WO2010113950A1 - ポリテトラフルオロエチレン及びその製造方法 - Google Patents
ポリテトラフルオロエチレン及びその製造方法 Download PDFInfo
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- WO2010113950A1 WO2010113950A1 PCT/JP2010/055708 JP2010055708W WO2010113950A1 WO 2010113950 A1 WO2010113950 A1 WO 2010113950A1 JP 2010055708 W JP2010055708 W JP 2010055708W WO 2010113950 A1 WO2010113950 A1 WO 2010113950A1
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- polytetrafluoroethylene
- fluorine
- ocf
- containing surfactant
- polymerization
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/26—Tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/26—Tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to polytetrafluoroethylene and a method for producing the same.
- the following methods are known as methods for producing polytetrafluoroethylene suitable for stretching.
- Patent Document 1 discloses non-melt secondary processable polytetrafluoroethylene by using potassium permanganate / oxalic acid as a polymerization initiator and polymerizing tetrafluoroethylene in the presence of ammonium perfluorooctanoate [PFOA]. It is described to obtain a resin.
- PFOA ammonium perfluorooctanoate
- Patent Document 2 describes that polytetrafluoroethylene is obtained by polymerizing tetrafluoroethylene in the presence of PFOA using a combination of potassium bromate and ammonium sulfite as a polymerization initiator.
- Patent Document 3 describes that polytetrafluoroethylene is obtained by polymerizing tetrafluoroethylene in the presence of CF 3 CF 2 OCF 2 CF 2 OCF 2 COONH 4 using disuccinic acid peroxide as a polymerization initiator. Has been.
- Patent Document 4 discloses a perfluorocarboxylic acid or perfluorocarboxylic acid having 5 to 6 carbon atoms bonded with fluorine atoms and a total number of carbon atoms and oxygen atoms constituting the main chain of 9 to 12. It is described that emulsion polymerization is carried out in an aqueous medium containing a salt and a radical scavenger.
- JP 2000-143727 A Patent No. 4452354
- Japanese Patent Laid-Open No. 2002-201217 Japanese Patent Laid-Open No. 2002-201217
- International Publication No. 2007/046345 Pamphlet International Publication No. 2009/001894 Pamphlet
- An object of the present invention is to provide polytetrafluoroethylene suitable for forming a porous polytetrafluoroethylene film by using a fluorine-containing surfactant having high water solubility and high volatility.
- the present invention has non-melt secondary workability, the standard specific gravity is 2.160 or less, the average primary particle diameter is 150 nm or more, the stress relaxation time is 500 seconds or more, and the Log POW is 3.
- Polytetrafluoroethylene obtained by emulsion polymerization of tetrafluoroethylene in the presence of 4 or less fluorine-containing surfactant and having a breaking strength of 29.7 N or more.
- the polytetrafluoroethylene of the present invention preferably has a breaking strength of 32.0 to 49.0 N.
- the fluorine-containing surfactant has a general formula: CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal atom), and a general formula: CF 3 CF 2 OCF 2 CF 2 OCF 2 COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal atom), It is preferably at least one fluorine-containing surfactant selected from the group consisting of
- the porous body obtained from the polytetrafluoroethylene of the present invention has a high breaking strength. Since the production method of the present invention has the above-described configuration, polytetrafluoroethylene particularly suitable for producing a porous body can be produced using a fluorine-containing surfactant having high water solubility and high volatility.
- Polytetrafluoroethylene of the present invention has non-melting secondary processability, a standard specific gravity of 2.160 or less, an average primary particle diameter of 150 nm or more, and a stress relaxation time. It is obtained by emulsion polymerization of tetrafluoroethylene in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less for 500 seconds or more, and has a breaking strength of 29.7 N or more.
- a compound with a large Log POW is concerned about the burden on the environment, and considering this, it is preferable to use a compound with a Log POW of less than 3.5. So far, in the production of fluorine-containing polymers by emulsion polymerization, ammonium perfluorooctanoate [PFOA] has been mainly used as a surfactant. Since PFOA has a Log POW of 3.5, the Log POW is 3.4 or less. It is preferable to switch to the fluorine-containing surfactant.
- a fluorine-containing surfactant having a Log POW of 3.4 or less has a problem of poor emulsifying ability.
- the stability of the aqueous dispersion during polymerization is important. If a fluorine-containing surfactant that is actually inferior in emulsifying ability is used, sufficient breakage is achieved. Strength cannot be obtained.
- polytetrafluoroethylene having rather high breaking strength can be obtained by using a small amount of a fluorine-containing surfactant having a sufficiently low emulsifying ability and initiating polymerization with a redox initiator.
- a fluorine-containing surfactant having a sufficiently low emulsifying ability and initiating polymerization with a redox initiator.
- the polytetrafluoroethylene of the present invention is a novel polytetrafluoroethylene that exhibits a breaking strength that cannot be predicted as that obtained in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less.
- the present invention is polytetrafluoroethylene obtained by emulsion polymerization of tetrafluoroethylene in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less, it is environmentally friendly and also contains a fluorine-containing surfactant. Since it can be easily washed, production is also easy.
- the polytetrafluoroethylene of the present invention preferably has a breaking strength of 32.0 to 49.0 N.
- the polytetrafluoroethylene of the present invention is obtained in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less, and in the presence of a surfactant having a Log POW of 2.5 or more or 3.0 or more. It may be obtained.
- LogPOW is a partition coefficient between 1-octanol and water
- LogP [where P is an octanol in a octanol / water (1: 1) mixture containing a fluorine-containing surfactant in phase separation. Represents the fluorine-containing surfactant concentration / fluorine-containing surfactant concentration ratio in water].
- a fluorine-containing anionic surfactant is preferable.
- fluorine-containing surfactant having a Log POW of 3.4 or less a general formula: CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOX (Wherein X represents a hydrogen atom, NH 4 or an alkali metal atom), and a general formula: CF 3 CF 2 OCF 2 CF 2 OCF 2 COOX (In the formula, X represents a hydrogen atom, NH 4 or an alkali metal atom.) It is preferably at least one fluorine-containing surfactant selected from the group consisting of
- fluorine-containing surfactant having a Log POW of 3.4 or less examples include CF 3 OCF 2 CF 2 OCF 2 CF 2 COONH 4 , CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 COOX (In the formula, X represents a hydrogen atom, NH 4 or an alkali metal atom.) Etc. can also be mentioned.
- examples of the counter ion forming the salt include an alkali metal ion or NH 4+ , and examples of the alkali metal ion include Na + and K +. .
- fluorine-containing surfactant having a Log POW of 3.4 or less examples include CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COOH, CF 3 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 , CF 3 include CF 2 OCF 2 CF 2 OCF 2 COOH, CF 3 CF 2 OCF 2 CF 2 OCF 2 COONH 4, CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 COOH, CF 3 OCF 2 CF 2 CF 2 OCHFCF 2 COONH 4 or the like It is done.
- the polytetrafluoroethylene of the present invention is obtained by polymerizing tetrafluoroethylene in the presence of a fluorine-containing surfactant having a Log POW of 3.4 or less.
- the Log POW is 3 .4 or less polytetrafluoroethylene obtained by polymerizing tetrafluoroethylene in the presence of a fluorine-containing surfactant.
- the polytetrafluoroethylene of the present invention is obtained by emulsion polymerization in the absence of a fluorine-containing surfactant having a Log POW of more than 3.4.
- the polytetrafluoroethylene [TFE polymer] of the present invention may be a TFE homopolymer or a copolymer of TFE and a modified monomer, which is non-melt processable (hereinafter referred to as “modified”). It may be referred to as “PTFE”). Modified PTFE can be obtained by polymerizing TFE and a known modified monomer.
- the modifying monomer examples include fluorine-containing olefins such as hexafluoropropylene [HFP] and chlorotrifluoroethylene [CTFE]; fluoro having an alkyl group having 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms ( Alkyl vinyl ether); cyclic fluorinated monomers such as fluorodioxole; perfluoroalkylethylene; ⁇ -hydroperfluoroolefin and the like.
- the supply of the modified monomer may be added all at once before the start of polymerization, or may be added continuously or intermittently.
- the modified PTFE preferably has a modified monomer content in the range of 0.001 to 2 mol%, and more preferably in the range of 0.001 to 1 mol%.
- the polytetrafluoroethylene may have a core-shell structure.
- the polytetrafluoroethylene having a core-shell structure include a modified polytetrafluoroethylene having a high molecular weight polytetrafluoroethylene core and a lower molecular weight polytetrafluoroethylene or modified polytetrafluoroethylene shell in the particle. Fluoroethylene is mentioned. Examples of such modified polytetrafluoroethylene include polytetrafluoroethylene described in JP-T-2005-527652.
- the polytetrafluoroethylene of the present invention has a standard specific gravity [SSG] of 2.160 or less, preferably 2.157 or less.
- SSG standard specific gravity
- Polytetrafluoroethylene having an SSG of 2.160 or less has a stretch ratio of the extruded product exceeding 3000% and is suitable for stretch molding.
- the SSG is an SSG defined in ASTM D4895-89 as an index of molecular weight of polytetrafluoroethylene having no melt molding processability.
- the polytetrafluoroethylene of the present invention has an average primary particle size of 150 nm or more and preferably 180 nm or more.
- the average primary particle diameter of polytetrafluoroethylene is larger, when paste extrusion molding is performed using the powder, an increase in the paste extrusion pressure is suppressed, and the film forming property is also excellent.
- the upper limit is not particularly limited, but may be 500 nm.
- the polytetrafluoroethylene of the present invention preferably has an extrusion pressure of 9.8 to 24.5 MPa, more preferably 9.8 to 20.0 MPa, and preferably 9.8 to 19.0 MPa. Further preferred.
- the polytetrafluoroethylene of the present invention has a stress relaxation time of 500 seconds or longer, preferably 600 seconds or longer, and more preferably 700 seconds or longer.
- the polytetrafluoroethylene of the present invention has stretchability, fibrillation, and non-melt secondary workability.
- the polytetrafluoroethylene of the present invention may be in the form of particles or powder.
- the polytetrafluoroethylene of the present invention is particularly suitable as a material for molding a porous body.
- the first production method of the present invention comprises a step of charging a fluorine-containing surfactant having a Log POW of 3.4 or less, water, and tetrafluoroethylene into a polymerization tank, and a redox in the polymerization tank. Including a step of introducing an initiator to start emulsion polymerization of tetrafluoroethylene and a step of recovering polytetrafluoroethylene, and the total amount of the fluorosurfactant to be added relative to the final polytetrafluoroethylene yield 1000 to 6000 ppm.
- the polytetrafluoroethylene of the present invention can be produced by the first production method of the present invention.
- the first production method of the present invention is characterized in that a fluorine-containing surfactant having a Log POW of 3.4 or less is used, and that the amount used is extremely small, and that a redox initiator is used.
- the emulsifying capacity of the fluorine-containing surfactant is sufficiently low, and the amount of the fluorine-containing surfactant to be used is small so that the generation of a new polymerization field is suppressed particularly in the latter half of the polymerization reaction. It will have been done.
- the polymerization reaction proceeds in a limited polymerization field in a state where almost no radicals are supplied, so the production of low molecular weight polytetrafluoroethylene and oligomers is suppressed, and high breaking strength is achieved. It is speculated that the polytetrafluoroethylene shown may be obtained.
- the first production method of the present invention includes a step of charging a fluorine-containing surfactant having a Log POW of 3.4 or less, water, and tetrafluoroethylene into a polymerization tank, and adding a polymerization initiator to the polymerization tank to introduce tetrafluoro A step of starting emulsion polymerization of ethylene and a step of recovering polytetrafluoroethylene.
- fluorine-containing surfactant having a Log POW of 3.4 or less are as described above.
- the fluorine-containing surfactant is added so that the final polytetrafluoroethylene yield is 1000 to 6000 ppm.
- the whole amount of the fluorine-containing surfactant may be added before the polymerization is started, or may be additionally added during the polymerization reaction.
- the preferable lower limit of the amount of the fluorine-containing surfactant used is 2000 ppm, and the preferable upper limit is 5000 ppm.
- the upper limit of the input amount of the fluorine-containing surfactant is important.
- the breaking strength of polytetrafluoroethylene decreases.
- the second production method of polytetrafluoroethylene of the present invention comprises one or more fluorine-containing surfactants represented by the following general formulas (I) to (III). It includes a step of emulsion polymerization of at least tetrafluoroethylene by adding a redox initiator in the presence thereof.
- the fluorine-containing surfactant is a fluoroethercarboxylic acid represented by the general formulas (I) to (III), which has higher solubility in water than ammonium perfluorooctanoate [PFOA], and Since it is highly volatile, it can be easily removed from polytetrafluoroethylene.
- PFOA ammonium perfluorooctanoate
- fluorine-containing surfactant As said fluorine-containing surfactant, general formula (I): CF 3 — (CF 2 ) m —O— (CF (CF 3 ) CF 2 O) n —CF (CF 3 ) COOX (I) (Wherein m represents an integer of 0 to 4, n represents an integer of 0 to 2, X represents a hydrogen atom, NH 4 or an alkali metal atom), General formula (II): CF 3 — (CF 2 ) m —O— (CF (CF 3 ) CF 2 O) n —CHFCF 2 COOX (II), (In the formula, m represents an integer of 0 to 4, n represents an integer of 0 to 2, and X represents a hydrogen atom, NH 4 or an alkali metal atom.) Formula (III): CF 3 — (CF 2 ) m —O— (CF (CF 3 ) CF 2 O) n —CH 2 CF 2 CO
- M is preferably an integer of 0 to 2, and more preferably 0.
- N is preferably 0 or 1.
- X represents a monovalent hydrogen atom, NH 4 (ammonium group) or an alkali metal atom.
- alkali metal atom examples include Li, Na, and K.
- X is preferably NH 4 or an alkali metal atom from the viewpoint of water solubility, and NH 4 is more preferable because it can be easily removed by heat treatment.
- said X it is also preferable that it is a hydrogen atom.
- the surface activity in water is improved compared to the salt, and for example, the surface tension at the same molar concentration is lower with carboxylic acid, and as a result, more stable and smaller polymer particles are obtained when used for polymerization.
- the obtained polymer colloid has high stability, the generation of aggregates during polymerization is small, and polymerization can be carried out to a high concentration.
- polytetrafluoroethylene can be efficiently produced by using at least one of the above-mentioned fluoroethercarboxylic acids as a fluorine-containing surfactant.
- two or more of the above-mentioned fluoroethercarboxylic acids may be used in combination as the fluorine-containing surfactant, or a molding having volatility or polytetrafluoroethylene.
- other compounds having surface activity other than the above-mentioned fluoroethercarboxylic acid may be used in combination.
- the other compounds having surface activity those described above can be used.
- the fluoroethercarboxylic acid is preferably added in a total addition amount of 0.0001 to 10% by mass with respect to the aqueous medium.
- a more preferred lower limit is 0.001% by mass
- a more preferred upper limit is 2% by mass
- a still more preferred upper limit is 1% by mass. If the amount is too small, the dispersion force may be insufficient. If the amount is too large, an effect commensurate with the amount added may not be obtained, and the polymerization rate may be lowered or the reaction may be stopped.
- the amount of the compound added is appropriately determined depending on the molecular weight of the target polytetrafluoroethylene.
- an aqueous medium and the fluorine-containing surfactant are charged into a pressure-resistant reaction vessel equipped with a stirrer, and after deoxygenation, tetrafluoroethylene [TFE] is charged to a predetermined temperature, and a polymerization initiator is added. Start the reaction. Since the pressure decreases as the reaction proceeds, additional TFE is added continuously or intermittently so as to maintain the initial pressure. When a predetermined amount of TFE is supplied, the supply is stopped, the TFE in the reaction vessel is purged, the temperature is returned to room temperature, and the reaction is terminated.
- TFE tetrafluoroethylene
- the polytetrafluoroethylene obtained by the second production method of the present invention has excellent characteristics as follows.
- the SSG of polytetrafluoroethylene can be 2.160 or less.
- Polytetrafluoroethylene having an SSG of 2.160 or less has a stretch ratio of the extruded product exceeding 3000% and is suitable for stretch molding.
- the SSG is an SSG defined in ASTM D4895-89 as an index of molecular weight of polytetrafluoroethylene having no melt molding processability.
- the average primary particle diameter of polytetrafluoroethylene can be 0.180 micrometer or more.
- the average primary particle diameter of polytetrafluoroethylene is larger, when paste extrusion molding is performed using the powder, an increase in the paste extrusion pressure is suppressed, and the film forming property is also excellent.
- the extrusion pressure of polytetrafluoroethylene can be 9.8 to 24.5 MPa, more preferably 9.8 to 20.0 MPa, and still more preferably. Can be 9.8 to 19.0 MPa.
- Polytetrafluoroethylene obtained by the second production method of the present invention is particularly suitable as a molding material for a porous body.
- the breaking strength of the porous body can be 29 N or more.
- the stress relaxation time of the porous body can be set to 500 seconds or longer, and more preferably 600 seconds or longer.
- the second production method of the present invention when a fluorine-containing surfactant having a Log POW of 3.4 or less is used and a fluorine-containing surfactant having a Log POW of more than 3.4 is not used, a high breaking strength is obtained.
- the input amount of the fluorine-containing surfactant must be controlled according to the first production method of the present invention.
- polytetrafluoroethylene particularly suitable for production of a porous body By using a redox initiator as a polymerization initiator, polytetrafluoroethylene particularly suitable for production of a porous body can be obtained.
- the addition amount of the redox initiator is appropriately determined depending on the molecular weight of the target polytetrafluoroethylene and the reaction rate, and is preferably 0.1 to 200 ppm relative to the final polytetrafluoroethylene yield, More preferably, it is ⁇ 100 ppm.
- a combination of a persulfate or an organic peroxide and a reducing agent such as sodium sulfite, a bisulfite such as sodium hydrogen sulfite, a bromate, diimine, or oxalic acid is mentioned.
- Examples of the redox initiator include potassium permanganate / oxalic acid, ammonium persulfate / bisulfite / iron sulfate, manganese triacetate / oxalic acid, cerium ammonium nitrate / oxalic acid, bromate / bisulfite and the like. And potassium permanganate / oxalic acid is preferred.
- either an oxidizing agent or a reducing agent may be previously charged in a polymerization tank, and then the other may be added continuously or intermittently to initiate polymerization.
- potassium permanganate / oxalic acid it is preferable to add oxalic acid to the polymerization tank and continuously add potassium permanganate thereto.
- the polymerization is preferably performed in the presence of 25 to 200 ppm of dicarboxylic acid with respect to the aqueous medium in order to reduce the amount of coagulum generated during the polymerization. More preferably, it is carried out in the presence of ⁇ 200 ppm of dicarboxylic acid. If the dicarboxylic acid content is less than 25 ppm with respect to the aqueous medium, a sufficient effect may not be obtained. If the dicarboxylic acid content exceeds 200 ppm, a chain transfer reaction may occur and the resulting polymer may have a low molecular weight. .
- the dicarboxylic acid is preferably 150 ppm or less. The dicarboxylic acid may be added before the start of the polymerization reaction or may be added during the polymerization.
- dicarboxylic acid examples include those represented by the general formula: HOOCRCOOH (wherein R represents an alkylene group having 1 to 5 carbon atoms). Succinic acid, malonic acid, glutaric acid, adipic acid, Pimelic acid is more preferred, and succinic acid is even more preferred.
- the polymerization can be performed under a pressure of 0.05 to 5.0 MPa.
- a preferable pressure range is 1.5 to 3.0 MPa.
- the aqueous medium is a medium for performing polymerization and means a liquid containing water.
- the aqueous medium is not particularly limited as long as it contains only water or contains water, and water and, for example, a fluorine-free organic solvent such as alcohol, ether, and ketone, and / or a boiling point of 40. It may contain a fluorine-containing organic solvent having a temperature of 0 ° C. or lower.
- the polymerization can be carried out at a temperature of 10 to 100 ° C.
- a preferred temperature range is 50-90 ° C.
- a known stabilizer, chain transfer agent or the like may be further added depending on the purpose.
- the stabilizer examples include saturated hydrocarbons having 12 or more carbon atoms that are substantially inert to the reaction and become liquid under the reaction conditions, and paraffin wax is preferred.
- dispersion stabilizers other than saturated hydrocarbons include fluorinated oils, fluorinated solvents, and silicone oils. The stabilizer can be used in an amount of 2 to 10 parts by mass with respect to 100 parts by mass of the aqueous medium.
- chain transfer agent known ones can be used, for example, saturated hydrocarbons such as methane, ethane, propane and butane, halogenated hydrocarbons such as chloromethane, dichloromethane and difluoroethane, and alcohols such as methanol and ethanol. Hydrogen and the like can be mentioned, but those in a gaseous state at normal temperature and pressure are preferable.
- the amount of the chain transfer agent used is usually 1 to 1000 ppm, preferably 1 to 500 ppm, based on the total amount of TFE supplied.
- the radical concentration in the system can be adjusted by adding a radical scavenger such as hydroquinone or catechol or adding a peroxide decomposing agent such as ammonium sulfite during the polymerization.
- a radical scavenger such as hydroquinone or catechol
- a peroxide decomposing agent such as ammonium sulfite
- ammonium carbonate an ammonium phosphate, etc.
- ammonium phosphate etc.
- the method for producing polytetrafluoroethylene of the present invention may also include a step of adding a modifying monomer to the polymerization tank.
- the supply of the modified monomer may be added all at once before the start of polymerization, or may be added continuously or intermittently.
- the method for producing polytetrafluoroethylene according to the present invention also includes a step of polymerizing TFE in an aqueous medium in the presence of the fluorine-containing surfactant to obtain an aqueous emulsion (seed dispersion), and the aqueous It may include a step of polymerizing TFE (seed polymerization) in the presence of an emulsion (seed dispersion).
- an aqueous dispersion having a solid content concentration of 20 to 70% by mass can be obtained.
- the aqueous dispersion contains the fluorine-containing surfactant and polytetrafluoroethylene.
- the average primary particle diameter of polytetrafluoroethylene is 50 to 500 nm.
- the production method of the present invention comprises a step of recovering an aqueous polytetrafluoroethylene dispersion, Agglomerating the polytetrafluoroethylene in the aqueous polytetrafluoroethylene dispersion; Recovering the agglomerated polytetrafluoroethylene, Drying the recovered polytetrafluoroethylene at 100 to 250 ° C .; and Mixing polytetrafluoroethylene obtained by drying with an extrusion aid, extruding at an extrusion pressure of 9.8 to 24.5 MPa, and forming into a bead; Heating the obtained bead at 200 to 230 ° C. to remove the extrusion aid and obtaining a bead-shaped polytetrafluoroethylene; Of these, it is preferable to include at least one step.
- the breaking strength of the porous body obtained from the stretched bead increases as the extrusion pressure for forming into the bead increases. Even if the PTFE of the present invention is molded at an extrusion pressure of 20 MPa or less, the obtained stretch bead exhibits a breaking strength of 29.7 N or more.
- Fine powder can be produced by aggregating the polytetrafluoroethylene contained in the aqueous dispersion.
- the aqueous dispersion of polytetrafluoroethylene can be used for various applications as a fine powder through aggregation, washing and drying.
- the aqueous dispersion obtained by polymerization of polymer latex or the like is usually diluted with water to a polymer concentration of 10 to 20% by mass.
- the pH is adjusted to neutral or alkaline, and then the mixture is stirred more vigorously than the stirring during the reaction in a vessel equipped with a stirrer.
- the agglomeration may be carried out while adding a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid as a coagulant.
- a water-soluble organic compound such as methanol or acetone
- an inorganic salt such as potassium nitrate or ammonium carbonate
- an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid
- the agglomeration may be continuously performed using an in-line mixer or the like.
- pigments for coloring and various fillers for improving mechanical properties are added, so that pigments and fillers are mixed uniformly into pigmented or filled polytetrafluoro. Ethylene fine powder can be obtained.
- the wet powder obtained by agglomerating the polytetrafluoroethylene is usually dried by using means such as vacuum, high frequency, hot air, etc. while keeping the wet powder not flowing so much, preferably in a stationary state.
- the drying can be performed at a drying temperature of 10 to 250 ° C., preferably 100 to 220 ° C., more preferably 100 to 200 ° C.
- the porous body is formed by extruding and rolling powdered polytetrafluoroethylene, and then unfired or semi-fired and stretched in at least one direction (preferably roll-stretched in the rolling direction and then stretched in the width direction by a tenter. ), Can be manufactured.
- stretching conditions a speed of 5 to 1000% / second and a stretching ratio of 500% or more are preferably employed.
- polytetrafluoroethylene is easily fibrillated to form a polytetrafluoroethylene porous body (film) comprising nodules and fibers.
- the porosity of the polytetrafluoroethylene porous body (membrane) is not particularly limited, but is generally preferably in the range of 50 to 99%, more preferably in the range of 70 to 98%.
- the porous body can be used in various forms such as membranes, fibers, rods, tubes, etc., and can be suitably used as various filters such as chemical filters and air filters, and further used in textile products and medical fields. It is also useful as a product material.
- each physical property was measured by the following method.
- Polymer solid content concentration 1 g of polytetrafluoroethylene aqueous dispersion was dried in an air dryer at 150 ° C. for 30 minutes, and the ratio of the mass of the heating residue to the mass (1 g) of the aqueous dispersion was determined. The numerical value expressed as a percentage is defined as the polymer solid content concentration.
- Standard specific gravity [SSG] A sample is prepared according to ASTM D-4895-89, and the specific gravity of the obtained sample is measured by a water displacement method.
- Lubricant (trade name: IP1620 (registered trademark), manufactured by Idemitsu Petrochemical Co., Ltd.) so as to be 18.0% by mass based on the total mass of fine powder and lubricant to 100 g of fine powder And mix for 3 minutes in a glass bottle at room temperature. The glass bottle is then left at room temperature (25 ° C.) for at least 1 hour before extrusion to obtain a lubricated resin.
- the lubricated resin is paste-extruded through an orifice (diameter 2.4 mm, land length 5 mm, introduction angle 30 °) at a reduction ratio of 100: 1 at room temperature to obtain a uniform beading (extruded product).
- the extrusion speed that is, the ram speed is 20 inches / minute (51 cm / minute).
- the extrusion pressure is a value obtained by measuring the load when the extrusion load is in an equilibrium state in paste extrusion and dividing by the cross-sectional area of the cylinder used for paste extrusion.
- Stretch is an increase in length due to stretching, and is usually expressed in relation to the original length. In the production method, the stretch rate is 100% / second, and the total stretch is 2400%.
- a bead for stress relaxation time measurement is prepared with a clamp interval of 1.5 inches (3.8 cm), a stretch rate of 1000% / second, and a total stretch of 2400%. Both ends of the bead are connected to a fixture to form a taut 8 inch (20 cm) bead sample. Keep the oven at 390 ° C. and insert the fixture into the oven through the (covered) slit on the side of the oven. The time required from the time of insertion into the oven until the bead sample breaks is measured as the stress relaxation time.
- each fluorine-containing surfactant used in the examples is as follows.
- Example 1 In a 6 L polymerization tank, 3600 g of ultrapure water, 180 g of paraffin wax, 5.4 g of a surfactant (CF 3 —O—CF (CF 3 ) CF 2 O—CF (CF 3 ) COONH 4 ), and 0.108 g of succinic acid Then, 0.0252 g of oxalic acid was charged, deaerated by nitrogen purge, and heated to 70 ° C. After the temperature in the polymerization tank was stabilized, tetrafluoroethylene gas was introduced to a pressure of 2.7 MPa.
- a surfactant CF 3 —O—CF (CF 3 ) CF 2 O—CF (CF 3 ) COONH 4
- the obtained polytetrafluoroethylene aqueous dispersion was diluted to a solid content concentration of 15% by mass and vigorously stirred in the presence of nitric acid in a vessel equipped with a stirrer to solidify the polytetrafluoroethylene.
- the coagulated polytetrafluoroethylene was separated and dried at 210 ° C. for 18 hours to obtain a fine powder of polytetrafluoroethylene.
- Various physical properties of the obtained fine powder were measured. The results are shown in Table 1.
- Example 2 In a 6 L polymerization tank, 3600 g of ultrapure water, 180 g of paraffin wax, 2.2 g of a surfactant (CF 3 —O—CF (CF 3 ) CF 2 O—CF (CF 3 ) COONH 4 ), and 0.108 g of succinic acid Then, 0.0252 g of oxalic acid was charged, deaerated by nitrogen purge, and heated to 70 ° C. After the temperature in the polymerization tank was stabilized, tetrafluoroethylene gas was introduced to a pressure of 2.7 MPa.
- a surfactant CF 3 —O—CF (CF 3 ) CF 2 O—CF (CF 3 ) COONH 4
- the stirring and the TFE supply were stopped, the TFE in the polymerization tank was purged, and the gas phase was then replaced with nitrogen, whereby the polytetrafluoroethylene aqueous dispersion (solid content 30. 9% by mass) was obtained.
- the amount of the fluorine-containing surfactant used was 3290 ppm relative to the final polytetrafluoroethylene yield.
- the obtained polytetrafluoroethylene aqueous dispersion was diluted to a solid content concentration of 15%, and vigorously stirred in the presence of nitric acid in a vessel equipped with a stirrer to solidify the polytetrafluoroethylene.
- the coagulated polytetrafluoroethylene was separated and dried at 210 ° C. for 18 hours to obtain a fine powder of polytetrafluoroethylene.
- Various physical properties of the obtained fine powder were measured. The results are shown in Table 1.
- Example 3 A 6 L polymerization tank was charged with 3600 g of ultrapure water, 180 g of paraffin wax, 5.4 g of surfactant CF 3 OCF 2 CF 2 OCF 2 CF 2 COONH 4 , 0.108 g of succinic acid, and 0.0252 g of oxalic acid, and then purged with nitrogen Was deaerated, and the temperature was raised to 70 ° C. After the temperature in the polymerization tank was stabilized, tetrafluoroethylene gas was introduced to a pressure of 2.7 MPa.
- the obtained polytetrafluoroethylene aqueous dispersion was diluted to a solid content concentration of 15%, and vigorously stirred in the presence of nitric acid in a vessel equipped with a stirrer to solidify the polytetrafluoroethylene.
- the coagulated polytetrafluoroethylene was separated and dried at 210 ° C. for 18 hours to obtain a fine powder of polytetrafluoroethylene.
- Various physical properties of the obtained fine powder were measured. The results are shown in Table 1.
- Example 4 A 6 L polymerization tank is charged with 3600 g of ultrapure water, 180 g of paraffin wax, 5.4 g of surfactant CF 3 CF 2 OCF 2 CF 2 OCF 2 COONH 4 , 0.108 g of succinic acid, and 0.0252 g of oxalic acid, and then purged with nitrogen Was deaerated, and the temperature was raised to 70 ° C. After the temperature in the polymerization tank was stabilized, tetrafluoroethylene gas was introduced to a pressure of 2.7 MPa.
- the obtained polytetrafluoroethylene aqueous dispersion was diluted to a solid content concentration of 15%, and vigorously stirred in the presence of nitric acid in a vessel equipped with a stirrer to solidify the polytetrafluoroethylene.
- the coagulated polytetrafluoroethylene was separated and dried at 210 ° C. for 18 hours to obtain a fine powder of polytetrafluoroethylene.
- Various physical properties of the obtained fine powder were measured. The results are shown in Table 1.
- the production method of the present invention can be suitably used particularly as a method for producing a high molecular weight polytetrafluoroethylene.
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Abstract
Description
CF3OCF(CF3)CF2OCF(CF3)COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)、及び、一般式:
CF3CF2OCF2CF2OCF2COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)、
からなる群より選択される少なくとも1種の含フッ素界面活性剤であることが好ましい。
本発明のポリテトラフルオロエチレンは、非溶融二次加工性を有し、標準比重が2.160以下であり、平均一次粒子径が150nm以上であり、応力緩和時間が500秒以上であり、LogPOWが3.4以下の含フッ素界面活性剤の存在下にテトラフルオロエチレンを乳化重合して得られ、29.7N以上の破断強度を有することを特徴とする。
CF3OCF(CF3)CF2OCF(CF3)COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)、及び、一般式:
CF3CF2OCF2CF2OCF2COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)
からなる群より選択される少なくとも1種の含フッ素界面活性剤であることが好ましい。
CF3OCF2CF2CF2OCHFCF2COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)
等も挙げることができる。
本発明の第1の製造方法は、LogPOWが3.4以下の含フッ素界面活性剤、水、及び、テトラフルオロエチレンを重合槽に投入する工程、重合槽にレドックス開始剤を投入してテトラフルオロエチレンの乳化重合を開始する工程、及び、ポリテトラフルオロエチレンを回収する工程、を含み、上記含フッ素界面活性剤の合計投入量が最終ポリテトラフルオロエチレン収量に対して1000~6000ppmであることを特徴とする。
しかしながら、重合条件を厳密に制御すれば、極めて不安定な重合場が高い破断強度を示すポリテトラフルオロエチレンを与えることが見出された。
乳化能が低い含フッ素界面活性剤を少量使用し、かつ、レドックス重合開始剤を使用することで、何故、高い破断強度を示すポリテトラフルオロエチレンが得られるのかは必ずしも明りょうではないが、両者の相乗効果ではないかと考えられる。
第1に、含フッ素界面活性剤の乳化能が充分に低いこと、加えて使用する含フッ素界面活性剤の量が少量であることで、特に重合反応の後半において新規な重合場の発生が抑制されているのであろう。第2に、レドックス開始剤を使用することによって、重合反応の前半においてのみ、重合の開始に必要な充分な量のラジカルが供給され、重合反応の後半ではラジカルはほとんど発生しない。
そうすると、重合反応の後半には、ほとんどラジカルが供給されない状態で、しかも限られた重合場において重合反応が進行するため、低分子量のポリテトラフルオロエチレンやオリゴマーの生成が抑制され、高い破断強度を示すポリテトラフルオロエチレンが得られるのではないかと推測される。
本発明の第2のポリテトラフルオロエチレンの製造方法は、下記一般式(I)~(III)で表される1種又は2種以上の含フッ素界面活性剤の存在下に、レドックス開始剤を添加して、少なくともテトラフルオロエチレンを乳化重合する工程を含むことを特徴とする。
CF3-(CF2)m-O-(CF(CF3)CF2O)n-CF(CF3)COOX (I)
(式中、mは0~4の整数、nは0~2の整数、Xは水素原子、NH4又はアルカリ金属原子を表す。)、
一般式(II):
CF3-(CF2)m-O-(CF(CF3)CF2O)n-CHFCF2COOX (II)、
(式中、mは0~4の整数、nは0~2の整数、Xは水素原子、NH4又はアルカリ金属原子を表す。)
一般式(III):
CF3-(CF2)m-O-(CF(CF3)CF2O)n-CH2CF2COOX (III)
(式中、mは0~4の整数、nは0~2の整数、Xは水素原子、NH4又はアルカリ金属原子を表す。)
で表されるフルオロエーテルカルボン酸の1種又は2種以上を使用する。
本発明の第1及び第2の製造方法は、それぞれ上述した特徴を有するが、その他の特徴は以下のとおりである。
ポリテトラフルオロエチレン水性分散体中のポリテトラフルオロエチレンを凝集させる工程、
凝集したポリテトラフルオロエチレンを回収する工程、
回収したポリテトラフルオロエチレンを100~250℃で乾燥させる工程、及び、
乾燥して得られたポリテトラフルオロエチレンを押出助剤と混合し、押出圧力9.8~24.5MPaで押出して、ビードに成形する工程、
得られたビードを200~230℃で加熱して押出助剤を除去し、ビード形状のポリテトラフルオロエチレンを得る工程、
のうち、少なくとも1つの工程を含むことも好ましい。
ポリテトラフルオロエチレン水性分散体1gを、送風乾燥機中で150℃、30分の条件で乾燥し、水性分散体の質量(1g)に対する加熱残分の質量の割合を百分率で表した数値をポリマー固形分濃度とする。
ポリテトラフルオロエチレン水性分散体を水で固形分濃度が0.15質量%になるまで希釈し、得られた希釈ラテックスの単位長さに対する550nmの投射光の透過率と、透過型電子顕微鏡写真により定方向径を測定して決定した数基準長さ平均粒子径とを測定して、検量線を作成する。この検量線を用いて、各試料の550nmの投射光の実測透過率から数平均粒子径を決定する。
ASTM D-4895-89に準拠して試料を作製し、得られた試料の比重を水置換法によって測定する。
微粉末100gに、微粉末及び潤滑剤を合わせた質量に基づき18.0質量%となるように潤滑剤(商品名:IP1620(登録商標)、出光石油化学社製)を添加し、室温にてガラスビン中で3分間混合する。次いで、ガラスビンを、押出前少なくとも1時間、室温(25℃)に放置し、潤滑化樹脂を得る。潤滑化樹脂をオリフィス(直径2.4mm、ランド長5mm、導入角30°)を通して、室温で100:1の減速比でペースト押出し、均一なビード(beading;押出成形体)を得る。押出スピード、すなわち、ラムスピードは、20インチ/分(51cm/分)とする。押出圧力は、ペースト押出しにおいて押出負荷が平衡状態になった時の負荷を測定し、ペースト押出に用いたシリンダーの断面積で除した値とする。
上記のペースト押出しにより得られたビードを230℃で30分加熱することにより、潤滑剤をビードから除去する。次に、ビード(押出成形体)を適当な長さに切断し、クランプ間隔が1.5インチ(38mm)または2.0インチ(51mm)のいずれかの間隔となるよう、各末端をクランプに固定し、空気循環炉中で300℃に加熱する。次いでクランプを所望のストレッチ(総ストレッチ)に相当する分離距離となるまで所望の速度(ストレッチ速度)で離し、ストレッチ試験を実施する。このストレッチ方法は、押出スピード(84cm/分でなく51cm/分)が異なることを除いて、本質的に米国特許第4,576,869号明細書に開示された方法に従う。『ストレッチ』とは、延伸による長さの増加であり、通常元の長さと関連して表される。上記作製方法において、上記ストレッチ速度は、100%/秒であり、上記総ストレッチは2400%である。
上記延伸試験で得られた延伸ビード(ビードをストレッチすることによって作製されたもの)について、25℃で300mm/分の速度で引っ張り試験を行い、破断した時点の強度を破断強度として測定する。
上記延伸試験において、クランプ間隔を1.5インチ(3.8cm)、ストレッチ速度を1000%/秒、総ストレッチを2400%とし、応力緩和時間測定用ビードを作製する。このビードの両方の末端を固定具につなげ、ぴんと張られた全長8インチ(20cm)のビードサンプルとする。オーブンを390℃に保ち、オーブン側部にある(覆われた)スリットを通して固定具をオーブン中に挿入する。オーブンに挿入した時点からビードサンプルが破断するまでに要する時間を応力緩和時間として測定する。
CF3-O-CF(CF3)CF2O-CF(CF3)COONH4:3.4
CF3OCF2CF2OCF2CF2COONH4:3.0
CF3CF2OCF2CF2OCF2COONH4:3.1
6Lの重合槽に、超純水3600g、パラフィンワックス180g及び界面活性剤(CF3-O-CF(CF3)CF2O-CF(CF3)COONH4)5.4g、コハク酸0.108g、シュウ酸0.0252gを仕込み、窒素パージによる脱気を行い、70℃まで昇温した。重合槽内の温度が安定したのち、テトラフルオロエチレンガスを導入し、2.7MPaの圧力とした。
6Lの重合槽に、超純水3600g、パラフィンワックス180g及び界面活性剤(CF3-O-CF(CF3)CF2O-CF(CF3)COONH4)2.2g、コハク酸0.108g、シュウ酸0.0252gを仕込み、窒素パージによる脱気を行い、70℃まで昇温した。重合槽内の温度が安定したのち、テトラフルオロエチレンガスを導入し、2.7MPaの圧力とした。
6Lの重合槽に、超純水3600g、パラフィンワックス180g及び界面活性剤 CF3OCF2CF2OCF2CF2COONH4 5.4g、コハク酸0.108g、シュウ酸0.0252gを仕込み、窒素パージによる脱気を行い、70℃まで昇温した。重合槽内の温度が安定したのち、テトラフルオロエチレンガスを導入し、2.7MPaの圧力とした。
6Lの重合槽に、超純水3600g、パラフィンワックス180g及び界面活性剤 CF3CF2OCF2CF2OCF2COONH4 5.4g、コハク酸0.108g、シュウ酸0.0252gを仕込み、窒素パージによる脱気を行い、70℃まで昇温した。重合槽内の温度が安定したのち、テトラフルオロエチレンガスを導入し、2.7MPaの圧力とした。
Claims (5)
- 非溶融二次加工性を有し、標準比重が2.160以下であり、平均一次粒子径が150nm以上であり、応力緩和時間が500秒以上であり、LogPOWが3.4以下の含フッ素界面活性剤の存在下にテトラフルオロエチレンを乳化重合して得られ、29.7N以上の破断強度を有することを特徴とするポリテトラフルオロエチレン。
- 破断強度が32.0~49.0Nである請求項1記載のポリテトラフルオロエチレン。
- 含フッ素界面活性剤は、一般式:
CF3OCF(CF3)CF2OCF(CF3)COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)、及び、一般式:
CF3CF2OCF2CF2OCF2COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)
からなる群より選択される少なくとも1種の含フッ素界面活性剤である請求項1又は2記載のポリテトラフルオロエチレン。 - LogPOWが3.4以下の含フッ素界面活性剤、水、及び、テトラフルオロエチレンを重合槽に投入する工程、
重合槽にレドックス開始剤を投入してテトラフルオロエチレンの乳化重合を開始する工程、
及び、
ポリテトラフルオロエチレンを回収する工程、を含み、
前記含フッ素界面活性剤の合計投入量が最終ポリテトラフルオロエチレン収量に対して1000~6000ppmである
ことを特徴とするポリテトラフルオロエチレンの製造方法。 - 含フッ素界面活性剤は、一般式:
CF3OCF(CF3)CF2OCF(CF3)COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)、及び、一般式:
CF3CF2OCF2CF2OCF2COOX
(式中、Xは水素原子、NH4又はアルカリ金属原子を表す。)
からなる群より選択される少なくとも1種の含フッ素界面活性剤である請求項4記載の製造方法。
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JP6194964B2 (ja) | 2017-09-13 |
US20120028046A1 (en) | 2012-02-02 |
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CN102356095B (zh) | 2015-12-02 |
US11827724B2 (en) | 2023-11-28 |
CN105218712A (zh) | 2016-01-06 |
JP5901290B2 (ja) | 2016-04-06 |
CN105218712B (zh) | 2017-10-27 |
EP2409996A1 (en) | 2012-01-25 |
EP2409996B1 (en) | 2014-12-03 |
EP2409996B2 (en) | 2018-01-31 |
JPWO2010113950A1 (ja) | 2012-10-11 |
EP2409996A4 (en) | 2012-11-28 |
CN102356095A (zh) | 2012-02-15 |
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