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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- Prior art keywords
- pfpe
- synthesis
- cfc
- polyethylene glycol
- reaction
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000010702 perfluoropolyether Substances 0.000 title abstract 5
- 230000002194 synthesizing effect Effects 0.000 title abstract 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 abstract 3
- 238000004334 fluoridation Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UAGZMXMHGIRPIY-UHFFFAOYSA-N [O].N1CCC1 Chemical compound [O].N1CCC1 UAGZMXMHGIRPIY-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- 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 |
Applications Claiming Priority (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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| Publication Number | Publication Date |
|---|---|
| CN106633031A true CN106633031A (en) | 2017-05-10 |
Family
ID=58822970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201611173636.1A Pending CN106633031A (en) | 2016-12-14 | 2016-12-14 | Method for synthesizing perfluoropolyether |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119143983A (en) * | 2024-11-13 | 2024-12-17 | 湖南天氟新材料有限公司 | A method for preparing perfluoropolyether compound |
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 | Process for preparing halogen-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 | Process for preparing halogen-containing polyethers |
| US5506309A (en) * | 1988-09-28 | 1996-04-09 | Exfluor Research Corporation | Perfluorinates polyethers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119143983A (en) * | 2024-11-13 | 2024-12-17 | 湖南天氟新材料有限公司 | A method for preparing perfluoropolyether compound |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |
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