CN107501538A - A kind of PFPE and preparation method thereof - Google Patents
A kind of PFPE and preparation method thereof Download PDFInfo
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- CN107501538A CN107501538A CN201710648176.1A CN201710648176A CN107501538A CN 107501538 A CN107501538 A CN 107501538A CN 201710648176 A CN201710648176 A CN 201710648176A CN 107501538 A CN107501538 A CN 107501538A
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- hexafluoropropene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 150000002978 peroxides Chemical class 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 16
- 150000001265 acyl fluorides Chemical group 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 125000002081 peroxide group Chemical group 0.000 claims abstract description 11
- 229920000570 polyether Polymers 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000012545 processing Methods 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 claims 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 14
- -1 ether peroxide Chemical class 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000005855 radiation Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 101100328843 Dictyostelium discoideum cofB gene Proteins 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001960 triggered effect Effects 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
- C08G65/002—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
-
- 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
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/24—Polymeric initiators
-
- 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
Landscapes
- 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)
- Polyethers (AREA)
Abstract
The invention discloses it is a kind of based on hexafluoropropene (HFP) and oxygen be raw material prepare high stable, chemical resistance PFPE (PFPE) preparation method.Fluorine gas is used as chemical initiator, hexafluoropropene is more than 1500 PFPE with oxygen copolymerization mean molecule quantity, in synthesis phase by hexafluoropropene, oxygen carries out low-temperature oxidation polymerization in the presence of initiator in 75~40 DEG C, then the poly- PFPE peroxide obtained eliminates peroxide group at 160~300 DEG C, wherein, the mol ratio of hexafluoropropene and initiator is not less than 25, the mass ratio for obtaining active oxygen (PO) and whole PFPE in the peroxide in polyethers is not higher than 0.015, reactor filling material is periodic table of elements group VIII metal, the PFPE that peroxide obtains after eliminating carries out end group processing with fluorine gas at 120~260 DEG C and is used for removing end group acyl fluorides group.
Description
Technical field
The present invention relates to it is a kind of based on hexafluoropropene (HFP) and oxygen be raw material prepare high stable, chemical resistance perfluor
The preparation method of polyethers (PFPE).
Background technology
PFPE based on hexafluoropropene is fluoridized oligomer, formula：
RfAnd Rf' can be CF3-,CF3CF2- group
Wherein, fluorine carbon replaces connection with oxygen atom, and these oligomer have a big boiling spread, from 50-70 under the conditions of 1mmHg
DEG C to 240-350 DEG C, -60 DEG C or lower of fusing point.
Meanwhile PFPE have complicated uniqueness attribute how high thermal stability (450 DEG C), in high-corrosion medium
Chemical stability, fire prevention, nontoxic, dielectric property is high, adhering performance is big temperature range is slightly variable, greasy property is good, resistance to
Radiation etc..Above-mentioned complicated attribute causes them to be applied in different modern technologies fields, such as dielectric fluid, heat carrier
(cooling agent), oil, lubricating oil etc..
In many flows for obtaining these PFPEs, HFPO is described as initiation material.It is for example, Chinese
Patent CN103030800 describes the preparation method of HMW PFPE, i.e., containing fluorous solvent and metal fluoride catalysis
HFPO polymerization is carried out in the presence of agent.Patent CN103788363 describes HFPO in aprotic solvent
In, polymerisation is completed as catalyst using phase transfer reagent and anhydrous alkali metal fluoride.Above-mentioned patent uses Hexafluoropropylene third
Alkane raw material, thus cost is higher, is not the PFPE preparation method of very economical.
Therefore, because hexafluoropropene and oxygen copolymerization PFPE technology are more reasonable, application is more extensive, photochemistry side
One of method seemingly most wide-scale distribution.The basis of this technology is that first stage perfluoroolefine forms perfluor through photooxidation and gathered
For ether peroxide as intermediate compound, the intermediate compound is applied to synthesis other products.It should be noted, however, that this
A little peroxide group (PFPE peroxide) contents may be higher, blast of easily decomposing.
In patent US3704214, the process that these PFPEs are obtained from hexafluoropropene and oxygen is described, liquid phase, temperature-
100~80 DEG C, 0.1~40bar of pressure, ultraviolet radiation wave-lengths are no less thanHowever, in this course, peroxide
When the content of compound reaches 20%, safe procedures will be threatened.
P.1706-1710, RUSSIAN JOURNAL OF APPLIED CHEMISTRY, Vol.82, Iss.9,2009, are reported
The method that road obtains poly(perfluoropropene) polyethers by hexafluoropropene and oxygen in -65 DEG C~30 times copolymerization, ultraviolet radiation, which is used as, draws
It is known to send out influence of the agent to polymerization.The reaction is carried out continuously, and reaction mass takes reaction zone out of by hexafluoropropene flowing, with every
L volume 0.2~1.0L/h speed constantly circulates.The isolated PFPE oxide of -20~+50 DEG C of heating mixtures is low
Molecular weight gas byproduct is extremely separated for -60 DEG C by cooling down gas phase with hexafluoropropene, and hexafluoropropene part returns to reaction zone.
The major defect of fluoroolefins photochemical oxidation process is：
- poor efficiency process
- complicated device sets (level Hermetic Package quartz lamp)
UV ray radiation source of-poor efficiency etc..
In the B1 of patent EP 1568730, a kind of method that acquisition PFPE is improved by photochemical oxidation method is described, is removed
It is outer to report 200~350 nanometers of the wavelength of ultraviolet radiation, perfluoroacryloyl fluiride (CF2=CFCOF, PFAF) as initiation
Agent introduces reaction mass.The fluoro free radical that separation starts polymerization process under the influence of ultraviolet radiation is finally mentioned, so
Production efficiency is improved, but at the same time, the device offering question that photochemistry is related to complexity is still present, but also occurs
One complicated PFAF synthesis phase.
In the radical copolymerization method of fluoroolefins and oxygen, being used under low temperature, without ultraviolet radiation can homolysis generation freedom
The compound of base is that initiator-such as fluorine gas carries out initiated polymerization, should be a kind of more advanced method.
In United States Patent (USP) US5149842, describe fluoroolefins and oxygen obtains the process of perfluoroalkoxy radical derivative, condition is
Liquid phase, temperature are not higher than 50 DEG C, containing one or more F-X groups, wherein X=F, Cl, O, or ultraviolet radiation is initiator.
However, when using element fluorine in the process, the oxygen content of peroxide is not less than 0.5%, and safe procedures are caused with larger threat.Its
The use of its initiator causes process complicated, because one complicated initiator synthesis phase of increase, in addition, is retouched all
Found in the example stated：1st, the separation input of initiator and oxygen makes plant construction more complicated；2nd, needed in reactor continuous defeated
Enter nitrogen, this also makes device become complicated, and causes alkene greater loss easily occur in reaction zone.
Russian patent RU2046127 " acquisition methods of poly(perfluoropropene) oxide " describes hexafluoropropene and oxygen copolymerization obtains
The method for taking poly(perfluoropropene) oxide, temperature -30~65 DEG C, the volume ratio that fluorine gas is initiator, fluorine gas and oxygen be not between
It is equal to (0.1-1.1) under disconnected or recurrence pattern:It is copolymerized when (98.9-99.9).This process can deposit in inert gas
In lower progress, the volume ratio of fluorine, oxygen and inert gas is respectively (0.1-2.5):(20—40):(57.5—79.9).So,
Obtain the poly(perfluoropropene) oxide with distribution of low molecular weight, the scope of the mean molecule quantity of target product 1000~2000
It is interior.
United States Patent (USP) US3665041 and document Plenum Press, 1994, p.435-437 describe from containing poly- perfluor third
The process of peroxide group is eliminated in olefinic oxide, it is also contemplated that the elimination mechanism of peroxide group, heat treatment process is most
Good temperature interval is 160~250 DEG C, with process -40~50 DEG C of ultraviolet radiation, while also other unlisted flows
Details.
United States Patent (USP) US 3847978 describes the side that peroxide group is largely eliminated from PFPE peroxide
Method, hydrogen, hydrogen iodide, hydroiodic acid etc. are used in the method for description.
The content of the invention
Present invention aims at provide a kind of preparation method of PFPE (PFPE).It is the liquid in the presence of initiator
Phase hexafluoropropene (HFP) occurs low-temperature oxidation with oxygen and polymerize, and generation further eliminated containing oxidation (per) fluoropolymer
Oxide groups so that PFPE activity peroxidating oxygen (PO) contents are less than 0.015 with molecular weight ratio.Eliminate peroxide group
Afterwards, these PFPE with acyl fluorides terminal functionality carry out end-stabilizing place by element fluorine at a temperature of 120~260 DEG C again
Reason, finally obtain the PFPE of no acyl fluorides end group.
A kind of PFPE, it is characterised in that the chemical structural formula of the PFPE is：
A–(RCFO)n–(OCF2)m–(CF2)z–B
Wherein：
—(RCF) and (OCF O2) group random distribution；
- A groups are-F ,-COF ,-CF2- COF, CF3-, CF3CF2-, CF3- O-, CF3CF2One kind in-O-group；
- B group is-COF or-CF2One kind in-COF groups；
—RCF- it is-CF (CF3)CF2–、–CF2CF2CF2–、–CF2CF2- one kind or combinations thereof；
- Z=0-2；
- n+m=6-60, n/m=20-1；
Molecular weight M is higher than 1500, and active oxygen (PO) mass content is not higher than the 0.015 of total PFPE weight.
A kind of preparation method of PFPE as claimed in claim 1, it is characterised in that comprise the following steps：
(1) synthesis of PFPE peroxide：Hexafluoropropene, oxygen and initiator are continuously passed through reactor respectively
In, reaction temperature is controlled at -75~40 DEG C, and oxidative pressure is 100~175KPa, and PFPE peroxide is obtained after oxidation；
The mol ratio of hexafluoropropene and initiator is more than or equal to 25；
(2) peroxide eliminates：Metal packing reactor is warming up to 160~300 DEG C first, in conveying PFPE mistake
Oxide after heat treatment eliminates the peroxide group in PFPE peroxide, obtained into the nickel packed column reactor
PFPE product；Wherein, above-mentioned metal is the metal of the VIIIth race in the periodic table of elements；
(3) end group is handled：PFPE is subjected to end group processing with fluorine gas in 120~260 ° of С, removes end group acyl fluorides base
Group.A kind of preparation method of PFPE according to claim 2, it is characterised in that：Fluorine gas volume is dense in the step (1)
Degree control is 0.5~1.5%.
After it is preferred that, the oxidation step of the step (1) is specially：After hybrid reaction material is passed through reactor, and from reaction
Device is flowed out in receiver, and reaction mass is separated into hexafluoropropene and the polyethers with acyl fluorides group, the hexafluoropropene isolated
It is fed again into after recovery in reactor, reacts 3h, obtain PFPE peroxide.
After it is preferred that, metal packing reactor is warming up to 160~280 DEG C in the step (2).
After it is preferred that, metal packing reactor is nickel packed column reactor in the step (2).
After it is preferred that, the mol ratio of hexafluoropropene and initiator is less than or equal to 200.
Due to using above-mentioned technical proposal, having the advantages that：
The present invention is a kind of preparation method of PFPE (PFPE).It is the liquid phase hexafluoropropene in the presence of initiator
(HFP) low-temperature oxidation occurring with oxygen to polymerize, generation further eliminates peroxide group containing oxidation (per) fluoropolymer,
So that PFPE activity peroxidating oxygen (PO) contents are less than 0.015 with molecular weight ratio.After eliminating peroxide group, these carry acyl
The PFPE of fluorine terminal functionality carries out end-stabilizing processing by element fluorine at a temperature of 120~260 DEG C again, is not had finally
There is the PFPE of acyl fluorides end group.Its specific beneficial effect show as it is following some：
1st, the present invention keeps the mol ratio of hexafluoropropene and fluorine to be higher than 25, when this ratio is less than 25, it was observed that destroying
Type product increase (COF2, low molecule acyl fluorides and other), the molecular weight product of acquisition reduce.And during higher than 25, product structure is steady
Fixed, accessory substance is few, and purity is high, can bring huge economic benefit and social benefit.
2nd, it is 160~280 DEG C that the present invention, which controls temperature when eliminating peroxide, when temperature is less than 160 DEG C, peroxidating
The content of thing group is high, when reaction temperature is higher than 280 DEG C, causes product to destroy and reduce mean molecule quantity M；And temperature is 160
At~280 DEG C, peroxide group can be quickly removed, product structure is stable.
3rd, from it is light-initiated unlike, using fluorine gas as initiator catalysis hexafluoropropene gather with oxygen copolymerization perfluor
Ether.Peroxide generation content is relatively low in polyether products, and risk of explosion is relatively low.
4th, due to being triggered using fluorine gas, so telomerisation device is simpler than light-initiated device, cost is cheap.
5th, the inert gases such as nitrogen are not used and do diluent gas, avoid making device because continuously inputting nitrogen into reactor
Become complicated, and cause alkene to occur greater loss in the reaction region.
Embodiment
With reference to specific embodiment, the invention will be further described：
Embodiment 1
(1) synthesis of PFPE peroxide：
570g liquid hexafluoropropene is concentrated in the 1.0L reactors of outfit blender/agitator, oxygen and initiator
Mixture be continuously passed through reactor, -67 DEG C of reaction temperature respectively.Hexafluoropropene transfer rate 11.42L/h, initiator fluorine gas
Speed 0.12L/h, oxygen rates 11.84L/h.The temperature of reactor is maintained at -67 DEG C, the reaction mass comprising target product
Flowed out to from reactor in the receiver of heat, when receiver temperature is 20~70 DEG C, reaction mass is separated into hexafluoropropene
With the polyethers with acyl fluorides group, isolate hexafluoropropene recovery be fed again into reactor (and obtain acyl fluorides group polyethers production
Thing is directly placed into collector), react 3 hours, obtain comprising the 372g products that active oxygen (PO) is 0.31%.
(2) peroxide eliminates：
The polyether products of acquisition include PFPE peroxide, are delivered to 245 DEG C, the nickel packed column reactor of 0.5L volumes
Handled, product input rate is 210g/h.After heat treatment, the compound concentration of peroxide reaches 0.01%, is produced
The mean molecule quantity of product is equal to 3100.
(3) end group is handled：PFPE is subjected to end group processing with fluorine gas in 120~260 ° of С, removes end group acyl fluorides base
Group.
In embodiment 2-9, the reaction condition of the step (1) and the obtained PFPE peroxide yield such as institute of table 1
State, the step (2) and step (3) are same as Example 1；
Implementation conditions and result of the embodiment 1-9 of table 1 in step (1)
In embodiment 10-16, the reaction condition and result of the step (2) are as described in Table 2, the step (1) and step
(3) it is same as Example 1；
Implementation conditions and result of the embodiment 10-16 of table 2 in step (1)
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made ground simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (7)
1. a kind of PFPE, it is characterised in that the chemical structural formula of the PFPE is：
A–(RCFO)n–(OCF2)m–(CF2)z–B
Wherein：
—(RCF) and (OCF O2) group random distribution；
- A groups are-F ,-COF ,-CF2- COF, CF3-, CF3CF2-, CF3- O-, CF3CF2One kind in-O-group；
- B group is-COF or-CF2One kind in-COF groups；
—RCF- it is-CF (CF3)CF2–、–CF2CF2CF2–、–CF2CF2- one kind or combinations thereof；
- Z=0-2；
- n+m=6-60, n/m=20-1；
Molecular weight M is higher than 1500, and active oxygen (PO) mass content is not higher than the 0.015 of total PFPE weight.
2. a kind of preparation method of PFPE as claimed in claim 1, it is characterised in that comprise the following steps：
(1) synthesis of PFPE peroxide：Hexafluoropropene, oxygen and initiator are continuously passed through in reactor respectively, instead
Answering temperature control, oxidative pressure is 100~175KPa, and PFPE peroxide is obtained after oxidation at -75~40 DEG C；Hexafluoro third
The mol ratio of alkene and initiator is more than or equal to 25；
(2) peroxide eliminates：Metal packing reactor is warming up to 160~300 DEG C first, in conveying PFPE peroxidating
Thing after heat treatment eliminates the peroxide group in PFPE peroxide, obtains perfluor into the nickel packed column reactor
Polyether product；Wherein, above-mentioned metal is the metal of the VIIIth race in the periodic table of elements；
(3) end group is handled：PFPE is subjected to end group processing with fluorine gas in 120~260 ° of С, removes end group acyl fluorides group.
A kind of 3. preparation method of PFPE according to claim 2, it is characterised in that：Fluorine gas in the step (1)
Product concentration control is 0.5~1.5%.
A kind of 4. preparation method of PFPE according to claim 2, it is characterised in that：The oxidation step of the step (1)
It is rapid to be specially：After hybrid reaction material is passed through reactor, and flowed out to from reactor in receiver, reaction mass is separated into six
Fluoropropene and the polyethers with acyl fluorides group, it is fed again into after the hexafluoropropene recovery isolated in reactor, reacts 3h, obtained complete
Perfluoroalkyl polyether peroxide.
A kind of 5. preparation method of PFPE according to claim 2, it is characterised in that：Metal is filled out in the step (2)
Material reactor is warming up to 160~280 DEG C.
A kind of 6. preparation method of PFPE according to claim 2, it is characterised in that：Metal is filled out in the step (2)
Material reactor is nickel packed column reactor.
A kind of 7. preparation method of PFPE according to claim 2, it is characterised in that：Hexafluoropropene and initiator rub
You are than being less than or equal to 200.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710648176.1A CN107501538A (en) | 2017-08-01 | 2017-08-01 | A kind of PFPE and preparation method thereof |
| PCT/CN2017/108606 WO2019024287A1 (en) | 2017-08-01 | 2017-10-31 | Perfluoropolyether and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710648176.1A CN107501538A (en) | 2017-08-01 | 2017-08-01 | A kind of PFPE and preparation method thereof |
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| CN107501538A true CN107501538A (en) | 2017-12-22 |
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| CN201710648176.1A Pending CN107501538A (en) | 2017-08-01 | 2017-08-01 | A kind of PFPE and preparation method thereof |
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| CN (1) | CN107501538A (en) |
| WO (1) | WO2019024287A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031762A (en) * | 2021-09-30 | 2022-02-11 | 四川弘氟新材料有限公司 | Preparation process of perfluoropolyether surfactant and perfluoropolyether surfactant |
| CN114276532A (en) * | 2021-12-29 | 2022-04-05 | 山东东岳高分子材料有限公司 | A kind of preparation method and device of peroxide perfluoropolyether |
| CN114507340A (en) * | 2020-11-17 | 2022-05-17 | 中昊晨光化工研究院有限公司 | Perfluoropolyether and preparation method thereof |
| WO2022267932A1 (en) * | 2021-06-25 | 2022-12-29 | 浙江巨化技术中心有限公司 | Composition, liquid cooling agent and applications thereof, and immersion cooling system |
| CN115975167A (en) * | 2022-12-19 | 2023-04-18 | 四川道弘新材料有限公司 | Method for synthesizing perfluoropolyether by gas phase method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
| CN1047313A (en) * | 1989-04-20 | 1990-11-28 | 奥西蒙特公司 | The method for preparing peroxidized perfluoropolyether |
| CN1166506A (en) * | 1996-04-23 | 1997-12-03 | 奥西蒙特公司 | Process for preparing perfluoropolyethers with bromo- or iodo-containing end groups |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6709067A (en) * | 1964-04-09 | 1968-01-08 | ||
| RU2046127C1 (en) * | 1993-12-29 | 1995-10-20 | Акционерное общество закрытого типа "Автоконинвест" | Process for preparing polyperfluoropropylene oxide |
| CN103788363A (en) * | 2013-12-25 | 2014-05-14 | 上海艾肯化工科技有限公司 | Method for preparing perfluoropolyether with high molecular weight |
-
2017
- 2017-08-01 CN CN201710648176.1A patent/CN107501538A/en active Pending
- 2017-10-31 WO PCT/CN2017/108606 patent/WO2019024287A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3665041A (en) * | 1967-04-04 | 1972-05-23 | Montedison Spa | Perfluorinated polyethers and process for their preparation |
| CN1047313A (en) * | 1989-04-20 | 1990-11-28 | 奥西蒙特公司 | The method for preparing peroxidized perfluoropolyether |
| CN1166506A (en) * | 1996-04-23 | 1997-12-03 | 奥西蒙特公司 | Process for preparing perfluoropolyethers with bromo- or iodo-containing end groups |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114507340A (en) * | 2020-11-17 | 2022-05-17 | 中昊晨光化工研究院有限公司 | Perfluoropolyether and preparation method thereof |
| CN114507340B (en) * | 2020-11-17 | 2023-06-23 | 中昊晨光化工研究院有限公司 | A kind of perfluoropolyether and preparation method thereof |
| WO2022267932A1 (en) * | 2021-06-25 | 2022-12-29 | 浙江巨化技术中心有限公司 | Composition, liquid cooling agent and applications thereof, and immersion cooling system |
| CN114031762A (en) * | 2021-09-30 | 2022-02-11 | 四川弘氟新材料有限公司 | Preparation process of perfluoropolyether surfactant and perfluoropolyether surfactant |
| CN114276532A (en) * | 2021-12-29 | 2022-04-05 | 山东东岳高分子材料有限公司 | A kind of preparation method and device of peroxide perfluoropolyether |
| CN115975167A (en) * | 2022-12-19 | 2023-04-18 | 四川道弘新材料有限公司 | Method for synthesizing perfluoropolyether by gas phase method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019024287A1 (en) | 2019-02-07 |
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Application publication date: 20171222 |