resisting, resistance to oxidation, radiation hardness, a corrosion-resistant, low characteristics such as volatilize, do not burn, and with can with plastics,
The good comprehensive performances such as elastomer, metal material be compatible, to become lubricant extremely reliable under harsh environment, extensively
Applied to the fields such as chemical industry, electronics, electrical, machinery, magnetic medium, nuclear industry, space flight.
As fluorination work product, the problems such as perfluoro polyether oil has raw material to be not easy to obtain, severe reaction conditions.In patent
The perfluoro fluorination in the lower situation of fluorine gas ratio is described in CN94116729, what reaction needed to protect in inert media
In the case of carry out；The perfluoro fluorination of poly- (tetrahydrofuran) diacetate esters is described in patent CN94116729, instrument detects fluorine
Change in product finally there are a large amount of-COOH, also illustrates that the reaction of unsaturated end group is carried out being entirely highly difficult.
Perfluoro polyether oil can be by, through photooxidation reaction, being given birth to hexafluoropropene or tetrafluoroethene under the action of telogen
At the intermediate product of Polyfluoroether oil, carbonyl or carboxyl end groups are then handled by different methods, obtain the fluothane of end group saturation
Base Polyfluoroether oil.Common method is that carbonyl hydrolysis becomes carboxyl, then becomes ester by methanol, or alkali reaction is added to generate
Then salt heats decarboxylation.All there is react insufficient, the problems such as process is cumbersome in use for these methods.In fluorine
Gas fluorination art, direct fluorination technology is very more, has various introductions, and direct fluorination reactor for perfluoro fluorination
Very comprehensively, but it is seldom for the introduction of perfluor organic matter terminal carboxyl group and carbonyl correlated response, and in fluorination process
The parameter for how controlling various links is not also detailed.
Summary of the invention
In view of the deficiencies of the prior art, present invention gained purpose is to propose a kind of preparation method of perfluoro polyether oil.
It is another object of the present invention to the perfluoro polyether oils that the method is prepared.
Realize the technical solution of above-mentioned purpose of the present invention are as follows:
A kind of preparation method of perfluoro polyether oil, comprising steps of
1) gas-liquid is placed in as raw material through unsaturated fluorine ether polymer obtained by photocatalysis using hexafluoropropene and/or tetrafluoroethene
In consersion unit；
2) it is passed through the gaseous mixture of fluorine gas and nitrogen into gas-liquid reaction equipment, the volume ratio of fluorine gas and nitrogen (or mole
Than) it is 1/4~1/1；
3) it was reacted by 6~12 hours, stops ventilation, material in gas-liquid reaction equipment is released, filtering, washing are produced
Object.
Wherein, the unsaturated fluorine ether polymer that hexafluoropropene and/or tetrafluoroethene are obtained through photocatalysis, product of formula are
CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCOF and/or CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCOOH；M in general formula
The unsaturated fluorine ether polymer of > 5 and n > 5 are raffinate, are the raw material of step 1).
Wherein, hexafluoropropene is through light-catalyzed reaction formula such as formula (1)
The preparation method of perfluoro polyether oil provided by the invention is fluorinationWithIt directly obtains
Raffinate, Bu Nengyong are then defined as when product n > 5 and m > that hexafluoropropene and/or tetrafluoroethene are obtained through photocatalysis
Make fluorine-containing surfactant.The present invention obtains the perfluoro polyether oil of high added value using this part raffinate, brings more preferably for enterprise
Economic benefit.
It being found in practice, in step 2), fluorine gas ratio is hardly reacted lower than 1/4, and when ratio is higher than 1/1, organic matter
It is easy chain rupture, so control fluorine gas ratio, most important to the product of fluorination reaction.Fluorine gas keeps constant speed and is passed through, with drum
The form of bubble is passed through in reactor, excessive velocities or slowly can all cause to react insufficient excessively.
Preferably, gas-liquid reaction equipment described in step 2) be bubble type gas-liquid reaction equipment, gas from liquid lower part into
Enter, be discharged above liquid.
It is highly preferred that in the step 2), the gaseous mixture volume of the fluorine gas and nitrogen that are passed through and the mass ratio of raw material are
2000L:2.5~3.5kg.
Wherein, reaction temperature is 30~200 DEG C, preferably 70~100 DEG C in the step 2).
In step 2), most preferably 70 DEG C~100 DEG C of the temperature of reactor, when fluorine gas ratio is higher, room temperature or low temperature shape
Under state, reaction is also that can carry out, but can be detained a large amount of HF in reacting, and subsequent processing work is increased, so step
It is carried out at 70 DEG C~100 DEG C in rapid C, does not need deacidification equipment in systems, HF can volatilized and be discharged while reaction
Reactor greatly reduces fluorinated systems complexity.
Wherein, the fluorine gas can obtain for electrolytic preparation, and the nitrogen is smart nitrogen of the purity 99.99% or more.
Wherein, the gaseous mixture of fluorine gas and nitrogen is passed through gas-liquid reaction equipment through pipeline, and magnetic alloy is breathed out in setting on the pipeline
Spinner flowmeter；The gas-liquid reaction equipment is provided with fluoro-containing plastic lining in inner wall or is made of Hastelloy material
Inner wall；The gas-liquid reaction equipment is provided with collet, is passed through hot water in collet.
The perfluoro polyether oil that preparation method of the present invention is prepared.
The beneficial effects of the present invention are:
The present invention is strict with control using the carboxyl and carbonyl in the direct fluorination treatment perfluor organic matter of higher concentration fluorine gas
Concentration of fluorine in fluorination process processed, avoid because concentration of fluorine it is too low do not react or it is excessively high and generate CF4And CF2O obtains fluorine
Change substantially complete effect.
The present invention obtains the perfluoro polyether oil of high added value using the raffinate of photocatalysis production perfluoro caprylic acid substitution emulsion,
Better economic benefit is brought for enterprise.
Polyfluoroether oil preparation method provided by the invention is suitable for perfluoro polyether carbonyl and converting carboxylate groups into saturation fluothane
The features such as base, it has step simple, fully reacting.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
In embodiment, unless otherwise specified, means used are the means of this field routine.
Embodiment 1:
Raw material is the perfluoro caprylic acid substitute raffinate that hexafluoropropene and tetrafluoroethene are obtained through photocatalysis, a large amount of in raffinate
Organic matter has general formula CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCOF and CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCOOH, m > 5, n > 5.
In fluoride system, the reactor of a 3L jacketed is used, reactor wall has fluoro-containing plastic lining, reactor
There is collet, is passed through hot water in collet.
2.7 ㎏ perfluoro caprylic acid substitute raffinates are added in reactor, reactor jacket is passed through controllable constant-temperature hot water, will be anti-
Device temperature is answered to maintain 70 DEG C.Fluorine gas is prepared using fluorine cell, Faradaic current 1000A, replaces 1.1m3Fluorine gas storage tank,
Exits and entrances valve is closed after collecting 3h；It suppresses into smart nitrogen (purity 99.99%, volume content) to the gauge pressure of fluorine gas storage tank and is
0.15MPa, with the progress of operation, fluorine gas and nitrogen ratios are a ranges in storage tank, with the replacement rate and generation when fluorine processed
The purity of fluorine gas is related, is averagely regarded as 0.85:2.5.
Mixed gas in fluorine gas storage tank breathes out magnetic alloy spinner flowmeter by setting on pipeline, pipeline, with 200L/h's
Constant flow rate is passed through in reactor, takes liquid phase air inlet, and liquid phase is contacted in the form of bubbling, is stopped ventilation after being passed through 10h, is used nitrogen
After gas displacement purging, liquid phase is released, is filtered with bottle,suction and filter paper, is obtained 2.34 ㎏ materials, 1.53 ㎏ transparent liquids are obtained after filtering
Body.
Mass spectrum and nmr analysis are free of carboxyl and carbonyl in liquid phase, to be saturated organic matter, structural formula CF3CF2CF2O
[CF2C(CF3)FO]m(CF2O)nCF3, molecular weight of product 12000.Raw material infrared spectrum before not being fluorinated is in 3448.71cm-
1,236,177cm-1 there is broad peak, in 1771.28cm-1,1730.30cm-1,983.67cm-1,800.74cm-1,
There is spike or acromion in 744.01cm-1,700.24cm-1,630.30cm-1, illustrate that raw material is the chemical combination for having carboxyl and carbonyl
Object；On product infrared spectrum after fluorination, there is broad peak in 1236.98cm-1, in 893.16cm-1,868.76cm-1,
There is spike or acromion in 809.37cm-1,746.32cm-1,713.38cm-1,529.47cm-1,467.38cm-1, illustrate product
In without carboxyl and carbonyl.
For product boiling point at 300 DEG C, appearance is transparency liquid.
Embodiment 2
2.7 ㎏ perfluoro caprylic acid substitute raffinates are added in reactor, reactor jacket is passed through controllable constant-temperature hot water, will be anti-
Device temperature is answered to maintain 80 DEG C.Fluorine gas uses calcirm-fluoride electrolytic preparation, and Faradaic current 1000A replaces 1.1m3Fluorine gas storage tank,
Exits and entrances valve is closed after collecting 3h；It suppresses into smart nitrogen (purity 99.99%, volume content) to the gauge pressure of fluorine gas storage tank and is
0.20MPa, the volume ratio of fluorine gas and nitrogen is 1:2 in storage tank at this time.
Mixed gas in fluorine gas storage tank breathes out magnetic alloy spinner flowmeter by setting on pipeline, pipeline, with 200L/h's
Constant flow rate is passed through in reactor, takes liquid phase air inlet, and liquid phase is contacted in the form of bubbling, is stopped ventilation after being passed through 10h, is used nitrogen
After gas displacement purging, liquid phase is released, is filtered with bottle,suction and filter paper, is obtained 2.56 ㎏ materials, 1.55 ㎏ transparent liquids are obtained after filtering
Body.
Other operations are the same as embodiment 1.
Mass spectrum and nmr analysis structural formula are CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCF3, molecular weight of product is
15000。
Embodiment 3
Raw material is the perfluoro caprylic acid substitute raffinate that tetrafluoroethene is obtained through photocatalysis, by 2.6 ㎏ perfluoro caprylic acid substitutes
Raffinate is added in reactor, and reactor jacket is passed through controllable constant-temperature hot water, and temperature of reactor is maintained 90 DEG C.Fluorine gas uses fluorine
Change calcium electrolytic preparation, Faradaic current 1000A replaces 1.1m3Fluorine gas storage tank, collect 3h after close exits and entrances valve；Into essence
It is 0.20MPa that nitrogen (purity 99.99%, volume content), which is suppressed to the gauge pressure of fluorine gas storage tank, at this time fluorine gas and nitrogen in storage tank
Volume ratio is 1:3.
Mixed gas in fluorine gas storage tank breathes out magnetic alloy spinner flowmeter by setting on pipeline, pipeline, with 200L/h's
Constant flow rate is passed through in reactor, takes liquid phase air inlet, and liquid phase is contacted in the form of bubbling, is stopped ventilation after being passed through 9h, is used nitrogen
After gas displacement purging, liquid phase is released, is filtered with bottle,suction and filter paper, is obtained 2.66 ㎏ materials, 1.80 ㎏ transparent liquids are obtained after filtering
Body.
Other operations are the same as embodiment 1.
Mass spectrum and nmr analysis structural formula are CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCF3, molecular weight of product is
11000。
Above embodiment be only preferred embodiments of the present invention will be described, not to the scope of the present invention into
Row limits, and without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to technical side of the invention
The all variations and modifications that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (5)
1. a kind of preparation method of perfluoro polyether oil, which is characterized in that comprising steps of
1) gas liquid reaction is placed in as raw material through unsaturated fluorine ether polymer obtained by photocatalysis using hexafluoropropene and/or tetrafluoroethene
In equipment；
2) it is passed through the gaseous mixture of fluorine gas and nitrogen into gas-liquid reaction equipment, the volume ratio of fluorine gas and nitrogen is 1/4~1/1,
The gaseous mixture volume of the fluorine gas and nitrogen that are passed through and the mass ratio of raw material are 2000L:2.5~3.5kg；The temperature reacted
It is 70~80 DEG C；
3) it was reacted by 9~12 hours, stops ventilation, material in gas-liquid reaction equipment is released, filtering, washing obtain product；
Wherein, the unsaturated fluorine ether polymer that hexafluoropropene and/or tetrafluoroethene are obtained through photocatalysis, general formula are
CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCOF and/or CF3CF2CF2O[CF2C(CF3)FO]m(CF2O)nCOOH；M in general formula
The unsaturated fluorine ether polymer of > 5 and n > 5 are the raw material of step 1).
2. preparation method according to claim 1, which is characterized in that gas-liquid reaction equipment described in step 2) is bubble type
Gas-liquid reaction equipment, gas from liquid lower part enter, are discharged above liquid.
3. preparation method according to claim 1 or 2, which is characterized in that the fluorine gas obtains, the nitrogen for electrolytic preparation
Gas is smart nitrogen of the purity 99.99% or more.
4. preparation method according to claim 1 or 2, which is characterized in that the gaseous mixture of fluorine gas and nitrogen is passed through through pipeline
Gas-liquid reaction equipment, the spinner flowmeter of magnetic alloy is breathed out in setting on the pipeline；The gas-liquid reaction equipment is provided in inner wall
Inner wall is made with Hastelloy material in fluoro-containing plastic lining；The gas-liquid reaction equipment is provided with collet, is passed through in collet
Hot water.
5. the perfluoro polyether oil that any preparation method of Claims 1 to 4 is prepared.
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| CN107382678B (en) * | 2017-07-11 | 2020-12-18 | 浙江巨圣氟化学有限公司 | Preparation method of perfluorobutyl methyl ether |
| CN110183643B (en) * | 2019-05-30 | 2021-12-14 | 上海欧勒奋生物科技有限公司 | Fluorination system of unstable terminal group of perfluoropolyether |
| CN111892705A (en) * | 2020-08-18 | 2020-11-06 | 中国石油化工股份有限公司 | Preparation method of saturated perfluoropolyether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3242218A (en) * | 1961-03-29 | 1966-03-22 | Du Pont | Process for preparing fluorocarbon polyethers |
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3242218A (en) * | 1961-03-29 | 1966-03-22 | Du Pont | Process for preparing fluorocarbon polyethers |
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
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