CN106317398A - Method for decomposition of peroxide in perfluoropolyether - Google Patents
Method for decomposition of peroxide in perfluoropolyether Download PDFInfo
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- CN106317398A CN106317398A CN201510382924.7A CN201510382924A CN106317398A CN 106317398 A CN106317398 A CN 106317398A CN 201510382924 A CN201510382924 A CN 201510382924A CN 106317398 A CN106317398 A CN 106317398A
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Abstract
The invention belongs to the field of organic chemistry, and relates to a method for decomposition of peroxide in perfluoropolyether, one or more of metal catalysts, metal oxide catalysts and metal fluoride catalysts are added to a perfluoropolyether product prepared by a photooxidation method, and the peroxide in the perfluoropolyether product is decomposed at the temperature of 80-150 DEG C. The method provided by the invention has the advantages of relatively thorough decomposition of fluorine-containing peroxide, short time and low requirements for equipment. The peroxide value of perfluoropolyether after treatment is low and the performance is stable. The method can also be used for treatment of similar fluorine-containing peroxide.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of from the PFPE of synthesis
Method except peroxide.
Background technology
PFPE (PFPE) is to only have the polymer of tri-kinds of elements of C, F, O in molecule,
It is liquid under room temperature.PFPE molecule has the C-H that higher C-F key instead of in hydro carbons
Key, and because of the existence of C-O and C-C strong covalent bond, and the spy that PFPE molecule is neutral
Point so that PFPE has higher chemical stability and oxidation stability and good change
Learn inertia and insulating property (properties).This perfluoropolyethers has the widest potential use, such as, work as end
Stable-CF is formed after base fluorination3Group, it is possible to as perfluoro polyether oil；When end group water
Form-COOH after solution and just can be used as emulsifying agent, be widely used in oil field, coating, fluorine-containing
Polymer emulsifier etc..PFPE preparation method mainly has two kinds: a kind of with perfluor ring
Ethylene Oxide is raw material, obtains with fluorion as polymerization catalyst in aprotic solvent；Another
Planting is with Fluorine containing olefine for raw material at low temperatures together with oxygen, uses ultra violet lamp, oxidation
Polymerization obtains the PFPE mixture that structure is different.The thick product of this ultraviolet oxidation polymerization
Thing contains the peroxy-radical of substantial amounts of instability.
In many applications, if existed containing unstable fluorine-containing peroxide, for answering
With having large effect, particularly in the production of fluoropolymer, use as emulsifying agent
Time, polymerization can be had a strong impact on, especially affect the speed of polymerization, because these are fluorine-containing
Peroxide itself can be as the initiator of a kind of polymer, and its stability is due to its point
The different of minor structure exist in erratic behavior, and the temperature height i.e. decomposed is different, energy size
Difference, time length is the most equal.
About containing fluorination alkyl-carbonyl peroxide thermal decomposition, Zhao, c (The Journal of
Organic Chemistry, 1982,47,2009) and Sawada, H (Journal of Fluorince
Chemistry,1990,46,423；Chemical Reviews, 1996,96,1779) give report,
They sum up thermodynamics and the power that part thermally decomposes containing fluoroalkanoyl and aroly peroxide
Learn principle, it is believed that due to the existence of hydrofluorocarbons this Electron absorption body, make-O-O-bond energy reduce,
Thus it is thermally-stabilised not as common acyl peroxide without fluorohydrocarbon.With common hydrocarbon organic mistake
Unlike peroxide breaks down, the invention reside in containing on a small quantity in the PFPE processing preparation
Fluorine peroxide impurity.With Zhao, c and Sawada, the decomposition hydrofluorocarbons that H et al. is theoretical
Unlike acyl peroxide, research worker of the present invention has found that the PFPE of preparation
In fluorine-containing amount of peroxides relatively little, arrived this small amount of degree, also just can be relatively
Stable.
Method disclosed in the patent of application number 201010146420.2, is in the basic conditions or water
The method irradiated through heating or ultraviolet light in solution eliminates these peroxy-radicals.Peroxynitrite decomposition
Group mainly makes the such group of O O break to form two relatively stable compounds.Point
Solve this kind of peroxide to be typically to carry out in aqueous, owing to there is HF, and with higher
Temperature, therefore for the equipment of common material, requirement can not be met.Must make
With requiring the highest equipment and parts thereof, thus produce higher cost of equipment.Additionally to building ring
Border and operating condition also have higher requirement.And owing to material corrosion is strong, equipment and
Parts are easily damaged, and therefore operating cost is the highest.
Summary of the invention
To sum up reason, we find a kind of fluorine-containing peroxidating decomposed in PFPE product hereby
The method of thing.
Realizing the object of the invention technical scheme is:
The decomposition method of peroxide in a kind of PFPE, by metallic catalyst, burning
One or more in thing catalyst, metal fluoride catalysts join prepared by photooxidation method
In PFPE product, at 80～150 DEG C, decompose the peroxide in PFPE product.
Wherein, described PFPE peroxide structure formula is: Rf-O-O-Rf,
One or more during wherein Rf is following structural:
A-O-(-C(Tf)(OCF3)CF2-O)m(Gf-O-O)n-(CF2O)p-(CF2OO)q-(CF(Tf)O)
R-,
Wherein: GfRepresentative-CF2CF2-、-CF2CH2-、-CF2CF(CF3)-、-CF(CF3)CF2-、
-CF2CFBr-、-CF2One in CFCl-；
TfFor-F or CF3；
End group A representative-CF3,-COF or-CF2One in COF；
M, n, p, q, r meet following condition:
(1) m, n, p, q, r are all no less than the integer of zero；
(2)n+q≥1；
(3)n+q≤m+p+r；
(4)m≥n+p+q+r。
Unlike decomposing from common hydrocarbon organic peroxide, the present invention processes emphatically preparation
A small amount of fluorine-containing peroxide impurity in PFPE.And and Zhao, c and Sawada, H
Et al. unlike theoretical decomposition hydrofluorocarbons acyl peroxide, it has been found that due to preparation
PFPE in a small amount of peroxide in there is the ether-oxygen bond of short alkyl, this may make this
The stability of class peroxide strengthens, and has disperseed the intensity of hydrofluorocarbons this Electron absorption body,
-O-O-bond energy is made to strengthen；Simultaneously because the fluorine-containing mistake in the fluorine-containing surfactant of preparation
Oxide amount is few, the most just can relatively stablize, and this can also can be seen that from our experiment.
Dividing of fluorine-containing peroxide a small amount of in the PFPE that in the present invention prepared by photooxidation method
Solution method is to be put in PFPE material by metallic catalyst, and under the conditions of uniform temperature
Decompose.PFPE end group is-COF, owing to not having water, does not the most just have HF by-product
Thing, therefore corrosivity decomposes fluorine-containing peroxide far below at aqueous solution.The most therefore the present invention
Requirement to equipment and parts thereof is not the most special.Most metal material and glass material
Equipment all can use.
The present invention propose method in, described metallic catalyst selected from gold, silver, rhodium, palladium,
One or more in platinum, copper, nickel, chrome catalysts；Metal oxide catalyst selected from gold,
Silver, rhodium, palladium, platinum, copper, nickel, chromium, ferrum oxide in one or more；Metal
Fluoride catalysts is potassium fluoride and/or cesium fluoride catalyst.
Further, the peroxide value of described PFPE product is 1～10 × 10-2
Mmol/g,.The addition of metallic catalyst or metal oxide catalyst is PFPE product
Weight 0.01～0.02%
Wherein, in metallic catalyst, the content of metal is 10～20%；Metal oxide catalyst
The content of middle metal-oxide is 10～20%.Described metal be gold, silver, rhodium, palladium, platinum,
One in copper, nickel, chromium.The generally addition of catalyst is the biggest, crosses oxygen value the lowest.
Or, metal fluoride catalysts addition is the weight of PFPE product
0.01～0.02%.
Preferably, decomposition temperature can be 80 DEG C～120 DEG C in room temperature.The time decomposed is 6～10
Hour.
The method have the advantages that
Metallic catalyst used in the present invention, can be that one or more metals can also be
Metal fluoride, metal-oxide, metal includes gold, silver, rhodium, palladium, platinum, copper, nickel
Deng；Metal-oxide includes the oxygen of the various metals such as gold, silver, rhodium, palladium, platinum, copper, nickel
Compound；Metal fluoride can be that potassium fluoride, cesium fluoride etc. are multiple.Metallic catalyst is with bone
Frame metal, metal gauze, metal dust, metallic particles, metal chip and evaporation of metal film
Apply etc. form.Metallic catalyst after the complete fluorine-containing peroxide of catalytic decomposition, can by from
The method such as the heart, filtration reclaims, and is continuing with, and therefore operating cost is extremely low.
The method that the present invention proposes, decomposes fluorine-containing peroxide ratio more thoroughly, and the time is short, right
Equipment requirements is low.PFPE peroxide value after process is low, stable performance.The method is same
Sample can also be used for the process of the fluorine-containing peroxide being similar to.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.
In embodiment, peroxide value uses iodometric titrationiodimetry titration.
Embodiment 1
Recording peroxide value is 4.2 × 10-2The PFPE of mmol/g photooxidation polymerization preparation
1Kg, is placed in 5L jacketed glass still, is subsequently adding the platinum C catalyst 10g of powder
(pt content 10%), reactor is with stirring, condensation reflux unit, computer heating control temperature in the kettle
To 80 DEG C, through synthesis under normal pressure 10 hours, then lower the temperature, sucking filtration separating catalyst and material,
(product after decomposition may have a small amount of low molecular compound to volatilize, separately to discharge product 0.98Kg
Part may be had to lose in separation process), iodimetric titration record product peroxide value 1.07 ×
10-5mmol/g。
Comparative example 1
Recording peroxide value is 4.2 × 10-2The PFPE of mmol/g photooxidation polymerization preparation
1Kg, is placed in 5L jacketed glass still, is subsequently adding the platinum C catalyst 10g of powder
(pt content 10%), reactor is with stirring, condensation reflux unit, computer heating control temperature in the kettle
To 80 DEG C, through synthesis under normal pressure 2 hours, then lower the temperature, sucking filtration separating catalyst and material,
(product after decomposition may have a small amount of low molecular compound to volatilize, separately to discharge product 0.98Kg
Part may be had to lose in separation process), iodimetric titration record product peroxide value 4.2 ×
10-4mmol/g。
Embodiment 2
Recording peroxide value is 4.2 × 10-2The PFPE of mmol/g photooxidation polymerization preparation
1Kg, is placed in 5L chuck rustless steel still, be subsequently adding KF metallic catalyst (KF crystal,
The easily moisture absorption) 10g, reactor, with stirring, computer heating control temperature in the kettle to 100 DEG C, passes through
Synthesis under normal pressure 6 hours, then lowers the temperature, discharge product 0.97Kg, and iodimetric titration records product peroxide
Change value 1.25 × 10-5mmol/g。
Embodiment 3
Recording peroxide value is 4.2 × 10-2The PFPE of mmol/g photooxidation polymerization preparation
1Kg, is placed in 5L chuck rustless steel still, is subsequently adding granular iron oxide-chromium oxide/carbon metal
Catalyst (iron oxide-chromium oxide content 10%) 10g, reactor is with stirring, computer heating control
Temperature in the kettle, to 100 DEG C, through synthesis under normal pressure 6 hours, is then lowered the temperature, discharge product 0.97Kg,
Iodimetric titration records product peroxide value 1.18 × 10-5mmol/g。
Although, the most with a general description of the specific embodiments the present invention is made
Detailed description, but on the basis of the present invention, it can be made some modifications or improvements, this
Will be apparent to those skilled in the art.Therefore, without departing from present invention spirit
On the basis of these modifications or improvements, belong to the scope of protection of present invention.
Claims (8)
1. the decomposition method of peroxide in a PFPE, it is characterised in that by metal
One in catalyst, metal oxide catalyst, metal fluoride catalysts joins light oxygen
In PFPE product prepared by change method, at 80～150 DEG C, decompose the mistake in PFPE product
Oxide.
Decomposition method the most according to claim 1, it is characterised in that described perfluor gathers
Ether peroxide structure formula is: Rf-O-O-Rf,
One or more during wherein Rf is following structural:
A-O-(-C(Tf)(OCF3)CF2-O)m(Gf-O-O)n-(CF2O)p-(CF2OO)q-(CF(Tf) O)
R-,
Wherein: GfRepresentative-CF2CF2-、-CF2CH2-、-CF2CF(CF3)-、-CF(CF3)CF2-、
-CF2CFBr-、-CF2One in CFCl-；
TfFor-F or CF3；
End group A representative-CF3,-COF or-CF2One in COF；
M, n, p, q, r meet following condition:
(1) m, n, p, q, r are all no less than the integer of zero；
(2) n+q >=1；
(3) n+q≤m+p+r；
(4) m >=n+p+q+r.
3. according to the decomposition method described in claim 1, it is characterised in that described metal
Catalyst one or many in gold, silver, rhodium, palladium, platinum, copper, nickel, chrome catalysts
Kind；Metal oxide catalyst is selected from gold, silver, rhodium, palladium, platinum, copper, nickel, chromium, ferrum
Oxide in one or more；Metal fluoride catalysts is potassium fluoride and/or cesium fluoride
Catalyst.
Decomposition method the most according to claim 1, it is characterised in that described perfluor gathers
The peroxide value of ether products is 1～10 × 10-2mmol/g。
5. according to the arbitrary described decomposition method of Claims 1 to 4, it is characterised in that metal
The addition of catalyst or metal oxide catalyst is the weight of PFPE product
0.01～0.02%, in metallic catalyst, the content of metal is 10～20%；Metal-oxide is urged
In agent, the content of metal-oxide is 10～20%.
6. according to the arbitrary described decomposition method of Claims 1 to 4, it is characterised in that metal
Fluoride catalysts addition is the 0.01～0.02% of the weight of PFPE product.
7. according to the arbitrary described decomposition method of Claims 1 to 4, it is characterised in that decompose
Temperature can be 80 DEG C～120 DEG C in room temperature.
8. according to the arbitrary described decomposition method of Claims 1 to 4, it is characterised in that decompose
Time be 6～10 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110658301A (en) * | 2019-10-29 | 2020-01-07 | 山东东岳高分子材料有限公司 | Method for measuring peroxide content in perfluoropolyether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847978A (en) * | 1968-07-01 | 1974-11-12 | Montedison Spa | Perfluorinated linear polyethers having reactive terminal groups at both ends of the chain and process for the preparation thereof |
| JPH05982A (en) * | 1991-06-27 | 1993-01-08 | Nippon Oil & Fats Co Ltd | Perfluoropolyether derivative |
| EP1980583A1 (en) * | 2007-04-10 | 2008-10-15 | Solvay Solexis S.p.A. | A method for preparing carbonylic perfluoropolyethers |
| CN101811008A (en) * | 2010-04-13 | 2010-08-25 | 中昊晨光化工研究院 | Method for decomposing fluorine-containing peroxide in fluorine-containing polyether surface active agent |
-
2015
- 2015-07-01 CN CN201510382924.7A patent/CN106317398B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3847978A (en) * | 1968-07-01 | 1974-11-12 | Montedison Spa | Perfluorinated linear polyethers having reactive terminal groups at both ends of the chain and process for the preparation thereof |
| JPH05982A (en) * | 1991-06-27 | 1993-01-08 | Nippon Oil & Fats Co Ltd | Perfluoropolyether derivative |
| EP1980583A1 (en) * | 2007-04-10 | 2008-10-15 | Solvay Solexis S.p.A. | A method for preparing carbonylic perfluoropolyethers |
| CN101811008A (en) * | 2010-04-13 | 2010-08-25 | 中昊晨光化工研究院 | Method for decomposing fluorine-containing peroxide in fluorine-containing polyether surface active agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110658301A (en) * | 2019-10-29 | 2020-01-07 | 山东东岳高分子材料有限公司 | Method for measuring peroxide content in perfluoropolyether |
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