CN101186669A - Method for preparing microemulsion of fluorinated ethylene propylene powder - Google Patents
Method for preparing microemulsion of fluorinated ethylene propylene powder Download PDFInfo
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- CN101186669A CN101186669A CNA2007101142902A CN200710114290A CN101186669A CN 101186669 A CN101186669 A CN 101186669A CN A2007101142902 A CNA2007101142902 A CN A2007101142902A CN 200710114290 A CN200710114290 A CN 200710114290A CN 101186669 A CN101186669 A CN 101186669A
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- perfluoroethylene
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Abstract
The invention discloses a microemulsion polymerization method of perfluoroethylene and hexafluoropropene copolymer, which uses monomer medium liquefied hexafluoropropene as organic phase, adds monomer medium liquefied hexafluoropropene, emulsifier and co-emulsifier into water, to form O/W type microemulsion, feeds perfluoroethylene and hexafluoropropylene initial mixture gas and complement mixture gas, uses oil-soluble free radical initiator to initialize reaction, after the reaction, heats to separate and recover liquefied hexafluoropropene, discharges water, heats obtained polymer powder, to remove non-decomposed initiator, decomposition product, and residual water and foreign materials. The product powder of the invention has uniform and small size, non block. And the invention uses liquefied hexafluoropropene as organic phase to avoid organic solvent pollution on product and environment.
Description
Technical field
The present invention relates to the rare preparation method of tetrafluoroethylene and hexafluoropropylene copolymer perfluoroethylene third, particularly the microemulsion preparation method of perfluoroethylene third rare powder.
Background technology
Perfluoroethylene-propylene (FEP) polymkeric substance has outstanding resistant of high or low temperature, chemical resistant properties, electrical property and non-stick property, weathering resistance etc., and wherein the most outstanding is electrical insulation capability.Excellent electrical insulating property and workability energy make FEP application as insulating material in electric wire, cable become topmost purposes.Another purposes of FEP is that pipe fitting, container, heat exchanger and Laboratory Instruments are manufactured in processing.The application of its non-stick property mainly is conveyer belt, the roller lid of mechanical industry.Make film and can be used on the solar collector, because of it has light weight, good weatherability and high sun power transfer rate.FEP can make the goods of various forms with the working method of general thermoplastics as extrusion molding, molding, spray process method.
Perfluoroethylene-propylene (FEP) is at first succeeded in developing in nineteen forty-six by the SAUER of U.S. DuPont company, prepares machinable FEP film in nearly 10 hours in 25～65MPa, 55～64 ℃ of following reactions.Through various countries scientist's effort, nowadays it can be by mass polymerization, solution polymerization, suspension polymerization and emulsion polymerization prepared on this basis.Because the whole bag of tricks exists different advantages and shortcoming, thereby be not that above-mentioned all polymerization techniques all are fit to suitability for industrialized production.Begin so far research through six the seventies, now industrialized polymerization process mainly contains three kinds: letex polymerization, suspension polymerization and supercritical polymerization.
The use of water soluble starter can produce a large amount of thermally labile end groups.In the fusion last handling process, the carboxylic acid terminal group of polymkeric substance can be decomposed, but can cause the finished product that unacceptable bubble and relatively poor appearance color are arranged.The hydrofluoric acid of Sheng Chenging may cause the corrosion of equipment simultaneously, the resultant metal ionic soil.At this moment except that relatively poor outward appearance, fluoropolymer products also has the very poor resistance to cracking energy and the wash-out power of fluorion.
Can find out that from document extensive work concentrates on and obtains and develop the method for stablizing the efficient economy of terminal group in this polymer process of melt-processed.The FEP that two approach production thermostabilitys are arranged.The first reduces the number of unstable end group in polymerization process.This can reduce the initiator add-on by using the non-aqueous solution medium, selects alternative chain-transfer agent, selects alternative polymerization starter.
US Patent No 3528954 with tetrafluoroethylene with comprise the fluorinated-olefin monomer of HFP, is made initiator with the perfluor superoxide, fluorine-containing organic solvent and in carry out polymerization, preferably 1,1,2-three fluoro-1,2,2-Halothane (freon-113).But this organic solvent can destroy atmospheric ozone layer.
European patent No4/21696 contains fluorous solvent such as CF with tetrafluoroethylene and the fluorinated-olefin monomer that comprises HFP in ozone safety
3(CF
2)
nCH
2CH
3And/or CF
3(CH
2)
nCarry out among the H.The deficiency of this technology is to separate to contain complexity of fluorous solvent, and the easy conglomeration of multipolymer.
Russ P No2109761, TFE and HFP copolymerization are to carry out in the solvent of monomer medium liquefaction HFP or atmospheric ozone safety.Heated polymerizable thing powder is removed remaining initiator.The multipolymer that obtains has mechanical and physical performance and higher thermostability preferably.This process time is long, and the copolymer powder size distribution of acquisition is inhomogeneous, contains the larger particles caking.
CN 1483747A improves the technology of Russ P No2109761, in material force feed that reaction is obtained or the finishing apparatus of transferring to sealing, monomer is removed by progressively heating up to separate with solvent, can be shortened preparation time and improve quality product.
The definition of conventional emulsion be the droplet diameter in the 1-10 mu m range, opaque non-thermodynamic stable system.Different with traditional emulsion, microemulsion one speech is proposed in nineteen forty-three by Hear and Schalmer the earliest.Stable, transparent or semitransparent colloidal dispersion system on the isotropy that microemulsion is made up of oil, water, emulsifying agent and assistant for emulsifying agent, the thermodynamics, its dispersed phase size is a nano level, in the 10-100nm scope.Wherein cosurfactant is a polar organic matter, generally adopts alcohols.In microemulsion system, it is to keep by one deck laminated film of emulsifying agent and assistant for emulsifying agent formation and interfacial layer that it is stable that microballon drips.
Although microemulsion is familiar with by people already,, just begin it is carried out more extensively and research more in depth up to the initial stage eighties.Since reported first such as stoffer in 1980 were polymerisation medium with the microemulsion, micro-emulsion polymerization had caused people's great attention as an important branch of letex polymerization.To this, domestic and international many scholars have carried out extensively and deep research.Barton, Dunn, Candan, Xu Xiangling etc., Jia Shijun etc. summarize research of microemulsion polymerization from different sides and comment.
Research of microemulsion polymerization relates generally to the monomer homopolymerization, and less to monomer copolymerization research.With regard to the micro-emulsion polymerization system, monomer mainly contains vinylbenzene, methyl methacrylate, butyl acrylate, acrylamide and sodium acrylate etc., and rare especially for the research of fluorine analog copolymer, only abroad reports to some extent.Research of microemulsion polymerization also is in the exploratory stage at present, also have a suitable segment distance from large-scale industrial application, but its prospect is very wide, for the every performance that improves polymkeric substance crucial realistic meaning is arranged.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of microemulsion preparation method of perfluoroethylene third rare powder.
Summary of the invention
Polymer micro-emulsion has its original characteristics, and microemulsion is the stabilising system on the thermodynamics, can spontaneously form; Microemulsion bead particle diameter is transparent or semitransparent or little blueness less than 100nm, and the uniform particle diameter that obtains is good and particle diameter is less.Utilize O/W type micro-emulsion polymerization technology, and adopt liquefied hexafluoropropene to prepare the product that perfluoroethylene third rare powder can obtain good quality as organic solvent.
Detailed Description Of The Invention
The microemulsion preparation method of perfluoroethylene third rare powder of the present invention adopts tetrafluoroethylene and R 1216 monomer polymerization reactions, it is characterized in that: add the liquid perfluorinated hydrocarbon of organic phase, emulsifying agent and co-emulsifier in water, form O/W type microemulsion; Wherein the liquid perfluorinated hydrocarbon of organic phase is a monomer medium liquefied hexafluoropropene; Use in the polymerization process to add the mixed gaseous monomer in advance, and add the mixed gaseous monomer methods continuously and under the oil soluble radical initiator causes, carry out tetrafluoroethylene and the monomeric polymerization of R 1216.
Used emulsifying agent can be anionic, and cationic or non-ionic type etc. has R
fThe EX structure, R
fFor containing the fluorinated alkyl of 4-16 carbon atom, E is the alkylidene group that contains 0-4 carbon atom, and X is carboxylate salt, sulfonate or ammonium salt.The carboxylate salt that preferably has fluorocarbon chain or fluorine polyester chain perhaps has the sulfonate of fluorocarbon chain or fluorine polyester chain, specifically is selected from ammonium perfluorocaprylate, or the perfluoro-pelargonic acid ammonium.In order to reach emulsifying effectiveness preferably, ionic and nonionic emulsifier can be united use simultaneously.
Used co-emulsifier is Fatty Alcohol(C12-C14 and C12-C18) emulsifying agent or amine emulsifying agent.Preferably, co-emulsifier is cetyl alcohol, polyethylene hydramine, Pentyl alcohol, lauryl amine, coco amine or stearylamine.
Used oil dissolubility radical initiator is the peroxide initiator, preferred diisopropyl peroxydicarbonate, tert-butyl hydroperoxide butyric ester, two (perfluor butyryl radicals) superoxide, perfluoro butyl superoxide or perfluoro propyl superoxide.More preferably two (perfluor butyryl radicals) superoxide, perfluoro butyl superoxide or perfluoro propyl superoxide.
Use in the polymerization process to add the mixed gaseous monomer in advance, and add the mixed gaseous monomer methods continuously and carry out tetrafluoroethylene and the monomeric polymerization of R 1216.Wherein, adding the shared ratio of tetrafluoroethylene in the mixed gaseous monomer (TFE) in advance is 5-30wt%, and adding the shared ratio of tetrafluoroethylene in the mixed gaseous monomer (TFE) is 70-98wt%.Wherein, add mixed gaseous monomer 600g in advance, the shared ratio of tetrafluoroethylene (TFE) is 5～30wt%; Add the mixed gaseous monomer, the shared ratio of tetrafluoroethylene (TFE) is 70～98wt%; The add-on of emulsifying agent and co-emulsifier is 0.1～20% of a monomer total mass; The add-on of oil soluble radical initiator is 0.01～0.05% of a monomer total mass.
The microemulsion preparation method of above-mentioned perfluoroethylene third rare powder, concrete steps are as follows:
In water, add emulsifying agent and co-emulsifier, polymeric kettle is cooled to-15～-18 ℃, feed R 1216 gas, make R 1216 liquefaction, form O/W type microemulsion.Feed tetrafluoroethylene and R 1216 monomer initial mixing gaseous monomer and add the mixed gaseous monomer.Squeeze into oil soluble radical initiator initiated polymerization.Polymerization temperature is 25-45 ℃ under the agitation condition, and pressure is 1.1-1.5MPa.Reaction finishes the back by the intensification separated product, at first is warmed up to 45-65 ℃, with the liquefied hexafluoropropene Separation and Recovery.Then water is emitted after finding time, the powder that obtains is carried out 120-200 ℃ of heating for some time under the vacuum state in another encloses container, remove undecomposed initiator and resolvent thereof and residual moisture, impurity, obtain perfluoroethylene propylene polymers powder.
Less with the polymeric powder particles median size that this polymerization process obtains, and particle diameter is even.Use monomer medium liquefied hexafluoropropene as oil phase, avoided the pollution of the use of organic solvent, and be easy to reclaim for product and environment.The product performance that obtain are good.
The FEP polymer powder that the inventive method makes has outstanding resistant of high or low temperature, chemical resistant properties, electrical property and non-stick property, weathering resistance etc., and wherein the most outstanding is electrical insulation capability.Excellent electrical insulating property and workability energy make FEP application as insulating material in electric wire, cable become topmost purposes.Another purposes of FEP is that pipe fitting, container, heat exchanger and Laboratory Instruments are manufactured in processing.The application of its non-stick property mainly is conveyer belt, the roller lid of mechanical industry.Make film and can be used on the solar collector, because of it has light weight, good weatherability and high sun power transfer rate.FEP can make the goods of various forms with the working method of general thermoplastics as extrusion molding, molding, spray process method.The polymer powder that obtains with the inventive method is moldable to be processed into various products.The polymer powder that obtains with the inventive method is moldable to be processed into various products.
Embodiment
Embodiment 1
In 5 liters of reactors, adding the 2500g deionized water, 60g ammonium perfluorocaprylate and Pentyl alcohol 20g vacuumize and are cooled to-18 ℃, add the 200g R 1216 then in reactor, feed the 600g initial monomeric mixture, wherein the mass ratio of tetrafluoroethylene and R 1216 is 15: 85.Be heated to 48 ℃ under agitation condition, squeeze into 3g afterwards and be dissolved among the R113, concentration is two (perfluor butyryl radicals) superoxide of 15%.At this moment, reactor pressure is 1.5Mpa.The continuation feeding is added monomer mixture and is kept this pressure, and the mass ratio of tetrafluoroethylene and R 1216 is 80: 20.The add-on of oil soluble radical initiator is 0.04% of a monomer total mass.Copolymerization proceeds to be added till the mix monomer 800g.Under agitation condition, be heated to 58 ℃, with unreacted MONOMER RECOVERY.Pressure 0.1Mpa after 1 hour.Find time, use nitrogen replacement.Material is emitted, with filter bag powder is received, water is released.Powder is positioned over another sealed vessel, vacuumizes, 190 ℃ were heated 4 hours, and removed residual initiator and resolvent thereof, monomer residue and impurity etc.Obtain not have the multipolymer white powder of caking.
Embodiment 2
In 5 liters of reactors, adding the 2500g deionized water, 60g ammonium perfluorocaprylate and cetyl alcohol 20g vacuumize and are cooled to-18 ℃, add the 200g R 1216 then in reactor, feed the 600g initial monomeric mixture, wherein the mass ratio of tetrafluoroethylene and R 1216 is 15: 85.Be heated to 48 ℃ under agitation condition, squeeze into 4g afterwards and be dissolved among the R113, concentration is 15% perfluoro butyl superoxide.At this moment, reactor pressure is 1.5Mpa.The continuation feeding is added monomer mixture and is kept this pressure, and the mass ratio of tetrafluoroethylene and R 1216 is 80: 20.The add-on of oil soluble radical initiator is 0.03% of a monomer total mass.Copolymerization proceeds to be added till the mix monomer 800g.Under agitation condition, be heated to 58 ℃, with unreacted MONOMER RECOVERY.Pressure 0.1Mpa after 1 hour.Find time, use nitrogen replacement.Material is emitted, with filter bag powder is received, water is released.Powder is positioned over another sealed vessel, vacuumizes, 190 ℃ were heated 4 hours, and removed residual initiator and resolvent thereof, monomer residue and impurity etc.Obtain not have the multipolymer white powder of caking.
Embodiment 3
In 5 liters of reactors, adding the 2500g deionized water, 60g ammonium perfluorocaprylate and Pentyl alcohol 20g vacuumize and are cooled to-18 ℃, add the 200g R 1216 then in reactor, feed the 600g initial monomeric mixture, wherein the mass ratio of tetrafluoroethylene and R 1216 is 15: 85.Be heated to 48 ℃ under agitation condition, squeeze into 3g afterwards and be dissolved among the R113, concentration is two (perfluor butyryl radicals) superoxide of 15%.At this moment, reactor pressure is 1.5Mpa.The continuation feeding is added monomer mixture and is kept this pressure, and the mass ratio of tetrafluoroethylene and R 1216 is 80: 20.The add-on of oil soluble radical initiator is 0.02% of a monomer total mass.Copolymerization proceeds to be added till the mix monomer 800g.Under agitation condition, be heated to 58 ℃, with unreacted MONOMER RECOVERY.Pressure 0.1Mpa after 1 hour.Find time, use nitrogen replacement.Material is emitted, with filter bag powder is received, water is released.Powder is positioned over another sealed vessel, vacuumizes, 185 ℃ were heated 4 hours, and removed residual initiator and resolvent thereof, monomer residue and impurity etc.Obtain not have the multipolymer white powder of caking.
Embodiment 4
In 5 liters of reactors, adding the 2500g deionized water, 60g ammonium perfluorocaprylate and cetyl alcohol 20g vacuumize and are cooled to-18 ℃, add the 200g R 1216 then in reactor, feed the 600g initial monomeric mixture, wherein the mass ratio of tetrafluoroethylene and R 1216 is 15: 85.Be heated to 50 ℃ under agitation condition, squeeze into 3g afterwards and be dissolved among the R113, concentration is two (perfluor butyryl radicals) superoxide of 15%.At this moment, reactor pressure is 1.5Mpa.The continuation feeding is added monomer mixture and is kept this pressure, and the mass ratio of tetrafluoroethylene and R 1216 is 80: 20.The add-on of oil soluble radical initiator is 0.05% of a monomer total mass.Copolymerization proceeds to be added till the mix monomer 800g.Under agitation condition, be heated to 58 ℃, with unreacted MONOMER RECOVERY.Pressure 0.1Mpa after 1 hour.Find time, use nitrogen replacement.Material is emitted, with filter bag powder is received, water is released.Powder is positioned over another sealed vessel, vacuumizes, 185 ℃ were heated 4 hours, and removed residual initiator and resolvent thereof, monomer residue and impurity etc.Obtain not have the multipolymer white powder of caking.
Embodiment 5
In 5 liters of reactors, adding the 2500g deionized water, 60g ammonium perfluorocaprylate and Pentyl alcohol 20g vacuumize and are cooled to-18 ℃, add the 200g R 1216 then in reactor, feed the 600g initial monomeric mixture, wherein the mass ratio of tetrafluoroethylene and R 1216 is 17: 83.Be heated to 48 ℃ under agitation condition, squeeze into 3g afterwards and be dissolved among the R113, concentration is two (perfluor butyryl radicals) superoxide of 15%.At this moment, reactor pressure is 1.5Mpa.The continuation feeding is added monomer mixture and is kept this pressure, and the mass ratio of tetrafluoroethylene and R 1216 is 82: 28.The add-on of oil soluble radical initiator is 0.01% of a monomer total mass.Copolymerization proceeds to be added till the mix monomer 800g.Under agitation condition, be heated to 55 ℃, with unreacted MONOMER RECOVERY.Pressure 0.1Mpa after 1 hour.Find time, use nitrogen replacement.Material is emitted, with filter bag powder is received, water is released.Powder is positioned over another sealed vessel, vacuumizes, 180 ℃ were heated 4 hours, and removed residual initiator and resolvent thereof, monomer residue and impurity etc.Obtain not have the multipolymer white powder of caking.
Claims (10)
1. the microemulsion preparation method of perfluoroethylene third rare powder adopts tetrafluoroethylene and R 1216 monomer polymerization reactions, it is characterized in that: add the liquid perfluorinated hydrocarbon of organic phase, emulsifying agent and co-emulsifier in water, form O/W type microemulsion; Wherein the liquid perfluorinated hydrocarbon of organic phase is a monomer medium liquefied hexafluoropropene; Use in the polymerization process to add the mixed gaseous monomer in advance, and add the mixed gaseous monomer methods continuously and under the oil soluble radical initiator causes, carry out tetrafluoroethylene and the monomeric polymerization of R 1216.
2. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1 is characterized in that used emulsifying agent has R
fThe EX structure, R
fFor containing the fluorinated alkyl of 4-16 carbon atom, E is the alkylidene group that contains 0-4 carbon atom, and X is carboxylate salt, sulfonate or ammonium salt.
3. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 2, it is characterized in that used emulsifying agent is the carboxylate salt of fluorocarbon chain or fluorine polyester chain, perhaps have the sulfonate of fluorocarbon chain or fluorine polyester chain, specifically be selected from ammonium perfluorocaprylate, or the perfluoro-pelargonic acid ammonium.
4. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1 is characterized in that used co-emulsifier is Fatty Alcohol(C12-C14 and C12-C18) emulsifying agent or amine emulsifying agent; Preferred co-emulsifier is cetyl alcohol, polyethylene hydramine, Pentyl alcohol, lauryl amine, coco amine or stearylamine.
5. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1; it is characterized in that used oil dissolubility radical initiator is the peroxide initiator, preferred diisopropyl peroxydicarbonate, tert-butyl hydroperoxide butyric ester, two (perfluor butyryl radicals) superoxide, perfluoro butyl superoxide or perfluoro propyl superoxide.
6. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 5 is characterized in that used oil dissolubility radical initiator is two (perfluor butyryl radicals) superoxide, perfluoro butyl superoxide or perfluoro propyl superoxide.
7. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1, it is characterized in that using in the polymerization process adding the shared ratio of tetrafluoroethylene in the mixed gaseous monomer (TFE) in advance and being 5-30wt%, adding the shared ratio of tetrafluoroethylene in the mixed gaseous monomer (TFE) is 70-98wt%.
8. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1, the dosage that it is characterized in that emulsifying agent and co-emulsifier is 0.1～20% of a total monomer weight.
9. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1, the dosage that it is characterized in that the oil soluble radical initiator is 0.01～0.05% of a total monomer weight.
10. the microemulsion preparation method of perfluoroethylene third rare powder as claimed in claim 1, it is characterized in that concrete steps are as follows: in water, add emulsifying agent and co-emulsifier, polymeric kettle is cooled to-15～-18 ℃, feed R 1216 gas, make R 1216 liquefaction, form O/W type microemulsion.Feed tetrafluoroethylene and R 1216 monomer initial mixing gaseous monomer and add the mixed gaseous monomer.Squeeze into oil soluble radical initiator initiated polymerization.Polymerization temperature is 25-45 ℃ under the agitation condition, and pressure is 1.1-1.5MPa.Reaction finishes the back by the intensification separated product, at first is warmed up to 45-65 ℃, with the liquefied hexafluoropropene Separation and Recovery.Then water is emitted after finding time, the powder that obtains is carried out 120-200 ℃ of heating for some time under the vacuum state in another encloses container, remove undecomposed initiator and resolvent thereof and residual moisture, impurity, obtain perfluoroethylene propylene polymers powder.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745338A (en) * | 2008-12-12 | 2010-06-23 | 山东东岳神舟新材料有限公司 | Method for preparing fluorine-containing polymer without containing perfluorocaprylic acid |
| CN102070740A (en) * | 2010-11-16 | 2011-05-25 | 巨化集团公司 | Preparation method of fluorine-containing microemulsion |
| CN101648122B (en) * | 2009-09-03 | 2012-05-02 | 中昊晨光化工研究院 | Preparation method for fluorine-contained emulsifier |
| CN102443091A (en) * | 2011-10-25 | 2012-05-09 | 中昊晨光化工研究院 | Condensation washing method for fluorinated ethylene-propylene resin |
| WO2012082707A1 (en) * | 2010-12-17 | 2012-06-21 | 3M Innovative Properties Company | Microemulsions and fluoropolymers made using microemulsions |
| CN102675519A (en) * | 2012-06-11 | 2012-09-19 | 江苏梅兰化工有限公司 | Method for preparing polyperfluorinated ethylene propylene from perfluorodiacyl peroxide initiator |
| CN103554318A (en) * | 2013-10-21 | 2014-02-05 | 应悦 | Method and device for preparing fluorine-containing polymer under micro-emulsion form |
| CN109796705A (en) * | 2018-12-20 | 2019-05-24 | 陕西省石油化工研究设计院 | A kind of low friction FEP composition and preparation method thereof |
| CN112126000A (en) * | 2020-09-30 | 2020-12-25 | 宁波横河模具股份有限公司 | Preparation method of high-sealing-performance sealing strip for vacuum sealing valve |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101745338A (en) * | 2008-12-12 | 2010-06-23 | 山东东岳神舟新材料有限公司 | Method for preparing fluorine-containing polymer without containing perfluorocaprylic acid |
| CN101745338B (en) * | 2008-12-12 | 2015-03-18 | 山东华夏神舟新材料有限公司 | Method for preparing fluorine-containing polymer without containing perfluorocaprylic acid |
| CN101648122B (en) * | 2009-09-03 | 2012-05-02 | 中昊晨光化工研究院 | Preparation method for fluorine-contained emulsifier |
| CN102070740B (en) * | 2010-11-16 | 2012-10-03 | 巨化集团公司 | Preparation method of fluorine-containing microemulsion |
| CN102070740A (en) * | 2010-11-16 | 2011-05-25 | 巨化集团公司 | Preparation method of fluorine-containing microemulsion |
| WO2012082707A1 (en) * | 2010-12-17 | 2012-06-21 | 3M Innovative Properties Company | Microemulsions and fluoropolymers made using microemulsions |
| US9212279B2 (en) | 2010-12-17 | 2015-12-15 | 3M Innovative Properties Company | Microemulsions and fluoropolymers made using microemulsions |
| CN102443091A (en) * | 2011-10-25 | 2012-05-09 | 中昊晨光化工研究院 | Condensation washing method for fluorinated ethylene-propylene resin |
| CN102443091B (en) * | 2011-10-25 | 2013-07-24 | 中昊晨光化工研究院 | Condensation washing method for fluorinated ethylene-propylene resin |
| CN102675519A (en) * | 2012-06-11 | 2012-09-19 | 江苏梅兰化工有限公司 | Method for preparing polyperfluorinated ethylene propylene from perfluorodiacyl peroxide initiator |
| CN103554318A (en) * | 2013-10-21 | 2014-02-05 | 应悦 | Method and device for preparing fluorine-containing polymer under micro-emulsion form |
| CN103554318B (en) * | 2013-10-21 | 2017-04-19 | 衢州市鼎盛化工科技有限公司 | Method and device for preparing fluorine-containing polymer under micro-emulsion form |
| CN109796705A (en) * | 2018-12-20 | 2019-05-24 | 陕西省石油化工研究设计院 | A kind of low friction FEP composition and preparation method thereof |
| CN112126000A (en) * | 2020-09-30 | 2020-12-25 | 宁波横河模具股份有限公司 | Preparation method of high-sealing-performance sealing strip for vacuum sealing valve |
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