Classifications

• • 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
• • 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
• • 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
  • C08F2/18—Suspension polymerisation
  • C08F2/20—Suspension polymerisation with the aid of macromolecular dispersing agents
• • 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
• • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
• • 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
  • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
  • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • 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
  • C08F116/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F116/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F116/14—Monomers containing only one unsaturated aliphatic radical
• • 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
  • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
• • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/26—Tetrafluoroethene
  • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers

Definitions

• the aromatic group includes, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group and the like. You may be doing it.
• the aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, for example, a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, and a 4-methanesulfonylphenyl group. And so on.
• the aliphatic oxy group may be saturated or unsaturated, and may have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, or the like.
• Examples of the aliphatic oxy group include an alkoxy group having a total carbon atom number of 1 to 8, preferably 1 to 6, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, and a methoxyethoxy group.
• perfluoropolyether is preferable.
• the hydrophobic group may be any of an alkylphenol group, a linear alkyl group and a branched alkyl group.
• the polyoxyalkylene chain may be composed of oxyethylene and oxypropylene. It is a polyoxyalkylene chain consisting of an average number of repetitions of an oxyethylene group of 5 to 20 and an average number of repetitions of an oxypropylene group of 0 to 2, and is a hydrophilic group.
• the number of oxyethylene units can include either the broad or narrow monomodal distribution normally provided, or the broader or bimodal distribution obtained by blending. When the average number of repetitions of the oxypropylene group is more than 0, the oxyethylene group and the oxypropylene group in the polyoxyalkylene chain may be arranged in a block shape or a random shape.
• Nonionic surfactants examples include Genapol X080 (product name, manufactured by Clariant), Neugen TDS-80 (trade name), and the Neugen TDS series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
• Leocol TD-90 trade name as an example Leocol TD series (manufactured by Lion), Lionol (registered trademark) TD series (manufactured by Lion), T-Det A138 (trade name) as an example T-Det A Examples include the series (manufactured by Harcros Chemicals) and the Tagitol (registered trademark) 15S series (manufactured by Dow Chemicals).
• the sugar is a hydrogen atom of a hydroxy group (and / or a hydroxyalkyl group) attached to a carbocyclic atom such that an ether or ester bond is formed between the long chain residue and the sugar moiety.
• the sugar-based polyol may contain one sugar unit or a plurality of sugar units.
• One sugar unit or a plurality of sugar units may be modified with the long chain portion as described above.
• Specific examples of glycoside polyol compounds include glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof.
• fatty alcohols examples include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), Eikosanoic acid and combinations thereof can be mentioned.
• alkyl glucosides are commercially available from Cognis GmbH, Dusseldorf, Germany under the trade names GLUCOPON or DISPONIL.
• the general formula (r1) -CF 2 -O- (CX 6 2) e - ⁇ O-CF (CF 3) ⁇ f - (O) g - (r1)
• X 6 is H, F or CF 3 independently, e is an integer of 0 to 3, f is an integer of 0 to 3, and g is 0 or 1).
• the divalent group to be used is preferable, and the general formula (r2): -CF 2 -O- (CX 7 2) e - (O) g - (r2)
• a divalent group represented by in the formula, X 7 is independently H, F or CF 3 , e is an integer of 0 to 3, and g is 0 or 1) is more preferred.
• M CH ((CF 2 CF 2 CH 2 OSO 3 M)
• the polymer (I) is preferably a polymer (1) containing a polymerization unit (1) based on the monomer represented by the general formula (1).
• CX 2 CY (-CZ 2- O-Rf-A) (1)
• X is the same or different, -H or F
• Y is -H, -F, an alkyl group or a fluorine-containing alkyl group
• Z is the same or different, -H, -F.
• Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms.
• A is -COOM, -SO. 3 M, -OSO 3 M or C (CF 3) 2 OM
• M is, -H, a metal atom, -NR 7 4, good imidazolium be substituted, may have a substituent
• the polymerization unit (1) is preferably a polymerization unit (1A) based on the monomer represented by the general formula (1A).
• CH 2 CF (-CF 2- O-Rf-A) (1A) (In the formula, Rf and A are the same as above.)
• the Rf is a fluorine-containing alkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, or a fluorine-containing alkylene group having a keto group having 2 to 100 carbon atoms. It is an alkylene group.
• the fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is an alkylene group that does not contain a structure in which an oxygen atom is a terminal and contains an ether bond between carbon carbons.
• the monomer represented by the general formula (2) is at least selected from the group consisting of the monomers represented by the general formulas (2a), (2b), (2c), (2d) and (2e).
• One type is preferable.
• CF 2 CF-O- (CF 2 ) n1- A (2a) (In the formula, n1 represents an integer from 1 to 10, and A is the same as above.)
• CF 2 CF-O- (CF 2 C (CF 3 ) F) n2- A (2b) (In the formula, n2 represents an integer of 1 to 5, and A is the same as the above definition.)
• CF 2 CF-O- (CFX 1 ) n3- A (2c) (In the formula, X 1 represents F or CF 3 , n 3 represents an integer of 1 to 10, and A is the same as the above definition.)
• CF 2 CF-O- (CF 2 CFX 1 O) n4- (CF 2 ) n6- A (2d) (In the formula
• n2 is preferably an integer of 3 or less in terms of dispersion stability of the obtained composition.
• X 1 is preferably ⁇ CF 3 in terms of dispersion stability of the composition
• n4 is preferably an integer of 5 or less in terms of water solubility
• A is , -COOM, where M is preferably H or NH 4 .
• n5 is preferably an integer of 5 or less in terms of water-soluble, A is preferably a -COOM, M is preferably H or NH 4.
• X 9 is H, F or CH 3 ;
• Rf 4 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms). Also mentioned is a monomer.
• the content of the polymerization unit (I) of the polymer (I) is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, still more preferably 5.0 mol% or more, based on the total polymerization units. 10 mol% or more is even more preferable, 20 mol% or more is particularly preferable, and 30 mol% or more is particularly preferable. More preferably 40 mol% or more, further preferably 60 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more, substantially 100 mol. % Is particularly preferable, and it is most preferably composed of only the polymerization unit (I).
• the polymer (12) may be a homopolymer consisting of only the polymerization unit (12) based on the monomer (12), or may be copolymerized with the polymerization unit (12) and the monomer (12). It may be a copolymer containing a polymerization unit based on other monomers. The other monomers are as described above.
• the polymerization unit (12) may be the same or different at each appearance, and the polymer (12) is a polymerization unit (12) based on two or more different monomers represented by the general formula (12). May include.
• the content of the polymerization unit based on the other monomer copolymerizable with the monomer (12) is in the order of preference with respect to all the polymerization units constituting the polymer (12). , 50 mol% or less, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, 1 mol% or less.
• the content of the polymerization unit based on the other monomer copolymerizable with the monomer (12) is particularly preferably 0 mol%, and the polymer (12) is the other monomer. Most preferably, it does not contain a polymerization unit based on.
• the polymer (11) is a novel polymer, which is simply obtained by polymerizing the monomer (11) represented by the general formula (11) in an aqueous medium. It is a production method of the polymer (11) for producing the polymer (11) of the polymer (11), and is produced by the production method (11) for maintaining the oxygen concentration in the reaction system of the polymerization at 500 volume ppm or less. be able to.
• the oxygen concentration in the polymerization reaction system is 500 volume ppm or less.
• the oxygen concentration in the reaction system is maintained at 500 volume ppm or less throughout the polymerization period of the monomer (11).
• the oxygen concentration in the reaction system is preferably 350 volume ppm or less, more preferably 300 volume ppm or less, further preferably 100 volume ppm or less, and particularly preferably 50 volume ppm or less.
• the oxygen concentration in the reaction system is usually 0.01 volume ppm or more.
• the molecular weight of the monomer (I) is preferably 500 or less, more preferably 400 or less. That is, the polymer (I) preferably contains substantially no dimer and trimmer having a molecular weight of 1500 or less, and more preferably substantially does not contain a dimer and trimmer having a molecular weight of 1200 or less.
• the polymerization of the monomer (I) produces a dimer and a trimmer of the monomer (I), and as a result, the dimer and the trimmer of the monomer (I) are contained in the polymer (I).
• the mechanism by which the monomer (I) dimer and trimmer are generated is not always clear, but in particular, the polymerization reaction in the polymerization system in which the monomer (I) accounts for the majority of the monomers present in the polymerization system. Therefore, it is presumed that the dimerization and trimerization of the monomer (I) occur at a non-negligible frequency.
• the crude composition obtained by the polymerization of the monomer (I) may be the composition obtained by the polymerization after the polymerization, or the composition obtained by the polymerization obtained by diluting or concentrating the composition after the polymerization. It may be the one which has been subjected to the dispersion stabilization treatment or the like. It is also preferable to adjust the viscosity of the crude composition by these treatments in order to smoothly proceed with ultrafiltration, microfiltration or dialysis membrane treatment.
• the content of the polymer of the monomer (I) in the crude composition is, for example, the method of adding water to the crude composition obtained by the polymerization of the monomer (I), that of the monomer (I). It can be adjusted by a method of concentrating the crude composition obtained by polymerization.
• the viscosity of the crude composition is preferably 25 mPa ⁇ s or less because ultrafiltration, microfiltration or dialysis membrane treatment proceeds smoothly.
• the viscosity of the crude composition can be determined by, for example, a method of adjusting the number average molecular weight of the polymer of the monomer (I), a method of adjusting the concentration of the polymer of the monomer (I) in the crude composition, or a crude composition. It can be adjusted by a method of adjusting the temperature of an object.
• the above ultrafiltration can be performed using an ultrafiltration membrane.
• the ultrafiltration can be performed using, for example, an ultrafiltration device having an ultrafiltration membrane, and a centrifugal ultrafiltration method, a batch type ultrafiltration method, a circulation type ultrafiltration method, or the like can be adopted.
• the material of the ultrafiltration membrane is preferably an organic material, more preferably chlorinated polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic nitrile, polysulfone, or polyethersulfone, and polypolysulfone. Acrylonitrile, polysulfone or polyvinylidene fluoride are more preferred.
• Examples of the material of the precision filtration membrane include cellulose-based, aromatic polyamide, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, polytetrafluoroethylene, ceramics, metal and the like. Be done. Among them, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, polypropylene, polycarbonate, or polytetrafluoroethylene are preferable, and polyvinylidene nitrile or polyvinylidene fluoride is particularly preferable.
• the end point of ultrafiltration, microfiltration or dialysis membrane treatment may be appropriately determined and is not limited. Further, in the above-mentioned ultrafiltration, microfiltration or dialysis membrane treatment, in order to improve the durability of the filtration membrane, backwashing with water may be performed about once with a filtration time of 1 to 24 hours as a guide.
• the polymerization temperature and polymerization pressure in the above polymerization are appropriately determined by the type of monomer used, the target molecular weight of PTFE, and the reaction rate.
• the amount of the polymer (I) at the start of the polymerization is preferably 1 mass ppm or more with respect to the aqueous medium.
• the amount of the polymer (I) at the start of polymerization is preferably 10 mass ppm or more, more preferably 50 mass ppm or more, still more preferably 100 mass ppm or more, still more preferably 200 mass ppm or more.
• the upper limit is not particularly limited, but for example, it is preferably 100,000 mass ppm, and more preferably 50,000 mass ppm. When the amount of the polymer (I) at the start of polymerization is within the above range, an aqueous dispersion liquid having further excellent dispersion stability can be obtained.
• the total amount of the polymer (I) added is preferably 0.0001 to 15% by mass with respect to 100% by mass of the aqueous medium.
• a more preferable lower limit is 0.001% by mass, and a more preferable upper limit is 1% by mass. If it is less than 0.0001% by mass, the dispersion force may be insufficient, and if it exceeds 15% by mass, the effect commensurate with the amount added cannot be obtained.
• the amount of the polymer (I) added is appropriately determined depending on the type of monomer used, the target molecular weight of PTFE, and the like.
• Polymerization of TFE is carried out in an aqueous medium in the presence of the polymer (I). It is also preferable to continuously add the polymer (I) during the polymerization of TFE.
• the continuous addition of the polymer (I) means, for example, the addition of the polymer (I) not all at once, but over time and without interruption or in divided portions.
• modified monomer (A) By the presence of the modified monomer (A), a larger amount of uncoagulated polymer can be generated during polymerization, and further, primary particles having a smaller average primary particle size and aspect ratio can be obtained. Can also be reduced.
• Examples of the metal atom include monovalent and divalent metal atoms, and examples thereof include alkali metals (Group 1) and alkaline earth metals (Group 2), with Na, K or Li being preferable.
• alkali metals Group 1
• alkaline earth metals Group 2
• Na, K or Li being preferable.
• Y 3 is ⁇ PO 3 M or ⁇ P (O) (OM) 2.
• Y 3 is -PO 3 M or -P (O) (OM) 2
• Y 3 is -COOM, -SO 3 M or -OSO 3 M
• M is H, a metal atom, NR 7y 4 , an imidazolium which may have a substituent, a substituent.
• Pyridineium, which may have a substituent, or phosphonium, R 7y which may have a substituent, may be an H or an organic group, and may be the same or different. Any two of them are bonded to each other and have a ring. May be formed.).
• the organic group in R 7y an alkyl group is preferable.
• an organic group of H or C 1-10 is preferable, an organic group of H or C 1-4 is more preferable, and an alkyl group of H or C 1-4 is further preferable.
• the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), and the like, and Na, K, or Li is preferable.
• Y 3 preferably -COOM or -SO 3 M, -COOM is more preferable.
• Y is an —H, —F, an alkyl group or a fluorine-containing alkyl group.
• the alkyl group may be an alkyl group containing no fluorine atom and may have 1 or more carbon atoms.
• the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
• the fluorine-containing alkyl group is an alkyl group containing at least one fluorine atom, and may have 1 or more carbon atoms.
• the fluorine-containing alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less, and even more preferably 3 or less.
• Y, -H, -F or -CF 3 is preferable, and -F is more preferable.
• fluorinated alkylene group -CF 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 CH 2 -, - CF (CF 3) - , -CF (CF 3) CF 2 -, - CF (CF 3) CH 2 - and the like.
• the fluorine-containing alkylene group is preferably a perfluoroalkylene group.
• CH 3- (CH 2 ) n- LM as represented by lauric acid and lauryl sulfate (n is an integer of 6 to 17 in the formula.
• L and M are the above-mentioned The same) can be mentioned.
• Mixtures of those in which R is an alkyl group having 12 to 16 carbon atoms and LM is sulfate or sodium dodecyl sulfate (SDS) can also be used.
• hydrophilic moieties of siloxane hydrocarbon surfactants are sulfate, sulfonate, phosphonate, phosphate ester, carboxylate, carbonate, sulfosuccinate, taurate (as free acid, salt or ester), phosphine oxide, betaine, betaine. It may contain one or more polar moieties containing ionic groups such as copolyol, quaternary ammonium salts. The ionic hydrophobic moiety may also include an ionically functionalized siloxane graft.
• anionic hydrocarbon-based surfactant examples include the general formula ( ⁇ ): R 10- COMM ( ⁇ ) (Wherein, R 10 is a is .M monovalent organic group containing 1 or more carbon atoms, H, a metal atom, NR 11 4, good imidazolium be substituted, substituted
• the compound ( ⁇ ) represented by ( ⁇ ) is a pyridinium which may have a group or a phosphonium which may have a substituent, and R 11 is an H or an organic group, which may be the same or different. Can be mentioned.
• R 11 an organic group of H or C 1-10 is preferable, and an organic group of H or C 1-4 is more preferable.
• Examples of the compound ( ⁇ ) include R 12- COMM (in the formula, R 12 may have a substituent and has a linear or branched alkyl group having 1 or more carbon atoms, an alkenyl group, an alkylene group or an alkenylene. It is a cyclic alkyl group having 3 or more carbon atoms, an alkenyl group, an alkylene group or an alkenylene group which may have a group or a substituent, and these may contain an ether bond. When the number of carbon atoms is 3 or more, the group may be contained. It may contain a monovalent or divalent heterocycle or may form a ring. M is the same as above), and anionic surfactants are also mentioned. Specifically, those represented by CH 3- (CH 2 ) n- COOM (in the equation, n is an integer of 2 to 28; M is the same as above) can be mentioned.
• substantially in the absence of a fluorine-containing surfactant means that the amount of the fluorine-containing surfactant is 10 mass ppm or less, preferably 1 mass ppm or less, with respect to an aqueous medium. Yes, more preferably 100 mass ppb or less, still more preferably 10 mass ppb or less, and even more preferably 1 mass ppb or less.
• Examples of the fluorine-containing surfactant include a fluorine-containing surfactant having a Log POW of 3.5 or less.
• the LogPOW is the partition coefficient between 1-octanol and water, and LogP [in the formula, P is the octanol when the octanol / water (1: 1) mixture containing the fluorine-containing interface active agent is phase-separated. Represents the concentration of the fluorine-containing surfactant in water / the concentration of the fluorine-containing surfactant in water].
• X n2 , X n3 and X n4 may be the same or different and may contain an ether bond of H, F or 1 to 6 carbon atoms, a linear or branched chain moiety or complete. It is a fluorinated alkyl group.
• Rf n5 is a linear or branched chain moiety or a fully fluorinated alkylene group that may contain an ether bond having 1 to 3 carbon atoms, and L is a linking group.
• Y 0 is defined above. However, a compound represented by X n2 , X n3 , X n4 and Rf n5 having a total carbon number of 18 or less) can be mentioned.
• the perfluorocarboxylic acid (I) represented by the general formula (I) and the ⁇ -H perfluorocarboxylic acid represented by the general formula (II) are represented.
• the PTFE may have a core-shell structure.
• the core-shell structure is a conventionally known structure, and is a structure of primary particles in an aqueous dispersion that can be produced by the method described in US Pat. No. 6,841,594.
• Examples of the PTFE having a core-shell structure include a core-shell structure including a core portion of a TFE homopolymer and a shell portion of a modified PTFE, a core-shell structure including a core portion of a modified PTFE and a shell portion of a TFE homopolymer, and a modified PTFE.
• a core-shell structure including a core portion of the above and a shell portion of the modified PTFE having a monomer composition different from that of the modified PTFE constituting the core portion can be mentioned.
• the PTFE having the core-shell structure for example, first, TFE and, if necessary, a modified monomer are polymerized to produce a core portion (TFE homopolymer or modified PTFE), and then TFE and, if necessary, a modified monomer are polymerized. It can be obtained by producing a shell portion (TFE homopolymer or modified PTFE).
• the shell portion means a portion constituting a predetermined thickness from the surface of the PTFE primary particle to the inside of the particle, and the core portion means a portion constituting the inside of the shell portion.
• the clamp is then separated at a desired speed (stretch rate) until a separation distance corresponding to the desired stretch (total stretch) is achieved and a stretching test is performed.
• This stretching method essentially follows the method disclosed in US Pat. No. 4,576,869, except that the extrusion speed (51 cm / min instead of 84 cm / min) is different.
• "Stretch" is an increase in length due to stretching and is usually expressed as a ratio to the original length. In the production method, the stretch rate is 1000% / sec and the total stretch is 2400%.
• the high molecular weight PTFE means a PTFE having non-melt processability and fibrillation property.
• the low molecular weight PTFE means PTFE having melt processability and not fibrillation property.
• a standard specific gravity is adopted as an index of the molecular weight of the high molecular weight PTFE
• a complex viscosity (melt viscosity) is adopted as an index of the molecular weight of the low molecular weight PTFE.
• the average primary particle size of low molecular weight PTFE primary particles can be measured by the dynamic light scattering method.
• a low molecular weight PTFE aqueous dispersion having a polymer solid content concentration adjusted to about 1.0% by mass was prepared, and a dynamic light scattering method was used to measure the measurement temperature at 25 ° C. and the refractive index of the solvent (water). It can be measured with 1.3328, the viscosity of the solvent (water) being 0.8878 mPa ⁇ s, and the number of integrations being 70 times.
• ELSZ-1000S manufactured by Otsuka Electronics Co., Ltd.
• the PTFE aqueous dispersion is obtained by blending a compounding agent such as a known pigment, thickener, dispersant, antifoaming agent, antifreezing agent, or film forming aid, or by further compounding another polymer compound. It can be used as a water-based coating coating. Further, as an additive application, it can be used as a binder for suppressing the falling off of the active material of the electrode, a binder application, a compound application such as an anti-drip agent, and a dust suppression treatment application for preventing the flying of earth and sand and dust.
• a compounding agent such as a known pigment, thickener, dispersant, antifoaming agent, antifreezing agent, or film forming aid
• the PTFE aqueous dispersion is also preferably used as a dust control treatment agent.
• the dust control treatment agent is a method for suppressing dust of a dust-generating substance by mixing it with a dust-generating substance and applying a compression-shearing action to the mixture at a temperature of 20 to 200 ° C. to fibril the PTFE. It can be used in methods such as Japanese Patent No. 2827152 and Japanese Patent No. 2538783.
• the above-mentioned PTFE aqueous dispersion can be suitably used for, for example, the dust control treatment agent composition described in International Publication No. 2007/004250, and is also suitable for the dust control treatment method described in International Publication No. 2007/000812. Can be used for.
• the aqueous dispersion obtained by the polymerization is subjected to (I) anion exchange resin or anion exchange resin and cation exchange in the presence of a nonionic surfactant.
• An aqueous dispersion can be produced.
• the nonionic surfactant is not particularly limited, but known ones can be used.
• the anion exchange resin is not particularly limited, but known ones can be used.
• the above-mentioned "mixed bed composed of a cation exchange resin and an anion exchange resin” is not particularly limited, and when both are filled in the same column, when both are filled in different columns, both are filled. This includes the case where it is dispersed in an aqueous dispersion.
• a known method is adopted as the method of concentration. Specific examples thereof include those described in International Publication No. 2007/046482 and International Publication No. 2014/084399. Examples thereof include phase separation, centrifugal sedimentation, cloud point concentration, electroconcentration, electrophoresis, filtration treatment using ultrafiltration, filtration treatment using a reverse osmosis membrane (RO membrane), nanofiltration treatment and the like.
• the above concentration can concentrate the PTFE concentration to 30 to 70% by mass depending on the application. Concentration may impair the stability of the dispersion, in which case a dispersion stabilizer may be added. As the dispersion stabilizer, the nonionic surfactant and various other surfactants may be added.
• the type of the known anionic surfactant is not particularly limited, but for example, the anionic surfactant described in International Publication No. 2013/146950 and International Publication No. 2013/146947.
• Agents can be used.
• those having a saturated or unsaturated aliphatic chain having 6 to 40 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 9 to 13 carbon atoms can be mentioned.
• the saturated or unsaturated aliphatic chain may be either a straight chain or a branched chain, and may have a cyclic structure.
• the hydrocarbon may be aromatic or may have an aromatic group.
• the hydrocarbon may have heteroatoms such as oxygen, nitrogen and sulfur.
• the amount of the anionic surfactant added depends on the type of the anionic surfactant and other compounding agents, but is preferably 10% by mass to 5000% by mass with respect to the solid content mass of PTFE. As the lower limit of the amount of the anionic surfactant added, 50 mass ppm or more is more preferable, and 100 mass ppm or more is further preferable. If the amount added is too small, the viscosity adjusting effect is poor.
• the upper limit of the amount of the anionic surfactant added is more preferably 3000 mass ppm or less, further preferably 2000 mass ppm or less. If the amount added is too large, the mechanical stability and storage stability of the aqueous dispersion may be impaired.
• methyl cellulose, alumina sol, polyvinyl alcohol, carboxylated vinyl polymer and the like can be blended in addition to the anionic surfactant.
• a pH adjuster such as aqueous ammonia can also be added for the purpose of adjusting the pH of the aqueous dispersion.
• the wet powder obtained by coagulating the PTFE is usually dried by means of vacuum, high frequency, hot air or the like while keeping the wet powder in a state where it does not flow so much, preferably in a stationary state. Friction between powders, especially at high temperatures, generally has an unfavorable effect on fine powder type PTFE. This is because particles made of this type of PTFE are easily fibrillated even by a small shearing force and have the property of losing the state of the original stable particle structure.
• the drying can be carried out at a drying temperature of 10 to 300 ° C. (preferably 10 to 250 ° C.), preferably 100 to 300 ° C. (preferably 100 to 250 ° C.) ° C.
• the PTFE powder preferably has an average particle size (average secondary particle size) of 100 to 2000 ⁇ m.
• the lower limit of the average secondary particle size is more preferably 200 ⁇ m or more, and further preferably 300 ⁇ m or more.
• the upper limit of the average secondary particle size is preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, and particularly preferably 700 ⁇ m or less.
• the average particle size is a value measured in accordance with JIS K 6891.
• DTA differential thermal
• ⁇ Stretching test> The stretching test and the measurement of the breaking strength A were carried out by the following method in accordance with the method described in JP-A-2002-201217.
• the lubricant was removed from the beads by heating the beads obtained by the above paste extrusion at 230 ° C. for 30 minutes.
• the beads (extruded body) were cut to an appropriate length, each end was fixed to a clamp so that the clamp interval was 1.5 inches (38 mm), and heated to 300 ° C. in an air circulation furnace. ..
• the clamp was separated at a desired speed (stretch speed) until the separation distance corresponding to the desired stretch (total stretch) was reached, and a stretching test (stretch test) was performed.
• ⁇ Appearance of stretched body> The appearance of the stretched bead (produced by stretching the bead) obtained in the above stretching test was visually observed and evaluated according to the following criteria. Uniformity: The appearance of the stretched bead was uniform. Non-uniformity: The appearance of the stretched bead was non-uniform, with cracks, swells, and sparseness observed in the stretched bead.
• the content of the polymer H was Mw46.0 ⁇ 10 4 , Mn12.2 ⁇ 10 4 , dimer, and trimmer with respect to the polymer H. It was 0.1% by mass or less.
• the concentration of the obtained polymer H aqueous solution H-2 was 2.1% by mass.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerisation Methods In General (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=75980136

Family Applications (1)

Country Status (5)

Cited By (2)

Citations (43)

Family Cites Families (6)

• 2020
  • 2020-11-19 EP EP20890067.0A patent/EP4063405A4/en active Pending
  • 2020-11-19 WO PCT/JP2020/043293 patent/WO2021100834A1/ja not_active Ceased
  • 2020-11-19 CN CN202080079997.8A patent/CN114729071A/zh active Pending
  • 2020-11-19 JP JP2021558460A patent/JP7417131B2/ja active Active
• 2022
  • 2022-05-18 US US17/747,655 patent/US12460025B2/en active Active

Patent Citations (44)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events