CN104892919A - Preparation method for polyhexafluoroepoxypropanediacyl fluoride - Google Patents
Preparation method for polyhexafluoroepoxypropanediacyl fluoride Download PDFInfo
- Publication number
- CN104892919A CN104892919A CN201510093456.1A CN201510093456A CN104892919A CN 104892919 A CN104892919 A CN 104892919A CN 201510093456 A CN201510093456 A CN 201510093456A CN 104892919 A CN104892919 A CN 104892919A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- propylene oxide
- metal fluoride
- trifluoromethyl
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an improved preparation method for polyhexafluoroepoxypropanediacyl fluoride. The preparation method comprises the steps of: in a polar non-proton carbon-hydrogen organic solvent, taking a composition of perfluoro-2,7-bis(trifluoromethyl)-3,6-dioxo-octyl-diacyl fluoride and alkali metal fluoride as an initiator, adding a fluorine-containing diluent at a low temperature, and introducing hexafluoroepoxypropane for performing ring-opening polymerization to prepare polyhexafluoroepoxypropanediacyl fluoride. The method is simple in operation steps and relatively low in cost, and the average molecular weight of prepared polyhexafluoroepoxypropanediacyl fluoride can reach 10,000.
Description
Technical field
The present invention relates to the polymerization of Propylene oxide hexafluoride, be specifically related to the preparation method of the two acyl fluorides of Propylene oxide hexafluoride.
Background technology
Hexafluoropropylene oxide homopolymer (i.e. polyhexafluoropropylene oxide acyl fluorides) has heat-resisting, resistance to oxidation, radiation hardness, the characteristic such as corrosion-resistant, non-combustible, be very reliable lubricant under severe condition, and be the key intermediate of the perfluoro polyether oil being widely used in the fields such as chemical industry, electronics, electrical equipment, machinery, nuclear industry, aerospace.Acyl fluorides end group simultaneously in polyhexafluoropropylene oxide acyl fluorides has very high reactive behavior, can react further and generate various derivative, therefore important Development volue is also had at fluorine-containing fine chemical fields, corresponding fluorocarbon surfactant can be synthesized in addition, also the emulsifying agent in letex polymerization can be used as, when polymericular weight is not too high, monomer droplet or polymer particle can be stoped to produce cohesion close to associating, stable dispersion.
Mention the two acyl fluorides of perfluor in US Patent No. 3250807 first to prepare perfluor pair alkoxide with alkaline metal fluoride cpd and cause Propylene oxide hexafluoride anionic ring-opening polymerization as initiator, two-stage process is adopted in US Patent No. 3660315, the first step is cesium fluoride and perfluor-2, 7-bis-trifluoromethyl-3, 6-dioxy suberoyl fluorine prepares the two alcohol salt initiators of perfluor in tetraethyleneglycol dimethyl ether, second step goes out two alcohol salt initiators clear liquid by centrifugation, cause Propylene oxide hexafluoride ring-opening polymerization, document [J] .Macromol.sci. simultaneously, chem.A8, 499 (1974) and [J] .P.Erdman, ACS Symposium Series 59 269 (1977) has studied single acyl fluorides and two acyl fluorides and cesium fluoride in great detail to be prepared alcohol salt initiators and causes the mechanism and kinetics that Propylene oxide hexafluoride is polymerized.1992, document [J] Makromol.Chem.193,2211-2219 (1992) passes through the higher two acyl fluorides of the use polymerization degree (such as formula I, wherein m+p=3 or 4) prepare alcohol salt initiators with cesium fluoride and cause Propylene oxide hexafluoride and to be polymerized but effect is general, and the two acyl fluorides used are difficult to prepare expensive.
Although disclose the synthetic method of the two acyl fluorides of polyhexafluoropropylene oxide in the prior art, but still there is many deficiencies in these methods, such as step is too loaded down with trivial details is unsuitable for suitability for industrialized production, and employing price is higher and drying dewaters more difficult cesium fluoride as catalyzer.
Summary of the invention
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, a kind of method improved the two acyl fluorides of polyhexafluoropropylene oxide and prepare is provided, utilize alkaline metal fluoride cpd as catalyzer, simultaneously after alkaline metal fluoride cpd reacts with two acyl fluorides, directly cause Propylene oxide hexafluoride as initiator without the need to centrifugation to be polymerized, by condition control most high energy access molecular-weight average 10000 the product of polyhexafluoropropylene oxide pair acyl fluorides.
Technical scheme of the present invention provides a kind of preparation method improving the two acyl fluorides of polyhexafluoropropylene oxide: in polar non-proton organic solvent, use perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine and alkali fluoride metal composites are as initiator, then-60 ~ 0 DEG C adds fluorine-containing thinner, then passes into Propylene oxide hexafluoride and carry out the two acyl fluorides of ring-opening polymerization preparation I compound polyhexafluoropropylene oxide, wherein, 9≤m+p≤60, fluorine-containing thinner is the C that fluorine atom replaces
2~ C
9the C that alkane or fluorine atom replace
2~ C
9alkene.
Detailed Description Of The Invention
According to the method that technique scheme of the present invention provides, comprise the steps:
A) polar aprotic solvent, perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine and powdery alkali metal fluoride are added in reactor, stirred at ambient temperature 12 ~ 48 hours;
B) reduce temperature in the kettle-60 ~ 0 DEG C, add fluorine-containing thinner, mix and blend, control temperature in the kettle-60 ~ 0 DEG C, add Propylene oxide hexafluoride and carry out polyreaction 1 ~ 8 hour;
C), after being polymerized, taking out the mixture reacted, under inert atmosphere protection, be heated to 100-160 DEG C of stirring and make product end group by-CF
2o
-m
+change-COF into completely, separating lower floor's product is the two acyl fluorides of polyhexafluoropropylene oxide; Wherein said perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine is formula II compound.
Wherein, described fluorine-containing thinner is the C that fluorine atom replaces
2~ C
9the C that alkane or fluorine atom replace
2~ C
9alkene.In some embodiments, fluorine-containing thinner is selected from Freon 113,1,1,1,3,3-3-pentafluorobutane, hexafluoropropylene dimmer, hexafluoropropylene trimer or R 1216.
In technique scheme, step b) described in polyreaction time from add Propylene oxide hexafluoride terminate rear timing.
Different according to thinner, feed postition is also different, Freon 113,1,1,1,3,3-3-pentafluorobutane, hexafluoropropylene dimmer, R 1216 trimerization owing to being liquid so adopt peristaltic pump to add with 10 ~ 30g speed per hour, optimal selection 20g per hour; R 1216 due to be gas adopt spinner-type flowmeter control add with 30 ~ 60g speed per hour, optimal selection 40g per hour.Simultaneously different according to thinner, the temperature controlled in still is also different, Freon 113,1,1,1,3,3-3-pentafluorobutane, hexafluoropropylene dimmer, hexafluoropropylene trimer add time control built in-30 ~-35 DEG C, optimal selection-32 DEG C, R 1216 adds time control built in-60 ~-40 DEG C, optimal selection-40 DEG C.Propylene oxide hexafluoride adds fashionable polymerization temperature and controls at-60 ~-20 DEG C, optimal selection-33 DEG C.
In some embodiments, step stirring a) continues about 12 ~ 48 hours.Step b) the stirring time length be as the criterion to mix, in some embodiments, stir continue about 1 hour.
In some embodiments, described inert atmosphere is nitrogen atmosphere.
According to the method that technique scheme of the present invention provides, in some embodiments, described polar aprotic solvent is selected from glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, own nitrile or adiponitrile.
According to the method that technique scheme of the present invention provides, in some embodiments, alkaline metal fluoride cpd is Potassium monofluoride.
According to the method that technique scheme of the present invention provides, in some embodiments, perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine, polar aprotic solvent, powdery alkali metal fluoride are through rectifying or the pre-treatment that dewaters: perfluor-2, the purity > 98% of 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine; Polar aprotic solvent water content <5ppm; Powdery alkali metal fluoride water-content <20ppm.
According to the method that technique scheme of the present invention provides, in some embodiments, the mol ratio of polar aprotic solvent and alkaline metal fluoride cpd is 1 ~ 20:1.5; The mol ratio of perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine and alkaline metal fluoride cpd is 1 ~ 20:1.5.In other embodiments, the mol ratio of polar aprotic solvent, perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine, alkaline metal fluoride cpd is 8:1:1.5.
According to the method that technique scheme of the present invention provides, in some embodiments, the rate-controlling of fluorine-containing thinner is added at 10 ~ 30g per hour; Propylene oxide hexafluoride adds rate-controlling at 30 ~ 60g per hour.In other embodiments, add the rate-controlling of fluorine-containing thinner at 10 ~ 20g per hour; Propylene oxide hexafluoride adds rate-controlling at 40 ~ 50g per hour.
According to the method that technique scheme of the present invention provides, in some embodiments, fluorine-containing thinner and Propylene oxide hexafluoride mol ratio are 1:1 ~ 10; Alkaline metal fluoride cpd and Propylene oxide hexafluoride mol ratio are 1:30 ~ 100.In other embodiments, fluorine-containing thinner and Propylene oxide hexafluoride mol ratio are 1:6; Alkaline metal fluoride cpd and Propylene oxide hexafluoride mol ratio are 1:60.
In some embodiments, step b) temperature of reaction be-40 ~-33 DEG C.
In some embodiments, step c) Heating temperature be 130 ~ 150 DEG C.
It should be noted that because commercially available Propylene oxide hexafluoride can contain a small amount of acidic impurities and moisture usually, therefore, step b of the present invention) described Propylene oxide hexafluoride need through super-dry and removing acidic substance.In some embodiments, Propylene oxide hexafluoride is through drying tower process, wherein drying tower is divided into two portions, first part adopts calcium hydroxide to fill a small amount of acid of removing Propylene oxide hexafluoride, second section adopts hydrolith to fill a small amount of water in removing Propylene oxide hexafluoride, acidic substance drop to 0.05wt%, and moisture is 5ppm.
The term "or" that the present invention uses represents alternatives, if properly, they can be combined, and that is, term "or" comprises each listed independent alternatives and their combination.Such as, " polar aprotic solvent is selected from glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, own nitrile or adiponitrile " represents that an alkali metal salt can be the one among glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, own nitrile, adiponitrile, also can be its more than one combination.
Definition of the present invention " room temperature " or " normal temperature " refer to the temperature range of 10 ~ 30 DEG C.
Unless explicitly stated otherwise in contrast, otherwise all scopes that the present invention quotes comprise end value.Such as, " temperature of reaction is-60 ~-30 DEG C " represents that the scope of the temperature T of polyreaction is-60 DEG C≤T≤-30 DEG C.
Numeral in the present invention is approximation, no matter whether uses the wording such as " left and right ", " approximately " or " about ".The numerical value of numeral likely there will be the difference such as 1%, 2%, 5%, 7%, 8%, 10%, 15% or 20%.
The present invention's beneficial effect is compared to existing technology, a kind of method improving the two acyl fluorides synthesis of polyhexafluoropropylene oxide is provided, utilize price lower and the relatively simple Potassium monofluoride of drying treatment substitutes cesium fluoride as catalyzer, simultaneously after Potassium monofluoride reacts with two acyl fluorides, directly cause Propylene oxide hexafluoride as initiator without the need to centrifugation to be polymerized, by condition control most high energy access molecular-weight average 10000 the product of polyhexafluoropropylene oxide pair acyl fluorides.
Embodiment
In order to further illustrate the present invention, be described in detail below in conjunction with the synthetic method of specific embodiment to the two acyl fluorides of the polyhexafluoropropylene oxide of improvement provided by the invention.
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, the some distortion made and improvement, all belong to protection scope of the present invention.
Molecular-weight average described in following examples be all by gel permeation chromatography (GPC) and Enantiomeric excess (
19f-NMR) detection gained is carried out.
Embodiment 1
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 20ml diethylene glycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend 24 is little of system clarification nothing precipitation; Then under agitation reduce reactor temperature to-32 DEG C, use peristaltic pump to add the 38ml after dewatering (56g) Refrigerant R 113 (R113) with 20g speed per hour, mix and blend 1 hour after adding; Control temperature in the kettle afterwards at-33 DEG C, add the Propylene oxide hexafluoride 300g through drying tower drying with 40g speed per hour, react 3 hours at-33 DEG C after adding; After polyreaction completes; using two mouthfuls of round-bottomed flasks to take out the mixture reaction mixture reacted under nitrogen protection is muddy shape; be heated to 140 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 3000.
Embodiment 2
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 50ml diethylene glycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend 24 is little of system clarification nothing precipitation; Then under agitation reduce reactor temperature to 0 DEG C, use peristaltic pump to add the 22ml after dewatering (56g) Refrigerant R 113 (R113) with 10g speed per hour, mix and blend 1 hour after adding; Control temperature in the kettle afterwards at 0 DEG C, add the Propylene oxide hexafluoride 300g through drying tower drying with 30g speed per hour, react 1 hour at-33 DEG C after adding; After polyreaction completes; two mouthfuls of round-bottomed flasks are used to take out the mixture reacted under nitrogen protection; reaction mixture is muddy shape; be heated to 130 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 1590.
Embodiment 3
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 50ml tetraethyleneglycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend 24 is little of system clarification nothing precipitation; Then under agitation reduce reactor temperature to-32 DEG C, use peristaltic pump to add the 35ml after dewatering (45g) 1,1,1,3,3-3-pentafluorobutane with 20g speed per hour, mix and blend 1 hour after adding; Control temperature in the kettle afterwards at-33 DEG C, add the Propylene oxide hexafluoride 300g through drying tower drying with 40g speed per hour, react 3 hours at-33 DEG C after adding; After polyreaction completes; two mouthfuls of round-bottomed flasks are used to take out the mixture reacted under nitrogen protection; reactant is muddy shape; be heated to 140 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 3600.
Embodiment 4
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 50ml tetraethyleneglycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend 24 is little of system clarification nothing precipitation; Then under agitation reduce reactor temperature to-32 DEG C, use peristaltic pump to add the 75ml after dewatering (135g) hexafluoropropylene trimer with 20g speed per hour, mix and blend 1 hour after adding; Control temperature in the kettle afterwards at-33 DEG C, add the Propylene oxide hexafluoride 300g through drying tower drying with 40g speed per hour, react 3 hours at-33 DEG C after adding; After polyreaction completes; two mouthfuls of round-bottomed flasks are used to take out the mixture reacted under nitrogen protection; reactant is muddy shape; be heated to 140 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 4200.
Embodiment 5
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 50ml tetraethyleneglycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend 48 is little of system clarification nothing precipitation; Then under agitation reduce reactor temperature to-40 DEG C, speed that spinner-type flowmeter controls to add R 1216 adds 30g R 1216 at 20g per hour, mix and blend 1 hour after adding to use drying tower to dewater; Control temperature in the kettle afterwards at-33 DEG C, add the Propylene oxide hexafluoride 250g through drying tower drying with 40g speed per hour, react 3 hours at-33 DEG C after adding; After polyreaction completes; two mouthfuls of round-bottomed flasks are used to take out the mixture reacted under nitrogen protection; reactant is muddy shape; be heated to 140 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 7000.
Embodiment 6
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 50ml tetraethyleneglycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend 12 is little of system clarification nothing precipitation; Then under agitation reduce reactor temperature to-40 DEG C, speed that spinner-type flowmeter controls to add R 1216 adds 46g R 1216 at 20g per hour, mix and blend 1 hour after adding to use drying tower to dewater; Control temperature in the kettle afterwards at-33 DEG C, add the Propylene oxide hexafluoride 300g through drying tower drying with 40g speed per hour, react 3 hours at-33 DEG C after adding; After polyreaction completes; two mouthfuls of round-bottomed flasks are used to take out the mixture reacted under nitrogen protection; reactant is muddy shape; be heated to 140 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 10000.
Embodiment 7
1L Monel metal autoclave pressure 180 DEG C of vacuum-nitrogen replacements are dewatered for 4 hours, then the 8.50g perfluor-2 after 5ppm, rectifying is less than by measuring water content through the 50ml tetraethyleneglycol dimethyl ether that dewaters, 7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine (after esterification GC purity assay 98.5%) and drying grind into powder 1.75g Potassium monofluoride after measured water content are less than 20ppm, join in reactor, at room temperature mix and blend finds that system clarification is without precipitation for 24 hours; Then under agitation reduce reactor temperature to-40 DEG C, speed that spinner-type flowmeter controls to add R 1216 adds 271g R 1216 at 30g per hour, mix and blend 1 hour after adding to use drying tower to dewater; Control temperature in the kettle afterwards at-33 DEG C, add the Propylene oxide hexafluoride 300g through drying tower drying with 60g speed per hour, react 3 hours at-40 DEG C after adding; After polyreaction completes; two mouthfuls of round-bottomed flasks are used to take out the mixture reacted under nitrogen protection; reactant is muddy shape; be heated to 150 DEG C under nitrogen protection afterwards; separating lower floor's product after being stirred to the obvious layering of mixture is the two acyl fluorides of polyhexafluoropropylene oxide, after the product esterification that takes a morsel through GPC and
19f-NMR detects, and molecular-weight average is about 9980.
Claims (9)
1. the preparation method of the two acyl fluorides of polyhexafluoropropylene oxide, it is characterized in that, in polar non-proton organic solvent, use perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine and alkaline metal fluoride cpd are as initiator, then-60 ~ 0 DEG C adds fluorine-containing thinner, then passes into Propylene oxide hexafluoride and carry out the two acyl fluorides of ring-opening polymerization preparation I compound polyhexafluoropropylene oxide, wherein, 9≤m+p≤60, fluorine-containing thinner is the C that fluorine atom replaces
2~ C
9the C that alkane or fluorine atom replace
2~ C
9alkene.
2. method according to claim 1, is characterized in that comprising following steps:
A) polar aprotic solvent, perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine and powdery alkali metal fluoride are added in reactor, stirred at ambient temperature 12 ~ 48 hours;
B) reduce temperature in the kettle-60 ~ 0 DEG C, add fluorine-containing thinner, mix and blend, control temperature in the kettle-60 ~ 0 DEG C, add Propylene oxide hexafluoride and carry out polyreaction 1 ~ 8 hour;
C) after being polymerized, taking out the mixture reacted, under inert atmosphere protection, be heated to 100-160 DEG C of stirring, separating lower floor's product is the two acyl fluorides of polyhexafluoropropylene oxide.
3. the method according to any one of claim 1 or 2, is characterized in that, described polar aprotic solvent is selected from glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, own nitrile or adiponitrile.
4. the method according to any one of claim 1 or 2, is characterized in that, described alkaline metal fluoride cpd is Potassium monofluoride.
5. the method according to any one of claim 1 or 2, is characterized in that, the purity > 98% of perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine; Polar aprotic solvent water content <5ppm; Alkaline metal fluoride cpd water-content <20ppm.
6. the method according to any one of claim 1 or 2, is characterized in that, the mol ratio of polar aprotic solvent and alkaline metal fluoride cpd is 1 ~ 20:1.5; The mol ratio of perfluor-2,7-bis-trifluoromethyl-3,6-dioxy suberoyl fluorine and alkaline metal fluoride cpd is 1 ~ 20:1.5.
7. the method according to any one of claim 1 or 2, is characterized in that, fluorine-containing thinner is selected from Freon 113,1,1,1,3,3-3-pentafluorobutane, hexafluoropropylene dimmer, hexafluoropropylene trimer or R 1216.
8. the method according to any one of claim 1 or 2, is characterized in that, adds the rate-controlling of fluorine-containing thinner at 10 ~ 30g per hour; Propylene oxide hexafluoride adds rate-controlling at 30 ~ 60g per hour.
9. the method according to any one of claim 1 or 2, is characterized in that, the mol ratio of fluorine-containing thinner and Propylene oxide hexafluoride is 1:1 ~ 10; Alkaline metal fluoride cpd and Propylene oxide hexafluoride mol ratio are 1:30 ~ 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510093456.1A CN104892919B (en) | 2014-03-04 | 2015-03-02 | A kind of preparation method of the double acyl fluorides of polyhexafluoropropylene oxide |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410077170 | 2014-03-04 | ||
| CN201410077170X | 2014-03-04 | ||
| CN201510093456.1A CN104892919B (en) | 2014-03-04 | 2015-03-02 | A kind of preparation method of the double acyl fluorides of polyhexafluoropropylene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104892919A true CN104892919A (en) | 2015-09-09 |
| CN104892919B CN104892919B (en) | 2018-08-10 |
Family
ID=54025916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510093456.1A Active CN104892919B (en) | 2014-03-04 | 2015-03-02 | A kind of preparation method of the double acyl fluorides of polyhexafluoropropylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104892919B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057230A (en) * | 2019-12-30 | 2020-04-24 | 天津市长芦化工新材料有限公司 | Double-end-group perfluoropolyether silane and preparation method thereof |
| CN111087604A (en) * | 2019-12-30 | 2020-05-01 | 天津市长芦化工新材料有限公司 | Diacyl fluorine hexafluoro propylene oxide polymer and preparation method thereof |
| CN111116326A (en) * | 2019-12-30 | 2020-05-08 | 天津市长芦化工新材料有限公司 | Polyol type fluorine-containing additive and preparation method thereof |
| CN113754877A (en) * | 2021-09-10 | 2021-12-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with low thermal conductivity coefficient |
| CN114395119A (en) * | 2021-12-31 | 2022-04-26 | 西安近代化学研究所 | Binary copolymerization perfluoropolyether and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6034207A (en) * | 1998-04-01 | 2000-03-07 | Shin-Etsu Chemical Co., Ltd. | Polymers of hexafluoropropene oxide and process of making |
| CN101652404A (en) * | 2007-04-06 | 2010-02-17 | 优迈特株式会社 | Fluorinated polyether compound, process for producing the same, and curable composition containing the same |
| CN101775130A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳神舟新材料有限公司 | Method for production and post-processing of hexafluoropropylene oxide homopolymer |
-
2015
- 2015-03-02 CN CN201510093456.1A patent/CN104892919B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6034207A (en) * | 1998-04-01 | 2000-03-07 | Shin-Etsu Chemical Co., Ltd. | Polymers of hexafluoropropene oxide and process of making |
| CN101652404A (en) * | 2007-04-06 | 2010-02-17 | 优迈特株式会社 | Fluorinated polyether compound, process for producing the same, and curable composition containing the same |
| CN101775130A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳神舟新材料有限公司 | Method for production and post-processing of hexafluoropropylene oxide homopolymer |
Non-Patent Citations (1)
| Title |
|---|
| 段友芦 等: "全氟环氧丙烷在氟化钾催化下的阴离子聚合", 《高分子通讯》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057230A (en) * | 2019-12-30 | 2020-04-24 | 天津市长芦化工新材料有限公司 | Double-end-group perfluoropolyether silane and preparation method thereof |
| CN111087604A (en) * | 2019-12-30 | 2020-05-01 | 天津市长芦化工新材料有限公司 | Diacyl fluorine hexafluoro propylene oxide polymer and preparation method thereof |
| CN111116326A (en) * | 2019-12-30 | 2020-05-08 | 天津市长芦化工新材料有限公司 | Polyol type fluorine-containing additive and preparation method thereof |
| CN111057230B (en) * | 2019-12-30 | 2022-07-15 | 天津市长芦化工新材料有限公司 | Double-end-group perfluoropolyether silane and preparation method thereof |
| CN113754877A (en) * | 2021-09-10 | 2021-12-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with low thermal conductivity coefficient |
| CN113754877B (en) * | 2021-09-10 | 2023-09-22 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol with low heat conductivity coefficient |
| CN114395119A (en) * | 2021-12-31 | 2022-04-26 | 西安近代化学研究所 | Binary copolymerization perfluoropolyether and preparation method thereof |
| CN114395119B (en) * | 2021-12-31 | 2023-06-09 | 西安近代化学研究所 | Binary copolymerization perfluoropolyether and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892919B (en) | 2018-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892919A (en) | Preparation method for polyhexafluoroepoxypropanediacyl fluoride | |
| US8236919B2 (en) | Process for preparing a polyether ether ketone | |
| JP4166574B2 (en) | Copolymer of perfluorovinyl ether monomer having sulfonamide group and method for producing the same | |
| CN105754027B (en) | A kind of partial fluorine ethylene polymer, preparation method and application | |
| CN105273178B (en) | A kind of preparation method of hexafluoropropylene oxide homopolymer | |
| CN101775130B (en) | Method for production and post-processing of hexafluoropropylene oxide homopolymer | |
| CN102964503A (en) | Preparation method of modified polytetrafluoroethylene suspension resin | |
| CN102174139B (en) | Method for preparing polytetrafluoroethylene resin for coating | |
| KR20060042211A (en) | Process for production of ethylene oxide copolymer | |
| CN103788363A (en) | Method for preparing perfluoropolyether with high molecular weight | |
| CN104558365B (en) | The preparation method of Meltability polytetrafluorethyletubular | |
| TW200305593A (en) | Production process for ethylene oxide copolymer | |
| TW202219110A (en) | Polyether ether ketone and method for producing polyether ether ketone | |
| JP2000256457A (en) | Propylene oxide polymerization catalyst composition and preparation of poly(propylene oxide) | |
| CN101302263B (en) | Ethylene-tetrafluoroethylene copolymer | |
| CN103193904A (en) | Method for preparing fluorine-containing polymer through dispersion method | |
| JP4779213B2 (en) | Coating material | |
| US9156779B2 (en) | Method for producing trifluoromethanesulfonic anhydride | |
| JP5320227B2 (en) | Method for producing vinylidene fluoride polymer having excellent acid resistance | |
| CN102329402A (en) | Preparation method of low-temperature-resistant binary fluorine rubber | |
| WO1999064484A1 (en) | Polymerization of vinyl ethers | |
| CN104086765B (en) | The preparation method of aliphatics coating polyether glycol | |
| CN115322280B (en) | Preparation method of environment-friendly polytetrafluoroethylene dispersion emulsion for finishing paint | |
| CN103694398A (en) | Modified PTFE (Polytetrafluoroethylene) suspension resin with high welding property and preparation method of modified PTFE suspension resin | |
| CN103755857B (en) | Low-temperature resistant fluorubber, and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 523871 Guangdong province Dongguan city Changan Town Sha Zhen'an Road No. 368 Applicant after: DONGGUAN DONGYANG GUANGKE R & D CO., LTD. Address before: 523871 Guangdong province Dongguan city Changan Town Sha Zhen'an Road No. 368 Applicant before: Dongyang, Dongguan City Chang'an light Aluminum research and development company limited |
|
| COR | Change of bibliographic data | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |