CN104277163A - Fluorine-containing carboxylic acid emulsifier and preparation method of fluorine-containing polymer - Google Patents

Fluorine-containing carboxylic acid emulsifier and preparation method of fluorine-containing polymer Download PDF

Info

Publication number
CN104277163A
CN104277163A CN201310272864.4A CN201310272864A CN104277163A CN 104277163 A CN104277163 A CN 104277163A CN 201310272864 A CN201310272864 A CN 201310272864A CN 104277163 A CN104277163 A CN 104277163A
Authority
CN
China
Prior art keywords
chf
cooy
cclf
preparation
fluoropolymer
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
Application number
CN201310272864.4A
Other languages
Chinese (zh)
Other versions
CN104277163B (en
Inventor
夏俊
马鹏飞
张宝亮
魏文涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Dongyue Polymer Material Co Ltd
Original Assignee
Shandong Dongyue Polymer Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong Dongyue Polymer Material Co Ltd filed Critical Shandong Dongyue Polymer Material Co Ltd
Priority to CN201310272864.4A priority Critical patent/CN104277163B/en
Publication of CN104277163A publication Critical patent/CN104277163A/en
Application granted granted Critical
Publication of CN104277163B publication Critical patent/CN104277163B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a fluorine-containing carboxylic acid emulsifier and a preparation method of a fluorine-containing polymer. The emulsifier is a compound represented by the general formula I of Rf-CHF-CF2-COOY, wherein Rf is perfluoroalkyl or partially fluorinated alkyl and is alkyl having a straight-chain structure, branched-chain structure or cyclic structure containing 1-8 carbon atoms, and Y is NH4, Li, Na, K or H. The emulsifier is used for preparation of the fluorine-containing polymer through a dispersion method under the action of an initiator and in an aqueous-phase system, especially preparation of the fluorine-containing polymer containing a tetrafluoroethylene monomer; the invention also provides the preparation method of the fluorine-containing polymer. The emulsifier has excellent emulsion performance in the preparation process of the fluorine-containing polymer, can better control the particle size of primary particles of an emulsion, and obtains the polymer with high molecular weight.

Description

A kind of preparation method containing carboxylic acid fluoride emulsifying agent and fluoropolymer
Technical field
The present invention relates to a kind of preparation method containing carboxylic acid fluoride or emulsifying salt agent and fluoropolymer, belong to dispersion method and produce fluoropolymer technical field.
Background technology
The fluorochemical surfactant that dispersion method production fluoropolymer field is most widely used is Perfluorocaprylic Acid, i.e. C 7f 15cOOH and derivative thereof, or be called " C8 ", be a kind of synthetic but not naturally occurring industrial raw material.The molecular structure of ammonium perfluorocaprylate (PFOA), while its excellent surface properties of imparting, has also been doomed its persistence in the environment and cumulative bad.Because containing full-fluorine group in PFOA molecule, and interconnective carbochain is long, finally causes PFOA to have strong thermostability and kinetic stability, adds PFOA molecule persistence in the environment.Show after deliberation, PFOA is all difficult to degraded under the metabolism standing heat-flash, illumination, chemical action, microbial process and higher vertebrate, and PFOA is one of organic pollutant of the most difficult degradation found in the world at present.PFOA pays close attention to as focus the harm that environment and HUMAN HEALTH may cause by some developed countries and non governmental organization at present.
American documentation literature US5789508, the tensio-active agent that US4025709, US5688884, CN101745338A etc. mention or emulsifying agent, due to the relation of molecular structure, can affect the quality product of polymkeric substance or reduce emulsifying effectiveness in polymerization process.Such as easily cause corrosion containing sulfonic acid group, affect resin quality; The structure of carbon containing hydrogen acid ether, easily at polymerization process generation chain tra nsfer.Meeting containing ether oxygen atom has influence on the surface property of emulsifying agent, reduces emulsifying effectiveness.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method containing carboxylic acid fluoride or emulsifying salt agent and fluoropolymer.
Technical scheme of the present invention is as follows:
For the preparation of an emulsifying agent for fluoropolymer, be the compound with general formula I, R f-CHF-CF 2-COOY, wherein, R fbe perfluoroalkyl or partially fluorinated alkyl, and be containing the linear chain structure of 1 to 8 carbon atoms, band branched structure or the alkyl of ring texture, described partially fluorinated R fnon-fluorine atom in group is H, Cl or Br atom, and nonfluorinated atom is preferably Cl atom; Y is NH 4, Li, Na, K or H.
According to the present invention, the preferred R of compound of general formula I fit is the perfluoroalkyl containing 3-8 carbon atom.Y is NH 4or H.Preferred R fcF 3cF 2cF 2cF 2-.
According to the present invention, the compound of general formula I is preferred further, is one of following compounds:
CF 3CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY。
In above compound, as emulsifying agent most preferably: CF 3cF 2cF 2cF 2-CHF-CF 2-COOY, Y are NH 4or H.
The compound of above-mentioned general formula I can pass through idoalkane R fi and perfluor or partially fluorinated monomer (as containing H or the monomer containing Cl) the obtained corresponding adduct of reaction, adduct and the reacted intermediate product of LiCl reoxidize and get final product.
Idoalkane R fi can be prepared by traditional method, and iodine pentafluoride, iodine and Fluorine containing olefine, as raw material, are obtained by catalysis under certain pressure, and catalyzer is as antimony trifluoride.Patent US3234294 has a detailed description.Adopt different Fluorine containing olefines as raw material, different idoalkane R can be obtained fi, Fluorine containing olefine be selected from tetrafluoroethylene, R 1216, trifluorochloroethylene, trifluoro-ethylene, vinylidene, vinyl fluoride one or more:
When employing tetrafluoroethylene is as raw material, prepare F (CF 2cF 2) ni;
When employing R 1216 is as raw material, prepare (CF 3) 2cFI;
When employing trifluorochloroethylene is as raw material, prepare F (C 2clF 3) ni;
When employing trifluoro-ethylene is as raw material, prepare F (C 2f 3h) ni.
With idoalkane R fi, as the raw material of reaction, carries out addition reaction with described Fluorine containing olefine, continues to react with trifluoro-ethylene, and when adduct number is 1, can obtain structure is R f-CHFCF 2the adduct of-I.R f-CHFCF 2-I reacts addition with vinylidene further, can obtain product R f-CHFCF 2-CH 2cF 2-I.By R f-CHFCF 2-CH 2cF 2-I and LiCl react and can obtain R f-CHFCF 2-CH=CF 2, product oxidation can be obtained R f-CHFCF 2-COOH.
Also R can be used f-CHFCF 2-I and Addition on ethylene obtain R f-CHFCF 2-CH 2cH 2-I, reoxidizes and obtains R f-CHFCF 2-COOH.
Or R f-CHFCF 2-I and trifluorochloroethylene addition obtain R f-CHFCF 2-CFClCF 2-I, is obtained by reacting R under zinc powder effect f-CHFCF 2-CF=CF 2, oxidation can obtain R further f-CHFCF 2-COOH.
The compound of above-mentioned general formula I uses as emulsifying agent, is applied to dispersion method and prepares fluoropolymer in aqueous phase system under initiator effect.
Preferably, the compound of above-mentioned general formula I is applied to the fluoropolymer of dispersion method preparation containing tetrafluoroethylene monomer as emulsifying agent.
More preferably, the compound of above-mentioned general formula I under initiator existence, prepares the tetrafluoroethylene of non-melt processing as emulsifying agent in aqueous phase system for dispersion method.
A preparation method for fluoropolymer, its for use in water medium have general formula I containing carboxylic acid fluoride or salt as emulsifying agent, under initiator exists, be polymerized fluorochemical monomer, it is characterized in that, described is the compound with general formula I containing carboxylic acid fluoride or emulsifying salt agent, R f-CHF-CF 2-COOY, wherein, R fbe perfluoroalkyl or partially fluorinated alkyl, and be containing the linear chain structure of 1 to 8 carbon atoms, band branched structure or the alkyl of ring texture, described partially fluorinated R fnon-fluorine atom in group is H, Cl or Br atom; Y is NH 4, Li, Na, K or H.
The preparation being used for dispersion method fluoropolymer containing carboxylic acid fluoride or salt as emulsifying agent that the present invention describes is R with traditional dispersion method unlike the emulsifying agent structure that the present invention adopts f-CHF-CF 2the preferred NH of-COOY, Y 4or H.Particularly preferred emulsifying agent is CF 2cF 2cF 2cF 2-CHF-CF 2-COOY, Y are NH4 or H.
Described initiator is selected from known water-soluble or oil-soluble initiator, such as: the redox system etc. being selected from the redox system of the redox system of ammonium persulphate, Potassium Persulphate, t-butylcumylperoxide, benzoyl peroxide, Diisopropyl azodicarboxylate, potassium permanganate, succinic acid peroxide, Potassium Persulphate and S-WAT, Potassium Persulphate and sodium pyrosulfate and ferrous sulfate, Potassium Persulphate and sodium pyrosulfate and Silver Nitrate.Initiator add-on is 0.1 ~ 500ppm of water weight.
Add the generation that paraffin can reduce condensation product, the add-on of paraffin is 0.1 ~ 12% of water weight.
The present invention is containing in carboxylic acid fluoride or emulsifying salt agent application process, and the fluorochemical monomer that can be polymerized, Oil repellent is at least 35wt%, includes fluorinated olefin or the fluorinated dioxoles of 2-10 carbon atom, and molecular formula is CY 2=CYOR or CY 2the fluorinated vinyl ether of=CYOR'OR, wherein the Y perfluor that to be H or F, R and R' be respectively containing 1 ~ 8 carbon atom or partially fluorinated alkyl and alkyl vinyl.R is preferably containing 1 ~ 4 carbon atom and is preferably perfluorination.R' is preferably containing 1 ~ 4 carbon atom and is preferably perfluorination.
Described fluorinated olefin is preferably containing 2 ~ 6 carbon atoms, comprises TFE, R 1216 (HFP), trifluorochloroethylene (CTFE), ethylene fluoride, vinylidene fluoride, trifluoro-ethylene, hexafluoro-isobutene, one of in perfluorobutyl ethylene or combination.
Preferred fluorinated dioxoles (cyclic fluorinated monomer) comprises perfluor-2,2-dimethyl-1,3-dioxole (PDD) and perfluor-2-methylene radical-4-methyl isophthalic acid, 3-dioxolane alkene (PMD).
Preferred fluoropolymer comprises the polymkeric substance containing tetrafluoroethylene monomer.The preferred polymkeric substance containing tetrafluoroethylene monomer comprises (per) fluoropolymer, tetrafluoroethylene (TFE) and has the multipolymer (especially the multipolymer of R 1216 HFP and perfluoroalkyl vinyl ether) of one or more fluorinated olefin of 2 ~ 8 carbon atoms.
Most preferred fluoropolymer is the multipolymer (application examples 2) of proplast (application examples 1) or tetrafluoroethylene and R 1216, trifluorochloroethylene and trifluoro-ethylene.
Fluoropolymer of the present invention can be glassy, plastic-like or elastomerics shape.Can be amorphous or partial crystallization, melt-processable or non-melt processing.Such as, what tetrafluoroethylene list polymers (pure PTFE) obtained is non-melt-processed resin, and the modified ptfe that tetrafluoroethylene and other fluoropolymer monomer copolymerizations obtain is melt-processable resin.
According to the present invention, when tetrafluoroethylene (TFE) is polymerized, the scope normally 0.3 ~ 7MPa of pressure, TFE keeps target pressure value with given pace press-in reactor usually simultaneously.If TFE uses as unique monomer, the polytetrafluoroethylene (PTFE) that the present invention is formed is homopolymer.In addition, the a certain amount of fluorochemical monomer that also can add except TFE to reactor comes and TFE copolymerization, non-TFE comonomer at least containing 0.5 % by mole in gained modification TFE polymkeric substance, modified TFE polymkeric substance improve its sinter time film forming properties, keep the PTFE performance in polymkeric substance (modified ptfe) simultaneously.Pure PTFE normally non-melt processing, such as, its melt viscosity 380 DEG C time more than 1*10 9.In U.S. Patent No. 3,819, in 594, melt viscosity is measured by tensile creep method at 380 DEG C.Add chain-transfer agent such as methyl alcohol or ethanol in polyreaction of the present invention and can obtain the PTFE of low melting viscosity, if observed value at 372 DEG C is 10 ~ 1*10 5pa.s.At present, comonomer is preferably moieties and contains the perfluoroalkyl vinyl ether of 1 ~ 8 carbon atom (being more preferably 1 ~ 3 carbon atom), perhalogeno alkene if trifluorochloroethylene, perfluoroalkyl alkene are as perfluorobutyl ethylene etc.Also the modifying comonomer more than 1 can be used in polymerization process.By being polymerized the polymer solids concentration of the emulsion obtained, be generally 20 ~ 60%(based on water).Polymerization process, by stopping stopping polymerization, then unreacted monomer in emptying reactor into TFE, stops reacting for some time with emptying can continuation before after TFE.
Method of the present invention can be used for manufacturing the TFE co-polymer of melt-processable, and increase comonomer consumption and effectively can improve resin melt-processable performance, add-on is according to the reactive behavior of comonomer.Usually the co-monomer content added is no less than 0.5mol% and can brings up to 15mol% or higher, and the fluorinated copolymer characteristic that this desirably obtains is determined.Usually, the melt viscosity of TFE multipolymer is 10 2to 10 6pa.s.Melt viscosity measuring method is shown in ASTM D1238.The copolymerization monomer participating in copolymerization added in reactor usually before copolyreaction starts, but if needed also to add in reaction process.Have multiple comonomer can with TFE copolymerization to obtain the TFE multipolymer of melt-processable in this area, and these kinds can be applied in the process of the present invention.The example of polymerisable comonomer comprises perfluoroolefine, such as HFP or moieties contain 1 ~ 8(and preferably 1 ~ 3) perfluoroalkyl vinyl ether (PAVE) of individual carbon atom.Multiple comonomer can participate in TFE co-polymer, the multipolymer of such as TFE and HFP and PAVE copolymerization.
Except whole emulsifying agents can being added before polymerization starts, also a part of emulsifying agent can be added in polymerization process.
The Primary particle size of fluoropolymer emulsion is preferably 50 ~ 500nm.The emulsifying agent R that the present invention adopts f-CHF-CF2-COOY, Y are NH 4, Li, Na, the preferred NH of K or H, Y 4or H, effectively can obtain above-mentioned suitable size of particles.
The methods such as the polymer emulsion particle in the present invention in dispersion polymerization process by any facilitated method agglomeration separation out, as violent stirring, selectively can add and have the electrolytic solution of low surface tension and/or not miscible with water solvent, freezing.Subsequently cohesion polymer solids resin is out separated and drying from liquid, thus obtain fluoropolymer resin.
Carrying out dry drying temperature is 10 DEG C ~ 250 DEG C, and more excellent is 100 DEG C ~ 200 DEG C.
In the present invention, the suitable mean particle size of polymer solids resin is at 300 ~ 700 μm.Mean particle size is measured with reference to ASTMD-1457.The apparent density of polymer solids resin is 0.35 to 0.65g/ml.Apparent density is measured with reference to JIS K-6891.
In addition, the fluoropolymer emulsion obtained according to the present invention also can concentrate further and obtain concentrated solution, for other side, as metallic paint, and woven fiber glass coating, impregnating.Concentrated method, known can adopt evaporation, is separated, electrodialysis and ultrafiltration etc.Concentrate and can obtain the fluoropolymer concentrated solution of concentration from 30 quality % ~ 70 quality %.Concentration process can affect the stability of dispersion, so can add dispersion stabilizer further.Dispersion stabilizer includes but not limited to, nonionogenic tenside, as poly-alkoxyl group ether, especially polyoxyethylene groups alkyl phenyl ether etc.
Dispersion stabilizer add-on is 0.5 ~ 20 quality % of fluoropolymer solids content.When total amount is lower than 0.5 quality %, concentrated solution stability can be bad, and when total amount is more than 20 quality %, exceeding part can not have obvious effect to raising dispersion stable.Dispersion stabilizer add-on lower limit more preferably 2 quality %, the upper limit 12 quality %.
Excellent results of the present invention: of the present invention containing carboxylic acid fluoride or emulsifying salt agent and use this emulsifying agent to prepare the method for fluoropolymer.Because ether oxygen atom should do not contained containing carboxylic acid fluoride or emulsifying salt agent, containing hydrogen atom, there is certain degradation property, bio-toxicity is little, be used for, in the preparation process of fluoropolymer, there is excellent emulsifying property as emulsifying dispersant, can control emulsion primary particle size preferably, the Primary particle size of fluoropolymer emulsion is 50 ~ 500nm, obtains high-molecular weight polymer.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph figure of ptfe emulsion in embodiment 5.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.
Embodiment 1, C 4f 9-CHF-CF 2-COONH 4synthesis
(1) C is prepared 4h 9-CHF-CF 2-CFH-CF 2i
173g(Mw=346,0.5M is added in 1L autoclave) C 4f 9i.After being cooled to-78 DEG C, autoclave is emptying and add 52g CF 2=CFH.Mixture reacts 15 hours at 210 DEG C, the C that rectifying separation is residual subsequently 4f 9i and C 4f 9i and CF 2the affixture of=CFH different ratios, when 20mmHg, boiling point is collect under 65 ~ 67 DEG C of conditions to obtain C 4f 9i and CF 2=CFH is in the adduct 52g of 1:2 ratio.
(2) C is prepared 4h 9-CHF-CF 2-CH=CF 2
Will containing 88gC 4h 9-CHF-CF 2-CFH-CF 2the 90mL dimethyl formamide of I and 11.0g LiCl mixture is slowly heated to 150 DEG C, keeps 3.5 hours under pressure 150-200mmHg.Be cooled to-10 DEG C after being evaporated by light constituent, after layering, collect lower floor's material.Through washing, rectifying under normal pressure, collects 106 ~ 108 DEG C of cuts and obtains 45.2g C 4h 9-CHF-CF 2-CH=CF 2.
(3) C is prepared 4h 9-CHF-CF 2-COOH
By 12.6g KMnO 4, 55g water, the dense H of 7.3g 2sO 4with 11.2g C 4h 9-CHF-CF 2-CH=CF 2mixture is heated to 80 ~ 90 DEG C of reactions 5 hours.Cool to room temperature subsequently, mixture Na 2s 2o 3mnO is removed in process 2, add 50mL10%H 2sO 4use extracted with diethyl ether subsequently.Ether layer 5%H 2sO 4rinse and use Na 2sO 4dry.Obtain 8.3g solid after removing ether, obtain 7.3g C from recrystallization normal hexane 4h 9-CHF-CF 2-COOH.
(4) C is prepared 4h 9-CHF-CF 2-COONH 4
7.3g C 4h 9-CHF-CF 2-COOH is dissolved in 25mL ether.Stirring at room temperature simultaneously, passes into excessive NH 3, obtain 7.0g white solid C 4h 9-CHF-CF 2-COONH 4.
Embodiment 2, C 4f 9-CHF-CF 2-COONH 4synthesis
I () prepares C 4f 9cFClCF 2i
171g C is added in 1L autoclave 4f 9i.After being cooled to-78 DEG C, emptying autoclave also adds 70g CF 2=CFCl.Mixture was 190-200 DEG C of reaction 5 hours, and rectifying separation subsequently, collects 220g C at 125 ~ 127 DEG C 4f 9cFClCF 2i.
(ii) C is prepared 4f 9cF=CF 2
Toward in 1L tetra-mouthfuls of glass reaction bottles that stirring rake and condenser are housed, add 500ml methyl alcohol and 85g zinc powder, drip C at 60 ~ 65 DEG C subsequently 4f 9cFClCF 2i, adds 230g altogether.Isolate zinc powder after dropwising, reaction mixture mixes with the HCl of 1N, with after washing.Collect lower floor rectifying obtains 132g C at 56 ~ 58 DEG C 4f 9cF=CF 2.
(iii) C is prepared 4f 9cFHCF 2cOOCH 3
Toward in 1L tetra-mouthfuls of glass reaction bottles that stirring rake and condenser are housed, add 500ml methyl alcohol, 120g C 4f 9cF=CF 2with 5g methylol S-WAT.Reaction mixture is heated to backflow, adds 3.5g tert-butyl hydroperoxide subsequently, isolates liquid phase, and under 84 ~ 86 DEG C (180mmHg) are collected in rectifying, cut obtains C 4f 9cFHCF 2cH 2oH.
Toward in 1L tetra-mouthfuls of glass reaction bottles that stirring rake and condenser are housed, add 350ml water, 68g KMnO 4with 19g NaOH.83gC is dripped at lower than 50 DEG C 4f 9cFHCF 2cH 2oH.Gained purees removes MnO after filtration 2.Use water flush cake, filtrate is transferred in rectifier unit also with the acidifying of 32g thiosulfonic acid.Add 50g methyl alcohol, collect through distillation the C that boiling point is 66 ~ 68 DEG C (180mmHg) 4f 9cFHCF 2cOOCH 3.
(iv) C is prepared 4f 9cFHCF 2cOONH 4
7g C 4f 9cFHCF 2cOOCH 3be dissolved in 25mL ether, stirring at room temperature simultaneously, passes into excessive NH 3, obtain 6.8g white solid C 4f 9cFHCF 2cOONH 4.
Embodiment 3, C 6f 13-CHF-CF 2-COONH 4synthesis
(1) C is prepared 6f 13-CHF-CF 2-CFH-CF 2i
185g C is added in 1L autoclave 6f 13i.After being cooled to-78 DEG C, autoclave is emptying and add 48g CF 2=CFH.Mixture reacts 27 hours at 215 DEG C, the C that rectifying separation is residual subsequently 6f 13i and C 6f 13i and CF 2the affixture of=CFH different ratios, when 20mmHg, boiling point is collect under 82 ~ 84 DEG C of conditions to obtain C 4f 9i and CF 2=CFH is in the adduct 55g of 1:2 ratio.
(2) C is prepared 6f 13-CHF-CF 2-CH=CF 2
Will containing 100g C 6f 13-CHF-CF 2-CFH-CF 2the 95mL dimethyl formamide of I and 10.5g LiCl mixture is slowly heated to 155 DEG C, keeps 3.5 hours under pressure 150-200mmHg.Be cooled to-10 DEG C after being evaporated by light constituent, after layering, collect lower floor's material.Through washing, rectifying under normal pressure, collects 139 ~ 141 DEG C of cuts and obtains 56.8g C 6f 13-CHF-CF 2-CH=CF 2.
(3) C is prepared 6f 13-CHF-CF 2-COOH
By 12.8g KMnO 4, 55g water, the dense H of 7.3g 2sO 4with 12.4g C 6f 13-CHF-CF 2-CH=CF 2mixture is heated to 80 ~ 90 DEG C of reactions 6 hours.Cool to room temperature subsequently, mixture Na 2s 2o 3mnO is removed in process 2, add 50mL10%H 2sO 4use extracted with diethyl ether subsequently.Ether layer 5%H 2sO 4rinse and use Na 2sO 4dry.Obtain 9.1g solid after removing ether, obtain 8.4g C from recrystallization normal hexane 6f 13-CHF-CF 2-COOH.
(4) C is prepared 6f 13-CHF-CF 2-COONH 4
8.4g C 6f 13-CHF-CF 2-COOH is dissolved in 30mL ether.Stirring at room temperature simultaneously, passes into excessive NH 3, obtain 8.1g white solid C 6f 13-CHF-CF 2-COONH 4.
Embodiment 4, CF 3cF (CF 3)-CHF-CF 2the synthesis of-COOY
(1) CF is prepared 3cF (CF 3)-CHF-CF 2-CFH-CF 2i
160g CF is added in 1L autoclave 3cF (CF 3) I.After being cooled to-78 DEG C, autoclave is emptying and add 50g CF 2=CFH.Mixture reacts 14 hours at 210 DEG C, the CF that rectifying separation is residual subsequently 3cF (CF 3) I and CF 3cF (CF 3) I and CF 2the affixture of=CFH different ratios, when 20mmHg, boiling point is collect under 54 ~ 56 DEG C of conditions to obtain CF 3cF (CF 3) I and CF 2=CFH is in the adduct 49g of 1:2 ratio.
(2) CF is prepared 3cF (CF 3)-CHF-CF 2-CH=CF 2
Will containing 92g CF 3cF (CF 3)-CHF-CF 2-CFH-CF 2the 90mL dimethyl formamide of I and 10.6g LiCl mixture is slowly heated to 150 DEG C, keeps 3.0 hours under pressure 150-200mmHg.Be cooled to-10 DEG C after being evaporated by light constituent, after layering, collect lower floor's material.Through washing, rectifying under normal pressure, collects 90 ~ 92 DEG C of cuts and obtains 53.8gCF 3cF (CF 3)-CHF-CF 2-CH=CF 2.
(3) CF is prepared 3cF (CF 3)-CHF-CF 2-COOH
By 13.5g KMnO 4, 55g water, the dense H of 7.5g 2sO 4with 11.0g CF 3cF (CF 3)-CHF-CF 2-CH=CF 2mixture is heated to 80 ~ 90 DEG C of reactions 5 hours.Cool to room temperature subsequently, mixture Na 2s 2o 3mnO is removed in process 2, add 55mL10%H 2sO 4use extracted with diethyl ether subsequently.Ether layer 5%H 2sO 4rinse and use Na 2sO 4dry.Obtain 9.1g solid after removing ether, obtain 8.6g CF from recrystallization normal hexane 3cF (CF 3)-CHF-CF 2-COOH.
(4) CF is prepared 3cF (CF 3)-CHF-CF 2-COONH 4
8.6g CF 3cF (CF 3)-CHF-CF 2-COOH is dissolved in 30mL ether.Stirring at room temperature simultaneously, passes into excessive NH 3, obtain 8.2g white solid CF 3cF (CF 3)-CHF-CF 2-COONH 4.
It should be noted that, the synthetic route of compound of the present invention and method are all the same, and just raw material is different.Those skilled in the art can prepare the compound of any one general formula I by feed change according to above-described embodiment.
Toxicity test 1
Adopt male SD rat, by the Compound C of preparation 4f 9-CHF-CF 2-COONH 4within continuous 7 days, carry out Orally administered according to the mode of 0,0.5,5.0,50mg/kg/day to difference group SD rat respectively.Anatomical results shows, feeding volume is the phenomenon that hepatomegaly appears in the rat group of 50mg/kg/day, and the rat group liver of below 50mg/kg/day shows no obvious abnormalities, and the feeding volume without visible deleterious effect level (NOAEL) is 50mg/kg/day.
Toxicity test 2
Be C by chemical formula 6f 13-CHF-CF 2-COONH 4compound carry out animal experiment in a manner mentioned above, the feeding volume without visible deleterious effect level is 5.0mg/kg/day.
Contrast toxicity test 1 and toxicity test 2 result show, emulsifying agent C 4f 9-CHF-CF 2-COONH 4and C 6f 13-CHF-CF 2-COONH 4compare, C 4f 9-CHF-CF 2-COONH 4bio-toxicity be relatively much smaller.
Embodiment 5: utilize emulsifying agent C 4f 9cFHCF 2cOONH 4prepare polytetrafluoroethyldispersion dispersion resin
1400Kg deionized water is added, 2.3kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L 4f 9cFHCF 2cOONH 4, 1000g succsinic acid and 60kg solid paraffin.At 65 DEG C, polymeric kettle TFE is emptying and replace three times.After replacing three times, oxygen level is less than 10ppm.Stirring velocity 45rpm, is increased to 2.7MPa with tetrafluoroethylene monomer by pressure, and the initiator ammonium persulfate (APS) 1.0g being dissolved in 1000ml deionized water adds with 100ml/ minute speed.After adding, keep pressure 2.7MPa with TFE.After supply 480kg TFE, reaction terminates.2.2 hours reaction times, ptfe emulsion concentration 25.3%, average particulate size 255nm.After reaction terminates, do not produce condensation product.Dispersion liquid emulsion is through cohesion, and washing and drying obtain 470kg polytetrafluoroethyldispersion dispersion resin.Size of particles 580 microns, SSG is 2.161.SSG(standard specific gravity) measured by ASTMD-4895 method.
Embodiment 6: utilize emulsifying agent C 4f 9cFHCF 2cOONH 4prepare modified polytetrafluoroethyldispersion dispersion resin
1400Kg deionized water is added, 2.3kg C in the horizontal stainless steel polymeric kettle of 2000L 4f 9cFHCF 2cOONH 4as emulsifying agent, 650g succinic acid and 100kg solid paraffin; At 80 DEG C, polymerization reaction kettle tetrafluoroethylene (TFE) is emptying and replace three times; After replacing three times, oxygen level is less than 10ppm, stirs with 45rpm speed, keeps polymerization reaction kettle temperature 80 DEG C, be filled with tetrafluoroethylene monomer and pressure is increased to 1.5MPa, the initiator ammonium persulfate (APS) 8g being dissolved in 1000ml deionized water adds with 100ml/ minute speed; Add initiator post-polymerization to start.Reaction beginning after 1.0 hours, add 1000g R 1216,1500g trifluorochloroethylene and 20g trifluoro-ethylene, is filled with tetrafluoroethylene (TFE) raised pressure to 2.7MPa and keeps this pressure.React after 4.5 hours, temperature is increased to 100 DEG C and stops adding tetrafluoroethylene (TFE) simultaneously; When Pressure Drop terminates to reaction during 0.4MP.Emulsion concentration 31.0%, primary particle mean sizes 235nm.After having reacted, emulsion obtains 618kg dispersion resin through cohesion, washing and drying.Size of particles 640 microns, SSG is 2.170.SSG(standard specific gravity) measured by ASTM D-4895 method.
In the mould of compression ratio 1600:1, carry out extrusion test to the resin obtained, extrusion pressure is 47.3MPa.Extrude rod straight, clean, smooth surface, elasticity is suitable for.

Claims (10)

1., for the preparation of an emulsifying agent for fluoropolymer, be the compound with general formula I, R f-CHF-CF 2-COOY, wherein, R fbe perfluoroalkyl or partially fluorinated alkyl, and be containing the linear chain structure of 1 to 8 carbon atoms, band branched structure or the alkyl of ring texture, described partially fluorinated R fnon-fluorine atom in group is H, Cl or Br atom, and nonfluorinated atom is preferably Cl atom; Y is NH 4, Li, Na, K or H.
2. emulsifying agent as claimed in claim 1, is characterized in that in the compound of general formula I, R fbe the perfluoroalkyl containing 3-8 carbon atom, Y is NH 4or H; Preferred R fcF 3cF 2cF 2cF 2-.
3. emulsifying agent as claimed in claim 1, is characterized in that the compound of general formula I is one of following compounds:
CF 3CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-COOY
CF 3-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CHF-CF 2-CHF-CF 2-COOY
CF 3-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CF 2-CHF-CHF-CF 2-COOY
CF 3-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CClF-CF 2-CHF-CF 2-COOY
CF 3-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF(CF 3)CF 2CF 2-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY
CF 3CF 2CF 2CF 2CF(CF 3)-CF 2-CClF-CHF-CF 2-COOY。
4. the application of emulsifying agent according to claim 1, prepares fluoropolymer for dispersion method under initiator effect in aqueous phase system.
5. the application of emulsifying agent as claimed in claim 4, is characterized in that, as emulsifying agent, for the fluoropolymer of dispersion method preparation containing tetrafluoroethylene monomer.
6. a preparation method for fluoropolymer, its for use in water medium have general formula I containing carboxylic acid fluoride or salt as emulsifying agent, under initiator exists, be polymerized fluorochemical monomer, it is characterized in that, described emulsifying agent is the compound with general formula I, R f-CHF-CF 2-COOY, wherein, R fbe perfluoroalkyl or partially fluorinated alkyl, and be containing the linear chain structure of 1 to 8 carbon atoms, band branched structure or the alkyl of ring texture, described partially fluorinated R fnon-fluorine atom in group is H, Cl or Br atom; Y is NH 4, Li, Na, K or H.
7. the preparation method of fluoropolymer as claimed in claim 6, it is characterized in that, described emulsifying agent is CF 2cF 2cF 2cF 2-CHF-CF 2-COOY, Y are NH4 or H.
8. the preparation method of fluoropolymer as claimed in claim 6, it is characterized in that, the described fluorochemical monomer for being polymerized, Oil repellent is at least 35wt%, includes fluorinated olefin or the fluorinated dioxoles of 2-10 carbon atom, and molecular formula is CY 2=CYOR or CY 2the fluorinated vinyl ether of=CYOR'OR, wherein the Y perfluor that to be H or F, R and R' be respectively containing 1 ~ 8 carbon atom or partially fluorinated alkyl and alkyl vinyl; R is preferably containing 1 ~ 4 carbon atom and is preferably perfluorination, and R' is preferably containing 1 ~ 4 carbon atom and is preferably perfluorination.
9. the preparation method of fluoropolymer as claimed in claim 8, it is characterized in that, described fluorinated olefin is 2 ~ 6 carbon atoms, comprises tetrafluoroethylene (TFE), R 1216 (HFP), trifluorochloroethylene (CTFE), ethylene fluoride, vinylidene fluoride, trifluoro-ethylene, hexafluoro-isobutene, one of in perfluorobutyl ethylene or combination.
10. the preparation method of fluoropolymer as claimed in claim 6, is characterized in that, the multipolymer of described fluoropolymer for being proplast or tetrafluoroethylene and R 1216 (HFP), trifluorochloroethylene and trifluoro-ethylene.
CN201310272864.4A 2013-07-01 2013-07-01 A kind of preparation method of emulsifying agent containing carboxylic acid fluoride and fluoropolymer Active CN104277163B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310272864.4A CN104277163B (en) 2013-07-01 2013-07-01 A kind of preparation method of emulsifying agent containing carboxylic acid fluoride and fluoropolymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310272864.4A CN104277163B (en) 2013-07-01 2013-07-01 A kind of preparation method of emulsifying agent containing carboxylic acid fluoride and fluoropolymer

Publications (2)

Publication Number Publication Date
CN104277163A true CN104277163A (en) 2015-01-14
CN104277163B CN104277163B (en) 2017-08-25

Family

ID=52252548

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310272864.4A Active CN104277163B (en) 2013-07-01 2013-07-01 A kind of preparation method of emulsifying agent containing carboxylic acid fluoride and fluoropolymer

Country Status (1)

Country Link
CN (1) CN104277163B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113728014A (en) * 2019-04-26 2021-11-30 大金工业株式会社 Method for producing aqueous fluoropolymer dispersion, method for treating wastewater, and aqueous fluoropolymer dispersion

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808651A (en) * 1986-09-17 1989-02-28 Hoechst Aktiengesellschaft Solutions of fluoropolymers, and their use
CN1876709A (en) * 2005-06-06 2006-12-13 旭硝子株式会社 Aqueous dispersion of polytetrafluorethylene and process for its production
CN101223231A (en) * 2005-07-13 2008-07-16 旭硝子株式会社 Aqueous dispersion of polytetrafluoroethylene and process for its production
US20090163653A1 (en) * 2006-08-31 2009-06-25 Asahi Glass Company, Limited Perfluorocarboxylic acid salt and process for producing it
CN101774902A (en) * 2010-01-13 2010-07-14 苏州大学 Preparation method of polyfluoro aliphatic carboxylic acid
JP4714991B2 (en) * 1998-07-07 2011-07-06 ダイキン工業株式会社 Production method of fluorine-containing polymer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4808651A (en) * 1986-09-17 1989-02-28 Hoechst Aktiengesellschaft Solutions of fluoropolymers, and their use
JP4714991B2 (en) * 1998-07-07 2011-07-06 ダイキン工業株式会社 Production method of fluorine-containing polymer
CN1876709A (en) * 2005-06-06 2006-12-13 旭硝子株式会社 Aqueous dispersion of polytetrafluorethylene and process for its production
CN101223231A (en) * 2005-07-13 2008-07-16 旭硝子株式会社 Aqueous dispersion of polytetrafluoroethylene and process for its production
US20090163653A1 (en) * 2006-08-31 2009-06-25 Asahi Glass Company, Limited Perfluorocarboxylic acid salt and process for producing it
CN101774902A (en) * 2010-01-13 2010-07-14 苏州大学 Preparation method of polyfluoro aliphatic carboxylic acid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.D.LAZERTE 等: "The Free-radical Catalyzed Addition of Alcohols and Aldehydes to Perfluoroolefins", 《J.AM.CHEM.SOC.》, vol. 77, no. 4, 20 February 1955 (1955-02-20), pages 910 - 914, XP 002948574, DOI: doi:10.1021/ja01609a033 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113728014A (en) * 2019-04-26 2021-11-30 大金工业株式会社 Method for producing aqueous fluoropolymer dispersion, method for treating wastewater, and aqueous fluoropolymer dispersion

Also Published As

Publication number Publication date
CN104277163B (en) 2017-08-25

Similar Documents

Publication Publication Date Title
CN102264777B (en) Fluoropolymer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer
US7659333B2 (en) Fluorinated surfactants for use in making a fluoropolymer
US8614265B2 (en) Method of making fluoropolymer dispersion
CN102264775B (en) Fluoropolymer produced by aqueous polymerization using dispersed particulate of fluorinated ionomer produced in situ
CN102264779B (en) Fluoropolymer particles having a nucleus of fluorinated ionomer
US20220389128A1 (en) Aqueous polymerization of fluorinated monomer using polymerization agent comprising fluoropolyether acid or salt and short chain fluorosurfactant
US7838608B2 (en) Fluorinated surfactants for making fluoropolymers
US9212279B2 (en) Microemulsions and fluoropolymers made using microemulsions
CN104844737A (en) Process for producing fluoropolymers
WO2007011633A1 (en) Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
WO2010056688A1 (en) Fluorosulfonates
CN103124749A (en) Process for producing polytetrafluoroethylene fine powder
KR20110086151A (en) Fluoroalkyl ether sulfonate surfactants
CN104231136A (en) Method for preparing fluorine-containing polymer by dispersion process
CN102428106B (en) Thermal reduction of fluoroether carboxylic acids or salts from fluoropolymer dispersions
CN104277163A (en) Fluorine-containing carboxylic acid emulsifier and preparation method of fluorine-containing polymer
WO2010038902A1 (en) Production method of fluoroethercarboxylic acid fluoride and fluoroethercarboxylic acid
CN104211840B (en) A kind of hypotoxicity emulsifying agent of fluoropolymer reaction and the preparation method of fluoropolymer
CN102264684A (en) Ethylene-tetrafluoroethylene carboxylic acids and salts
WO2024020783A1 (en) Reactive fluorosurfactant, and preparation method therefor and use thereof
CN117510742A (en) Non-fluorine surfactant and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant