CN106633031A - Method for synthesizing perfluoropolyether - Google Patents
Method for synthesizing perfluoropolyether Download PDFInfo
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- CN106633031A CN106633031A CN201611173636.1A CN201611173636A CN106633031A CN 106633031 A CN106633031 A CN 106633031A CN 201611173636 A CN201611173636 A CN 201611173636A CN 106633031 A CN106633031 A CN 106633031A
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- pfpe
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- polyethylene glycol
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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
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing perfluoropolyether. Polyethylene glycol dimetyl ether is taken as a raw material; the polyethylene glycol dimetyl ether, CFC-113 and hexachloroethane react to generate the perfluoropolyether at a suitable reaction temperature under the action of a catalyst; the synthesizing method specifically comprises the following steps: mixing the CFC-113 and the hexachloroethane in a certain proportion, so that the polyethylene glycol dimetyl ether serving as a starting reactant can be dissolved; adding benzene so as to further accelerate a fluoridation; continuously introducing 20% F2/N2 mixed gas under a certain pressure to obtain a final product. In raw materials, the molecular weight of the polyethylene glycol dimetyl ether is 1,000 to 10,000. The CFC-113 and the hexachloroethane are in the mass ratio of (1-9):(1-9). The concentration of the polyethylene glycol dimetyl ether in a mixed solvent is 0.01 to 0.9 g/mL. The reaction pressure is 0 to 0.15 MPa. The gas introducing speed of the 20 percent F2/N2 mixed gas is 1 to 5 L/h. According to the method for synthesizing the perfluoropolyether disclosed by the invention, the raw materials are easy to prepare; the reaction yield is improved; the operation is simple; the perfluoropolyether is easy to purify and can be produced in large scale.
Description
Technical field
The present invention relates to fluoride-containing PMMA field, and in particular to a kind of method of synthesis PFPE.
Background technology
PFPE is a kind of high molecular polymer, is at normal temperatures oily liquids that colorless and odorless is transparent.Molecular structure
In only contain tri- kinds of elements of C, F, O, polymer viscosity increases with the increase of molecular weight, and C-F keys are to master in its molecular structure
The shielding action of chain makes it have heat-resisting, resistance to oxidation, corrosion-resistant, resistance to irradiation and the characteristic such as does not fire.By it through stabilization processes
The fluorine ether oil for preparing afterwards, is a kind of good special lubricating oil under can apply to harsh environment, is widely used in aviation boat
The fields such as its industry, electronics industry, electrical industry and nuclear industry.
At present, the synthetic technology of PFPE mainly includes two classes, and the first kind is using HFPO or tetrafluoro oxygen
Azetidine carries out anionic polymerisation, and this method cost of material is higher, causes the route production cost higher.Equations of The Second Kind is to adopt
With tetrafluoroethene or the photooxidation polymerization technique of hexafluoropropene, although this technology production cost is relatively low, complex process
And with larger danger, reaction unit need to consume a large amount of liquid nitrogen, keep in repair and safeguard extremely difficult.
The content of the invention
The purpose of the present invention is the deficiency existed for existing technology, it is proposed that a kind of high working efficiency prepares perfluor
The method of propionyl fluoride.
Technical problem solved by the invention employs the following technical solutions to realize a kind of method of synthesis PFPE, with
NHD is raw material, in suitable reaction temperature, and in the presence of catalyst, NHD and CFC-
113 and carbon trichloride reaction generate PFPE, reactive chemistry formula is as follows
The synthetic method is comprised the following steps that：Mixed under certain proportion with CFC-113 and carbon trichloride and cause it
Initial reactant NHD can be dissolved, benzene is added further to promote fluorination reaction, under a certain pressure continuously
It is passed through 20%F2/N2Gaseous mixture obtains final product.
The molecular weight of NHD is 1000～10000 in the raw material.
The mass ratio of the CFC-113 and carbon trichloride is 1～9: 1～9, preferably 1: 3 or 1: 4.
Concentration of the NHD in mixed solvent is 0.01～0.9g/mL, preferably 0.1～0.2g/
mL。
The reaction pressure is 0～0.15MPa.
The 20%F2/N2The draft speed of gaseous mixture is 1～5L/h.
Beneficial effects of the present invention are：A kind of method of synthesis PFPE is proposed, raw material is easily prepared, improves reaction
Yield, simple to operate, easily purifying, can be amplified production.
Specific embodiment
Technical scheme is elaborated with reference to specific embodiment.
Embodiment 1：A kind of method of synthesis PFPE, with NHD as raw material, in suitable reaction temperature,
And in the presence of catalyst, NHD is with CFC-113 and carbon trichloride reaction generates PFPE, reactive chemistry
Formula is as follows
The synthetic method is comprised the following steps that：Mixed under certain proportion with CFC-113 and carbon trichloride and cause it
Initial reactant NHD can be dissolved, benzene is added further to promote fluorination reaction, under a certain pressure continuously
It is passed through 20%F2/N2Gaseous mixture obtains final product.The molecular weight of NHD is 1000～10000 in the raw material.
The mass ratio of the CFC-113 and carbon trichloride is 1～9: 1～9, preferably 1: 3 or 1: 4.The NHD
Concentration in mixed solvent is 0.01～0.9g/mL, preferably 0.1～0.2g/mL.The reaction pressure be 0～
0.15MPa.The 20%F2/N2The draft speed of gaseous mixture is 1～5L/h.
Embodiment 2, preparation 5L autoclaves, are arranged in series cooling tube (0 DEG C), and activity on the gas vent of autoclave
Charcoal absorption tower and KOH absorption towers, CFC-113 (150mL), carbon trichloride (550mL) and benzene (0.5g) are added in reactor, are protected
Hold as 25 DEG C, stir while being passed through 20%F with the speed of 3L/h2/N2Gaseous mixture, while with 24h by NHD
(molecular weight 2000) (106g) and CFC-113 (150mL), the mixture of carbon trichloride (500mL) is added in reactor, is pressed afterwards
Power rises to 0.1Mpa, and temperature rises to 40 DEG C and maintains 5h.Terminate reaction afterwards, reaction solution is taken out, solvent is distilled off, obtain
To product 92g, yield 33%.
Embodiment 3, preparation 10L autoclaves, are arranged in series cooling tube (0 DEG C) on the gas vent of autoclave, and living
Property charcoal absorption tower and KOH absorption towers, CFC-113 (150mL), carbon trichloride (1350mL) and benzene (0.5g) are added into reactor
In, 25 DEG C are remained, stir while being passed through 20%F with the speed of 3L/h2/N2Gaseous mixture, while with 24h by polyethylene glycol
(101g) and CFC-113 (150mL), the mixture of carbon trichloride (1300mL) adds reactor to dimethyl ether (molecular weight 2000)
In, afterwards pressure rises to 0.1Mpa, and temperature rises to 40 DEG C and maintains 5h.Terminate reaction afterwards, reaction solution is taken out, distillation is removed
Solvent is removed, product 77g, yield 29% is obtained.
Embodiment 4, preparation 5L autoclaves, are arranged in series cooling tube (0 DEG C), and activity on the gas vent of autoclave
Charcoal absorption tower and KOH absorption towers, CFC-113 (150mL), carbon trichloride (550mL) and benzene (0.5g) are added in reactor, are protected
Hold as 25 DEG C, stir while being passed through 20%F with the speed of 3L/h2/N2Gaseous mixture, while with 24h by NHD
(molecular weight 1000) (98g) and CFC-113 (150mL), the mixture of carbon trichloride (500mL) is added in reactor, is pressed afterwards
Power rises to 0.1Mpa, and temperature rises to 40 DEG C and maintains 5h.Terminate reaction afterwards, reaction solution is taken out, solvent is distilled off, obtain
To product 93g, yield 35%.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement is both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (7)
1. it is a kind of synthesis PFPE method, it is characterised in that：With NHD as raw material, temperature is suitably being reacted
Degree, and in the presence of catalyst, NHD is with CFC-113 and carbon trichloride reaction generates PFPE, reaction
Chemical formula is as follows
2. it is according to claim 1 synthesis PFPE method, it is characterised in that：The concrete steps of the synthetic method
It is as follows：Being mixed under certain proportion with CFC-113 and carbon trichloride allows it to dissolve initial reactant polyethylene glycol diformazan
Ether, adds benzene that 20%F is continuously passed through further to promote fluorination reaction, under a certain pressure2/N2Gaseous mixture obtains final product.
3. it is according to claim 1 and 2 synthesis PFPE method, it is characterised in that：Polyethylene glycol in the raw material
The molecular weight of dimethyl ether is 1000～10000.
4. it is according to claim 1 and 2 synthesis PFPE method, it is characterised in that：The CFC-113 and hexachloroethanc
The mass ratio of alkane is 1～9: 1～9, preferably 1: 3 or 1: 4.
5. it is according to claim 2 synthesis PFPE method, it is characterised in that：The NHD is mixed
Concentration in bonding solvent is 0.01～0.9g/mL, preferably 0.1～0.2g/mL.
6. it is according to claim 2 synthesis PFPE method, it is characterised in that：The reaction pressure be 0～
0.15MPa。
7. it is according to claim 2 synthesis PFPE method, it is characterised in that：The 20%F2/N2Gaseous mixture it is logical
Gas speed is 1～5L/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611173636.1A CN106633031A (en) | 2016-12-14 | 2016-12-14 | Method for synthesizing perfluoropolyether |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611173636.1A CN106633031A (en) | 2016-12-14 | 2016-12-14 | Method for synthesizing perfluoropolyether |
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| CN201611173636.1A Pending CN106633031A (en) | 2016-12-14 | 2016-12-14 | Method for synthesizing perfluoropolyether |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101757A (en) * | 1984-10-16 | 1987-01-31 | 大金工业株式会社 | The method for preparing fluor containing polyethers |
| US5506309A (en) * | 1988-09-28 | 1996-04-09 | Exfluor Research Corporation | Perfluorinates polyethers |
-
2016
- 2016-12-14 CN CN201611173636.1A patent/CN106633031A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101757A (en) * | 1984-10-16 | 1987-01-31 | 大金工业株式会社 | The method for preparing fluor containing polyethers |
| US5506309A (en) * | 1988-09-28 | 1996-04-09 | Exfluor Research Corporation | Perfluorinates polyethers |
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