CN104231136A - Method for preparing fluorine-containing polymer by dispersion process - Google Patents
Method for preparing fluorine-containing polymer by dispersion process Download PDFInfo
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- CN104231136A CN104231136A CN201310239328.4A CN201310239328A CN104231136A CN 104231136 A CN104231136 A CN 104231136A CN 201310239328 A CN201310239328 A CN 201310239328A CN 104231136 A CN104231136 A CN 104231136A
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Abstract
The invention relates to a method for preparing a fluorine-containing polymer by a dispersion process, which comprises the following steps: carrying out polymerization reaction on a fluorine-containing monomer in the presence of an emulsifier and an initiator in a water phase system at 50-150 DEG C under the reaction pressure of 0.3-7 MPa, and after the reaction finishes, carrying out aggregation separation, water washing and drying on the fluorine-containing polymer in the reaction emulsion to obtain the solid fluorine-containing polymer; or concentrating the reaction emulsion until the concentration of the fluorine-containing polymer in the concentrated solution is 30-70 wt% to obtain the fluorine-containing polymer concentrated solution, wherein the emulsifier accounts for 0.01-2.0 wt% of the water in the reaction system in the polymerization process. By adopting the emulsifier, the fluorine-containing polymer, which has excellent properties and lower toxicity than the prior art, can be obtained, and the service performance and biological toxicity have the optimal balance.
Description
Technical field
The present invention relates to a kind of method that dispersion method prepares fluoropolymer, belong to technical field of fluorine chemical industry.
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 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.
Current domestic and international many fluorine chemical manufacturers all in the substitute of active development PFOA, and have carried out extensive work.Mention such as: morning twilight chemical research institute is at Chinese patent literature CN101648122A(application number 200910092202.2) and adopt Fluorine containing olefine to prepare the tensio-active agent containing ether segment by dioxygen oxidation at low temperatures, the tensio-active agent that this method obtains contains a large amount of side chains, dispersed bad in the course of the polymerization process.Ju Hua group is at Chinese patent literature CN102504063A(application number 201110338501) the middle tensio-active agent adopting the fluorine-containing ether segment of chloride atom, the toxicity of this tensio-active agent is comparatively large, can not meet eco-friendly requirement completely.United States Patent (USP) 5789508,4025709, the tensio-active agents mentioned such as 5688884,5763552, due to the relation of molecular structure, can affect the quality product of polymkeric substance in polymerization process.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide a kind of dispersion method to prepare the method for fluoropolymer.The present invention is particularly useful for making the fluoropolymer containing tetrafluoroethylene monomer, is especially particularly useful for making polytetrafluoroethyldispersion dispersion resin or the emulsion of non-melt processing.
A kind of dispersion method prepares the method for fluoropolymer, to comprise in aqueous phase system under emulsifying agent and initiator participate in, fluorochemical monomer is adopted to carry out polyreaction, temperature of reaction 50 ~ 150 DEG C, reaction pressure 0.3 ~ 7MPa, after having reacted, by the fluoropolymer agglomeration separation in reaction emulsion, water washing, drying, obtained solid-state fluoropolymer;
Or concentrate the emulsion of having reacted, to concentrated solution, the concentration of fluoropolymer is 30% ~ 70wt%, obtains fluoropolymer concentrated solution;
In described polymerization process, the add-on of emulsifying agent in reaction system is 0.01 ~ 2.0% of water weight, and described emulsifying agent has following general formula:
C
4F
9-CH
2-CF
2-COOM
Wherein, wherein M is H, Li, Na, K or NH
4.
Preferred according to the present invention, described dispersion method prepares the method for fluoropolymer, adds the step of paraffin before being also included in polyreaction.Preferred further, the add-on of paraffin is 0.1 ~ 12% of water weight.Add the generation that paraffin can reduce condensation product.
Preferred according to the present invention, described fluorochemical monomer is the fluorinated olefin of 2 ~ 10 carbon atoms, fluorinated dioxoles, cyclic fluorinated monomer, and/or structure is CY
2=CYOR or CY
2the fluorinated vinyl ether of=CYOR'OR; Wherein, the Y perfluor that to be H or F, R or R' be respectively containing 1 ~ 8 carbon atom or partially fluorinated alkyl or alkyl vinyl.
Preferred further according to the present invention, described R is the perfluoroalkyl of 1 ~ 4 carbon atom; R' is the perfluoroalkyl of 1 ~ 4 carbon atom.
Preferred further according to the present invention, described fluorinated olefin is the fluorinated olefin of 2 ~ 6 carbon atoms.Further preferred, described fluorinated olefin is selected from tetrafluoroethylene (TFE), R 1216 (HFP), trifluorochloroethylene (CTFE), ethylene fluoride, vinylidene fluoride, trifluoro-ethylene, hexafluoro-isobutene or perfluorobutyl ethylene.
More excellent, when described fluorochemical monomer is tetrafluoroethylene with the mixing of other fluorochemical monomers, the molar content of other fluorochemical monomers is more than 0.5%; Optimum, the molar content of other fluorochemical monomers is 0.5% ~ 15%.
If tetrafluoroethylene uses as unique monomer, product is polytetrafluoroethylene (PTFE) homopolymer.If a certain amount of fluorochemical monomer added except tetrafluoroethylene to reactor comes and tetrafluoroethylene copolymerization, gained modification TFE polymkeric substance improves film forming properties during sintering, keep the PTFE performance in polymkeric substance (modified ptfe) simultaneously, increase comonomer consumption and effectively can improve resin melt-processable performance, add-on is according to the reactive behavior of comonomer, and the melt viscosity of TFE multipolymer is 10
2to 10
6pa.s.Melt viscosity measuring method is shown in ASTM D1238.At present, comonomer is preferably moieties to contain 1 ~ 8(is more preferably 1 ~ 3) perfluoroalkyl vinyl ether of individual carbon atom, perhalogeno alkene is 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 aqueous dispersion obtained, be generally 20 to 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.
More excellent, when described fluorochemical monomer is tetrafluoroethylene, also comprise the step adding chain-transfer agent, the add-on of chain-transfer agent is 0.01 ~ 500ppm of the water yield; Optimum, described chain-transfer agent is methyl alcohol or ethanol.
PTFE homopolymer 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.Chain-transfer agent add the PTFE that can obtain low melting viscosity, if observed value at 372 DEG C is 10 ~ 1*10
5pa.s.
Preferred further according to the present invention, described cyclic fluorinated monomer is perfluor-2,2-dimethyl-1,3-dioxole (PDD) or perfluor-2-methylene radical-4-methyl isophthalic acid, 3-dioxolane (PMD).
Described fluoropolymer is (per) fluoropolymer, specifically proplast, tetrafluoroethylene and have the multipolymer of one or more fluorinated olefin and the multipolymer of perfluoroalkyl vinyl ether of 2 ~ 8 carbon atoms.
Preferred according to the present invention, described fluorochemical monomer is the fluorochemical monomer of Oil repellent >=35wt%.
Preferred according to the present invention, described initiator amount is 0.1 ~ 500ppm of water weight.Initiator can be selected from known water-soluble or oil-soluble initiator; Preferred further, described initiator is selected from ammonium persulphate, Potassium Persulphate, t-butylcumylperoxide, benzoyl peroxide, Diisopropyl azodicarboxylate, potassium permanganate, succinic acid peroxide, the redox system of Potassium Persulphate and S-WAT, the redox system of Potassium Persulphate, sodium pyrosulfate and ferrous sulfate, or, the redox system of Potassium Persulphate, sodium pyrosulfate and Silver Nitrate.
Preferred according to the present invention, described emulsifying agent add-on is 0.05 ~ 1.5% of water weight.
Described emulsifying agent C
4f
9-CH
2-CF
2-COOH, C
4f
9-CH
2-CF
2-COO Li, C
4f
9-CH
2-CF
2-COO Na, C
4f
9-CH
2-CF
2-COOK or C
4f
9-CH
2-CF
2-COONH
4all can adopt this area customary preparation methods preparation.
Except whole emulsifying agents can being added before polymerization starts, also a part of emulsifying agent can be added in polymerization process.
The methods such as the polymer emulsion particle that in the present invention, dispersion polymerization obtains 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 from liquid.Drying obtains fluoropolymer dispersion resin.
Preferred according to the present invention, the temperature of described drying is 10 DEG C ~ 250 DEG C, and further preferably, the temperature of described drying is 100 DEG C ~ 200 DEG C.
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.
Concentrate and can adopt evaporation, be separated, the method that this area such as electrodialysis and ultrafiltration is conventional.
Preferred further according to the present invention, above-mentioned enrichment step also comprises the step adding dispersion stabilizer, and dispersion stabilizer is selected from nonionogenic tenside, more excellent, and dispersion stabilizer is selected from poly-alkoxyl group ether or polyoxyethylene groups alkyl phenyl ether.
More excellent, above-mentioned dispersion stabilizer add-on is 0.5 ~ 20% of fluoropolymer solids content quality; Optimum, above-mentioned dispersion stabilizer add-on is 2 ~ 12% of fluoropolymer solids content quality.When dispersion stabilizer add-on is lower than fluoropolymer solids content quality 0.5%, concentrated solution stability is bad, and when dispersion stabilizer add-on exceedes fluoropolymer solids content quality 20%, exceeding part can not have obvious effect to raising dispersion stable.
Preferred according to the present invention, also comprise the step adding pH adjusting agent.Preferred further, described pH adjusting agent is succsinic acid or oxalic acid.The add-on of pH adjusting agent is this area common technology, and the needs that those skilled in the art can react according to raw material etc. add, thus adjust ph 4 ~ 10.
It can be glassy, plastic-like or elastomerics shape that the present invention manufactures fluoropolymer.Can be amorphous or partial crystallization, melt-processable or non-melt processing.
Above-mentioned steps and condition if no special instructions, all can operate by this area conventional steps and condition.
Beneficial effect
1, the present invention adopts C
4f
9-CH
2-CF
2-COOM, wherein M is H, Li, Na, K or NH
4as the emulsifying agent in fluoropolymer preparation process, the fluoropolymer of excellent property can either be obtained, and toxicity is much lower relative to prior art, C
4f
9-CH
2-CF
2-COOM possesses best balance in use properties and bio-toxicity.
2, the present invention adopts C
4f
9-CH
2-CF
2-COOM, wherein M is H, Li, Na, K or NH
4as the emulsifying agent in fluoropolymer preparation process, the Primary particle size of obtained fluoropolymer emulsion is preferably 50 ~ 500nm, can effectively obtain suitable size of particles, the suitable mean particle size of obtained fluoropolymer is at 300 ~ 700 μm, and the apparent density of fluoropolymer is 0.35 to 0.65g/ml.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited thereto.
In embodiment, mean particle size measuring method is carried out with reference to the method recorded in ASTM D-1457, and apparent density measuring method is carried out with reference to reference to the method recorded in JIS K-6891.
The preparation of emulsifying agent:
C
4f
9-CH
2-CF
2the synthesis of-COOH
I () prepares C
4f
9-CH
2-CF
2-CH
2-CF
2i
173g(Mw=346,0.5M is added in 1L autoclave) C
4f
9i.Be cooled to-78 DEG C, after reactor of finding time, add 52g CF
2=CH
2.Mixture is heated to 210 DEG C of reactions 15 hours, the C that rectifying separation unreacted is complete subsequently
4f
9i and C
4f
9i and CF
2=CH
2the affixture of different ratios, collects tower top temperature C under 82 ~ 84 DEG C of conditions in the rectifying of 25mmHg pressure
4f
9i and CF
2=CH
2by the product that the addition of 1:2 obtains, collect 47.0g altogether.
(ii) C is prepared
4f
9-CH
2-CF
2-CH=CF
2
Will containing 82g C
4f
9-CH
2-CF
2-CH
2-CF
2i and 11.0g LiCl mixture adds 90mL dimethyl formamide, is slowly heated to 150 DEG C, keeps 3.5 hours, be then cooled to-10 DEG C under pressure 150-200mmHg.Material layering, collects lower floor's material, after washing and rectifying, obtain 47.6g C
4f
9-CH
2-CF
2-CH=CF
2, under 760mmHg, boiling point is 106 ~ 108 DEG C.
(iii) C is prepared
4f
9-CH
2-CF
2-COOH
By 12.2g KMnO
4, 49g water, the dense H of 7.1g
2sO
4with 10.5g C
4f
9-CH
2-CF
2-CH=CF
2mixture is heated to 80 ~ 90 DEG C of reactions 4.5 hours.Cool to room temperature subsequently, mixture Na
2sO
3process removes MnO
2, add 50mL10%H
2sO
4, use extracted with diethyl ether subsequently.Ether layer 5%H
2sO
4rinse and use Na
2sO
4dry.Obtain 6.7g solid after removing ether, in normal hexane, recrystallization obtains 6.3g C
4f
9-CH
2-CF
2-COOH product.(composed by Enantiomeric excess, hydrogen and confirm structure,
19f NMR result shows chemical shift corresponding to each fluorion respectively :-83.1 ,-127.3 ,-125.0 ,-113.1, and-115.4,
1the hydrogen ion chemical shift that H NMR result display CH2 is corresponding is 2.8).
(iv) C
4f
9-CH
2-CF
2-COONH
4synthesis
Get the C that 6.0g is obtained
4f
9-CH
2-CF
2-COOH is dissolved in 25mL ether.Stirring at room temperature simultaneously, passes into excessive NH
3.Obtain 5.7g white solid C
4f
9-CH
2-CF
2-COONH
4.
Embodiment 1
1400Kg deionized water is added, 2.1kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L
4f
9-CH
2-CF
2-COONH
4, 1000g succsinic acid (pH value regulator) and 60kg solid paraffin.At 65 DEG C, polymeric kettle tetrafluoroethylene (TFE) is emptying and replace three times.Stirring velocity 45rpm, is increased to 2.7MPa with tetrafluoroethylene by pressure, is dissolved in 1000ml deionized water by 1.0g ammonium persulphate (APS), adds with 100ml/ minute speed.After adding, keep pressure 2.7MPa with tetrafluoroethylene (TFE).Supply 480kg tetrafluoroethylene (TFE) reacts end afterwards.2.3 hours reaction times, fluoropolymer mass concentration 25.1%, mean primary particle size 253nm in emulsion.After reaction terminates, do not produce condensation product.Dispersion liquid is through cohesion, and washing and drying obtain 470kg powder.Size of particles 580 microns, SSG is 2.164.SSG(standard specific gravity) measured by ASTM D-4895 method.
Embodiment 2
1400Kg deionized water is added, 2.3kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L
4f
9-CH
2-CF
2-COONH
4, 850g succsinic acid and 70kg solid paraffin.At 70 DEG C, polymeric kettle tetrafluoroethylene (TFE) is emptying and replace three times.Stirring velocity 45rpm, adds 1.5kg R 1216, then with tetrafluoroethylene, pressure is increased to 2.5MPa, is dissolved in 1000ml deionized water by 1.2g ammonium persulphate (APS), adds with 100ml/ minute speed.After adding, keep pressure 2.5MPa with tetrafluoroethylene (TFE).Supply 500kg tetrafluoroethylene (TFE) reacts end afterwards.3.2 hours reaction times, fluoropolymer mass concentration 26.2%, mean primary particle size 270nm in emulsion.After reaction terminates, do not produce condensation product.Dispersion liquid is through cohesion, and washing and drying obtain 490kg powder.Size of particles 550 microns, SSG is 2.186.SSG(standard specific gravity) measured by ASTM D-4895 method.
Embodiment 3
1400Kg deionized water is added, 2.2kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L
4f
9-CH
2-CF
2-COONH
4, 650g succsinic acid and 100kg solid paraffin.At 80 DEG C, polymeric kettle tetrafluoroethylene (TFE) is emptying and replace three times.Stirring velocity 45rpm, still temperature 80 DEG C, is increased to 1.5MPa with tetrafluoroethylene monomer by pressure, is dissolved in 1000ml deionized water by 8g ammonium persulphate (APS), adds with 100ml/ minute speed.Add initiator post-polymerization to start, reaction beginning after 1.0 hours, adds 1000g R 1216,1500g trifluorochloroethylene and 20g trifluoro-ethylene, keeps this pressure with tetrafluoroethylene (TFE) raised pressure to 2.7MPa.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.Fluoropolymer substrate concentration 30.8% in emulsion, average particulate size 240nm.Dispersion liquid is through cohesion, and washing and drying obtain 620kg powder.Size of particles 660 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 47.8Mpa.Extrude rod straight, clean, smooth surface, elasticity is suitable for.
Comparison study example 1
1400Kg deionized water is added, 2.1kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L
4f
9-CH
2-CH
2-CF
2-COONH
4(as described in patent US5763552), 1000g succsinic acid and 60kg solid paraffin.At 65 DEG C, polymeric kettle TFE is emptying and replace three times.Stirring velocity 45rpm, is increased to 2.7MPa with tetrafluoroethylene monomer by pressure, is dissolved in 1000ml deionized water by 1.0g ammonium persulphate (APS), adds with 100ml/ minute speed.After adding, keep pressure 2.7MPa with TFE.After supply 450kg TFE, reaction terminates.In 3.5 hours reaction times, in polymerization reaction kettle, there is 20kg condensation product, fluoropolymer substrate concentration 23.0%, mean primary particle size 320nm in emulsion.After condensation product is filtered, by the tetrafluoroethylene agglomeration separation in the emulsion of having reacted, after water washing, drying, obtain 410kg polytetrafluoroethyldispersion dispersion resin.Size of particles 580 microns, SSG is 2.192.
Comparison study example 2
1400Kg deionized water is added, 2.1kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L
6f
13-CH
2-CF
2-COONH
4(as described in patent US5763552), 1000g succsinic acid and 60kg solid paraffin.At 65 DEG C, polymeric kettle TFE is emptying and replace three times.Stirring velocity 45rpm, is increased to 2.7MPa with tetrafluoroethylene monomer by pressure, is dissolved in 1000ml deionized water by 1.0g ammonium persulphate (APS), adds with 100ml/ minute speed.After adding, keep pressure 2.7MPa with TFE.After supply 480kg TFE, reaction terminates.2.4 hours reaction times, fluoropolymer substrate concentration 25.2%, mean primary particle size 290nm in emulsion.After reaction terminates, do not produce condensation product.Dispersion liquid is through cohesion, and washing and drying obtain 468kg powder.Size of particles 590 microns, SSG is 2.165.
Comparison study example 3
1400Kg deionized water is added, 2.1kg emulsifying agent C in the horizontal stainless steel polymeric kettle of 2000L
2f
5-CH
2-CF
2-COONH
4, 1000g succsinic acid and 60kg solid paraffin.At 65 DEG C, polymeric kettle TFE is emptying and replace three times.Stirring velocity 45rpm, is increased to 2.7MPa with tetrafluoroethylene monomer by pressure, is dissolved in 1000ml deionized water by 1.0g ammonium persulphate (APS), adds with 100ml/ minute speed.After adding, keep pressure 2.7MPa with TFE.React because speed cannot proceed too slowly after supply 250kg TFE.In 5.6 hours reaction times, in polymerization reaction kettle, there is 40kg condensation product, fluoropolymer substrate concentration 12.0%, mean primary particle size 380nm in emulsion.After condensation product is filtered, by the tetrafluoroethylene agglomeration separation in the emulsion of having reacted, after water washing, drying, obtain 190kg polytetrafluoroethyldispersion dispersion resin.Size of particles 610 microns, SSG is 2.227.
Analyze known by embodiment 1 and Comparison study example 1 ~ 3: if containing CH in emulsifying agent
2when unit is too much, emulsion intercalation method decreases, and the increasing of the polymerization process chain tra nsfer situation caused due to H atom in emulsifying agent, the polymkeric substance SSG finally obtained can be higher; If fluorine-containing groups very little in emulsifying agent, emulsifying agent dispersing property in the course of the polymerization process can be affected, and polymerization system stability becomes very poor, and system shifts to an earlier date breakdown of emulsion cohesion, cannot obtain required polymkeric substance.C
4f
9-CH
2-CF
2-COONH
4and C
6f
13-CH
2-CF
2-COONH
4use as emulsifying agent and can obtain good polymkeric substance.
Toxicity simultaneous test 1
Adopt male SD rat, by C
4f
9-CH
2-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 simultaneous test 2
By C
6f
13-CH
2-CF
2-COONH
4carry 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, the emulsifying agent C that the present invention is used
4f
9-CH
2-CF
2-COONH
4and C
6f
13-CH
2-CF
2-COONH
4compare, bio-toxicity is much smaller relatively.
Claims (10)
1. a dispersion method prepares the method for fluoropolymer, to comprise in aqueous phase system under emulsifying agent and initiator participate in, fluorochemical monomer is adopted to carry out polyreaction, temperature of reaction 50 ~ 150 DEG C, reaction pressure 0.3 ~ 7MPa, after having reacted, by the fluoropolymer agglomeration separation in reaction emulsion, water washing, drying, obtained solid-state fluoropolymer;
Or concentrate the emulsion of having reacted, to concentrated solution, the concentration of fluoropolymer is 30% ~ 70wt%, obtains fluoropolymer concentrated solution;
In described polymerization process, the add-on of emulsifying agent in reaction system is 0.01 ~ 2.0% of water weight, and described emulsifying agent has following general formula:
C
4F
9-CH
2-CF
2-COOM
Wherein, wherein M is H, Li, Na, K or NH
4.
2. the method for claim 1, is characterized in that, described fluorochemical monomer is the fluorinated olefin of 2 ~ 10 carbon atoms, fluorinated dioxoles, cyclic fluorinated monomer, and/or structure is CY
2=CYOR or CY
2the fluorinated vinyl ether of=CYOR'OR; Wherein, the Y perfluor that to be H or F, R or R' be respectively containing 1 ~ 8 carbon atom or partially fluorinated alkyl or alkyl vinyl.
3. method as claimed in claim 2, it is characterized in that, described R is the perfluoroalkyl of 1 ~ 4 carbon atom; R' is the perfluoroalkyl of 1 ~ 4 carbon atom.
4. method as claimed in claim 2, it is characterized in that, described fluorinated olefin is the fluorinated olefin of 2 ~ 6 carbon atoms; Further preferred, described fluorinated olefin is selected from tetrafluoroethylene (TFE), R 1216 (HFP), trifluorochloroethylene (CTFE), ethylene fluoride, vinylidene fluoride, trifluoro-ethylene, hexafluoro-isobutene or perfluorobutyl ethylene.
5. method as claimed in claim 4, is characterized in that, when described fluorochemical monomer is tetrafluoroethylene with the mixing of other fluorochemical monomers, the molar content of other fluorochemical monomers is more than 0.5%; Optimum, the molar content of other fluorochemical monomers is 0.5% ~ 15%.
6. method as claimed in claim 4, it is characterized in that, when described fluorochemical monomer is tetrafluoroethylene, also comprise the step adding chain-transfer agent, the add-on of chain-transfer agent is 0.01 ~ 500ppm of the water yield; Optimum, described chain-transfer agent is methyl alcohol or ethanol.
7. method as claimed in claim 2, it is characterized in that, described cyclic fluorinated monomer is perfluor-2,2-dimethyl-1,3-dioxole (PDD) or perfluor-2-methylene radical-4-methyl isophthalic acid, 3-dioxolane (PMD).
8. the method for claim 1, is characterized in that, described initiator amount is 0.1 ~ 500ppm of water weight; Initiator is selected from water-soluble or oil-soluble initiator; Preferred further, described initiator is selected from ammonium persulphate, Potassium Persulphate, t-butylcumylperoxide, benzoyl peroxide, Diisopropyl azodicarboxylate, potassium permanganate, succinic acid peroxide, the redox system of Potassium Persulphate and S-WAT, the redox system of Potassium Persulphate, sodium pyrosulfate and ferrous sulfate, or, the redox system of Potassium Persulphate, sodium pyrosulfate and Silver Nitrate.
9. the method for claim 1, is characterized in that, described emulsifying agent add-on is 0.05 ~ 1.5% of water weight.
10. the method for claim 1, is characterized in that, enrichment step also comprises the step adding dispersion stabilizer, and dispersion stabilizer is selected from nonionogenic tenside; More excellent, dispersion stabilizer is selected from poly-alkoxyl group ether or polyoxyethylene groups alkyl phenyl ether.
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| CN107406529A (en) * | 2015-03-16 | 2017-11-28 | 阿科玛股份有限公司 | modified fluoropolymer |
| CN110467695A (en) * | 2018-05-10 | 2019-11-19 | 中昊晨光化工研究院有限公司 | A kind of ethylene-tetrafluoroethylene copolymer and preparation method thereof |
| CN111234269A (en) * | 2020-03-18 | 2020-06-05 | 山东东岳高分子材料有限公司 | Preparation method of filled polytetrafluoroethylene dispersion resin |
| CN116144008A (en) * | 2021-11-23 | 2023-05-23 | 中昊晨光化工研究院有限公司 | Stabilizer and application thereof in preparation of fluorine-containing polymer |
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| CN110467695A (en) * | 2018-05-10 | 2019-11-19 | 中昊晨光化工研究院有限公司 | A kind of ethylene-tetrafluoroethylene copolymer and preparation method thereof |
| CN110467695B (en) * | 2018-05-10 | 2020-11-03 | 中昊晨光化工研究院有限公司 | Ethylene-tetrafluoroethylene copolymer and preparation method thereof |
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| CN116144008A (en) * | 2021-11-23 | 2023-05-23 | 中昊晨光化工研究院有限公司 | Stabilizer and application thereof in preparation of fluorine-containing polymer |
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