WO2011148795A1 - 含フッ素ポリマー水性分散液 - Google Patents
含フッ素ポリマー水性分散液 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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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
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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
- C08F14/22—Vinylidene fluoride
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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
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5337—Esters of phosphonic acids containing also halogens
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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
- 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
- C08F214/22—Vinylidene fluoride
Definitions
- the present invention relates to a fluoropolymer aqueous dispersion. More specifically, the invention relates to a fluoropolymer aqueous dispersion using an emulsifier with low bioaccumulation ability and excellent in mechanical stability.
- Perfluoroalkyl group-containing carboxylic acids are widely used in the emulsion polymerization reaction of fluorine-containing monomers as fluorine-based surfactants that act as emulsifiers.
- fluorine-containing monomers as fluorine-based surfactants that act as emulsifiers.
- perfluorooctanoic acid C 7 F 15 COOH or a salt thereof (hereinafter abbreviated as “PFOA”) is known to be a surfactant excellent in monomer emulsifiability and latex stability.
- PFOA perfluorinated chemical substances
- PFOA perfluorinated compound represented by PFOA
- PFOA has a high affinity to the polymer and therefore, after aggregation of the polymer latex obtained by the emulsion polymerization method, the amount of adhesion of PFOA to the fluoropolymer and the residual amount are large, which are reduced It is strongly desired to
- Patent Document 1 describes the general formula F (CF 2 CF 2 ) n CH 2 CH 2 SO 3 M (M: monovalent cation) It is described that a mixture of an aggregate number n of 2 to 8 and an average value of 2 to 6 and an aggregate number n of 2 to 6 is used as a dispersant.
- this perfluoroalkylethane sulfonic acid (salt) is used as a fluorine-containing surfactant, chain transfer is caused during the polymerization reaction, and therefore, it can not be avoided that the polymer obtained is lowered in molecular weight.
- Patent Document 2 proposes using a compound represented by
- this compound is not only inferior to PFOA in terms of the emulsifiability of the monomer and the stability of the latex, but also in homopolymerization and copolymerization of vinylidene fluoride.
- the polymerization rate of the vinylidene fluoride as a monomer is low due to low micelle solubility, and the stability of the resulting polymer latex is also poor
- polyether carboxylic acid (salt) is easy to foam, not only is the handling of the latex obtained by the polymerization reaction not only easy, but it is also described that the amount of aggregates in the latex is also large compared to PFOA ( Patent Document 3).
- polyfluoroalkyl phosphonic acid ester is widely used as a synthetic raw material of a mold release agent.
- the mold release performance when used as a mold release agent is most easily expressed in a compound having 8 to 12 carbon atoms of a perfluoroalkyl group, and in particular, CF 3 (CF 2 ) 7 CH 2 which is a compound containing a perfluorooctyl group.
- CH 2 P (O) (OC 2 H 5 ) 2 Is preferably used for this type of application (see Patent Documents 4 to 7).
- telomer compounds having a perfluoroalkyl group having a carbon number of 8 or more can not avoid generation and contamination of highly bioaccumulative perfluorooctanoic acids in the production process. Therefore, manufacturers of such telomer compounds are making progress in withdrawal from their production and substitution to compounds having a perfluoroalkyl group having 6 or less carbon atoms.
- the orientation on the surface of the treated substrate is significantly reduced, and the melting point and the glass transition point Tg are significantly lower than the compound having 8 carbon atoms. It will be greatly affected by operating environment conditions such as temperature, humidity, stress, contact of organic solvents and the like. Therefore, the required performance can not be obtained, and the durability is also affected.
- the fluorine-containing polymer resin which is a fluorine-containing polymer
- the fluorine-containing polymer elastomer has heat resistance, oil resistance, and chemical resistance.
- Vulcanized molded products are widely used as various sealing materials such as oil seals, O-rings, packings, and gaskets.
- An aqueous dispersion of a fluorine-containing polymer used for this type of application is required to have sufficient stability against mechanical processing such as passing through a metal sieve during use. .
- An object of the present invention is to provide a fluoropolymer aqueous dispersion using a low bioaccumulation emulsifying agent and excellent in mechanical stability.
- the object of the present invention is to use the general formula C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OM 1 ) (OM 2 ) [I ]
- M 1 is a hydrogen atom, an alkali metal, an ammonium base or an organic amine base
- M 2 is an alkali metal, an ammonium base or an organic amine base
- n is an integer of 1 to 6 and a is 1 to 4
- the fluorine-containing polymer aqueous dispersion is preferably obtained by emulsion-polymerizing a fluorine-containing monomer in the presence of an aqueous solution of a polyfluoroalkyl phosphonate emulsifier represented by the general formula [I].
- the polyfluoroalkyl phosphonate emulsifier according to the present invention is a compound having a perfluoroalkyl group having 6 or less carbon atoms which is said to have low bioaccumulation ability, and is further excellent in emulsification performance.
- a fluoropolymer aqueous dispersion having an emulsification performance comparable to that of ammonium acid and produced using an aqueous solution of this emulsifier can form a stable emulsion. The emulsion stability is well maintained even after standing at room temperature or for 1 month at 40 ° C.
- this fluoropolymer aqueous dispersion is excellent in mechanical stability and, for example, almost no change in the dispersed particle size is observed even after passing through a metal sieve ten times.
- the polyfluoroalkyl phosphonic acid used as an emulsifier after forming a salt has the general formula C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) 2 [II] (Where n is an integer of 1 to 6; a is an integer of 1 to 4; b is an integer of 1 to 3; c is an integer of 1 to 3); n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OR) 2 [III] It is produced by hydrolyzing a polyfluoroalkyl phosphonic acid diester represented by (wherein R is an alkyl group having 1 to 4 carbon atoms).
- the polyfluoroalkyl phosphonic acid diester [III] used as the starting material for this reaction is polyfluoroalkyl iodide C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c I [IV] And trialkyl phosphite P (OR) 3 to obtain.
- Polyfluoroalkyl iodides [IV] are known compounds and are described in Patent Documents 8-9.
- polyfluoroalkyl iodides [IV] include trialkyl phosphites such as trialkyl phosphite P having an alkyl group having 1 to 4 carbon atoms such as trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite and the like.
- the polyfluoroalkyl phosphonic acid diester [III] which is a raw material, can be obtained by reacting (OR) 3 and performing a de-RI reaction. Incidentally, if ethylene is not added adjacent to the terminal group I of the polyfluoroalkyl iodide [IV], the de-RI reaction with the trialkyl phosphite does not proceed.
- the hydrolysis reaction of the polyfluoroalkylphosphonic acid diester [III] is easily carried out by stirring at about 90 to 100 ° C. in the presence of an acidic catalyst such as an inorganic acid represented by concentrated hydrochloric acid.
- the reaction mixture can be filtered under reduced pressure, washed with water, filtered, washed with acetone, filtered, etc. to obtain the target polyfluoroalkylphosphonic acid [II] with a good yield of about 90%. .
- Polyfluoroalkylphosphonates used as emulsifiers C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OM 1 ) (OM 2 ) [ I]
- Is a polyfluoroalkyl phosphonic acid C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) 2 [II]
- alkali metal hydroxide for example, sodium hydroxide, potassium hydroxide and the like are preferably used.
- organic amines include monoethylamine, monoisopropylamine, diethylamine, diisopropanolamine, dicyclohexylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, triethanolamine, tris (2-hydroxyethyl) amine, pyridine, morpholine or derivatives thereof Etc. are preferred.
- the alkali metal hydroxide, ammonia or organic amine forms a mono salt when used in equimolar amount with respect to the polyfluoroalkyl phosphonic acid, and forms a di salt when used twice as much. Let Generally, when it is used in the required theoretical molar number or more and used in an equimolar amount or more and less than 2 times the molar amount, a mixture of a mono salt and a di salt is formed.
- the polyfluoroalkyl phosphonate is used as an aqueous solution dissolved in an aqueous medium which is water or an aqueous solution of a water-soluble organic solvent or an organic solvent solution dissolved in an organic solvent.
- organic solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aprotic polarides such as acetonitrile, dimethylformamide, diethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone.
- a solvent is used.
- the emulsifying ability of polyfluoroalkyl phosphonate is, for example, in the case of an aqueous solution of ammonium 2- (perfluorohexyl) ethyl phosphonate, its critical micelle concentration [CMC] is found at around an emulsifier concentration of about 0.8% by weight, and the emulsifier concentration is about A constant low surface tension is exhibited at 1.0 wt% or more.
- the aqueous fluoropolymer dispersion of the present invention is preferably obtained by emulsion-polymerizing a fluoromonomer in the presence of an aqueous solution of a polyfluoroalkyl phosphonate emulsifier (fluorinated emulsifier) represented by the general formula [I].
- a polyfluoroalkyl phosphonate emulsifier fluorinated emulsifier
- the amount of fluorinated emulsifier used may be varied depending on the properties such as the solids concentration and the average particle size of the resulting aqueous dispersion. Generally, the amount of fluorinated emulsifier is about 0.001 to 5% by weight, preferably about 0.005 to 2% by weight, particularly preferably about 0.005 to 1% by weight, based on the weight of the aqueous medium used for the polymerization reaction .
- the emulsion polymerization reaction is initiated in the presence of such a fluoroemulsifier, and additional fluoroemulsifier can also be added during the polymerization reaction.
- at least one other fluorinated emulsifier and non-fluorinated emulsifier can be used in combination.
- the emulsion polymerization reaction of the fluorine-containing monomer using this emulsifier is carried out in the same manner as in the case of using the conventional perfluorooctanoic acid (salt) PFOA emulsifier.
- the emulsion polymerization reaction is preferably performed in the presence of an inorganic peroxide, an azo compound, an organic peroxide, etc., a water-soluble inorganic peroxide such as ammonium persulfate, sodium persulfate, potassium persulfate or sodium hydrogen sulfite, It is carried out using a redox system with a hydrogen sulfite such as sodium sulfite, thiosulfate, hydrazine, or a reducing agent such as azodicarboxylate as a catalyst, in which case to adjust the pH in the polymerization system, phosphate (Na 2 ) An electrolyte substance having a buffering ability such as HPO 4 , NaH 2 PO 4 , KH 2 PO 4 or the like or a borate (Na 2 B 2 O 7 or the like) or NaOH may be added and used.
- an inorganic peroxide an azo compound, an organic peroxide, etc., a
- the emulsion polymerization reaction is carried out using about 0.01 to 1% by weight, preferably about 0.05 to 0.5% by weight, more preferably about 0.05 to 0.3% by weight of a polymerization initiator based on the fluoropolymer to be produced, and about 0 to 100 C., preferably about 5 to 80.degree. C., for about 1 to 48 hours, under pressure conditions of about 0.1 to 10 MPa, preferably about 0.2 to 5 MPa.
- the polymerization initiator may be added again during the polymerization reaction, if necessary.
- VdF vinylidene fluoride
- VF vinyl fluoride
- HFP hexafluoropropylene
- TFE tetrafluoroethylene
- PFP pentafluoropropylene
- CTFE monochlorotrifluoroethylene
- FAVE perfluoro (alkyl vinyl ether) having a C 1 to C 3 alkyl group, perfluoro (alkoxy alkyl vinyl ether) [FOAVE], etc.
- the copolymerization reaction is preferably carried out as a division method from the viewpoint of the uniformity of the composition of the obtained fluorine-containing polymer, particularly the fluorine-containing copolymer elastomer.
- Examples of the polymer of the fluorine-containing monomer include the following, and a resinous or elastomeric fluorine-containing polymer can be formed depending on the copolymer composition and the like.
- esters such as ethyl malonate and ethyl acetate, ethers such as dimethyl ether and methyl tertiary butyl ether, alcohols such as methanol, ethanol and isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like ketones, alkanes C 1 ⁇ C 5, chloroform, carbon tetrachloride, various ones such as halogenated hydrocarbons dichloroethane used.
- iodine-containing perfluoro compounds such as ICF 2 CF 2 I and ICF 2 CF 2 CF 2 CF 2 I
- iodine-containing bromine perfluoro compounds such as ICF 2 CF 2 Br and ICF 2 CF 2 CF 2 CF 2 Br are linked. It can be used as a transfer agent, and these compounds can also play a role of forming a crosslinking site in peroxide crosslinking.
- the alkyl group is a -10 alkyl group or a fluoroalkyl group, and these groups may contain an ether bond.
- R 4 an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, These groups may contain an ether bond.
- X Br, I It may be a compound represented by
- a bromine group-containing vinyl ether as represented by the following general formula is used.
- BrRf-O-CF CF 2 BrR f: Bromine group-containing perfluoroalkyl group
- CF 2 BrCF 2 OCF CF 2
- CF 2 Br (CF 2 ) 2 OCF CF 2
- CF 2 Br (CF 2 ) 3 OCF CF 2
- ROCF CFBr
- ROCBr CF 2 (R: lower alkyl group or fluoroalkyl group).
- iodine containing monomer compounds of the general formula IRf-O-CF CF 2 IRf: An iodine group-containing perfluorovinyl ether represented by an iodine group-containing perfluoroalkyl group is used, preferably perfluoro (2-iodoethyl vinyl ether).
- bromine-containing or iodine-containing monomer compounds are preferably used alone or in combination of two or more in consideration of crosslinking conditions, their reactivity, etc., and preferably about 0.001 to 5 mol%, relative to the total amount of fluorine-containing monomers Is used in a proportion of about 0.01 to 1 mol%. Below this ratio, the compression set characteristics of the resulting vulcanizate deteriorate, whereas when it is used above this, the elongation of the vulcanizate decreases.
- iodine-containing bromine compounds general formula RBr n I m (R: fluorohydrocarbon group having 1 to 10 carbon atoms, chlorofluorohydrocarbon group, chlorohydrocarbon group or hydrocarbon group, n, m: 1 or The compounds represented by 2) are used, and specific examples thereof are described in, for example, Patent Document 10.
- Coagulation of the obtained fluoropolymer latex is preferably carried out by salting out, for example, an aqueous calcium chloride solution having a concentration of about 0.1 to 5% by weight, preferably about 0.3 to 3% by weight is used. The steps of filtration, water washing and drying are applied to the coagulated fluoropolymer.
- the molecular weight of these fluorine-containing polymers is, in the case of fluorine-containing resins, the weight-average molecular weight Mw of about 10,000 to 1,000,000, preferably 50,000 to 800,000, and in the case of fluorine-containing elastomers, the processing of their compositions.
- Solution viscosity sp sp / c (1 wt / vol% methyl ethyl ketone solution, 35 ° C.) is about 0.3 to 1.5 dl / g, preferably about 0.4 to 1.3 dl / g, as a molecular weight indicator, taking into consideration the properties and mechanical properties. g.
- Vulcanization of the fluorine-containing elastomer is carried out by an organic peroxide when having a bromine group or an iodine group, and by polyol vulcanization or the like in other cases.
- Examples of the organic peroxide used in the peroxide vulcanization method include 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (third (Butyl pyoxy) hexyne-3, benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxybenzene, 1 1,1-Bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, ⁇ , ⁇ '-bis (tert-butylperoxy)- p-Diisopropylbenzene, 2,5-dimethyl-2,5-di (benzoylperoxy)
- polyfunctional unsaturated compounds such as tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, and triallyl trimellitate are generally used as co-crosslinking agents.
- N, N'-m-phenylenebismaleimide, diallyl phthalate, tris (diallylamine) -s-triazine, triallyl phosphite, 1,2-polybutadiene, ethylene glycol diacrylate, diethylene glycol diacrylate etc. are used in combination.
- Each of the above components to be incorporated into the peroxide curing system is generally a co-crosslinking agent in a proportion of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight of organic peroxide per 100 parts by weight of the fluorine-containing elastomer. Is used in a proportion of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight.
- polyol crosslinking agent 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) perfluoropropane [bisphenol AF] , Hydroquinone, catechol, resorcin, 4,4'-dihydroxydiphenyl, 4-4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 2,2-bis (4-hydroxyphenyl) butane, and other polyhydroxy aromatics
- these polyol crosslinking agents are used in a proportion of about 0.5 to 10 parts by weight, preferably about 1 to 5 parts by weight, per 100 parts by weight of the fluorine-containing elastomer Be
- quaternary onium salts such as quaternary ammonium salts and quaternary phosphonium salts are used in an amount of about 0.1 to 30 parts by weight, preferably about 0.2 to 20 parts by weight, per 100 parts by weight of the fluorine-containing elastomer. Used in proportions of parts.
- a polyol crosslinking agent or quaternary phosphonium salt, or both of them a compound obtained by reacting a bisphenol compound with 2 molar amounts of quaternary phosphonium halide, ie, a bisphenol compound having a quaternary phosphonium base at both ends It can also be used alone or in combination with other vulcanizing agents.
- Each of the above-mentioned vulcanized components may be blended as it is with a fluorine-containing elastomer and kneaded, or diluted with carbon black, silica, clay, talc, diatomaceous earth, barium sulfate or the like to obtain a fluorine-containing elastomer It is also used as a masterbatch dispersion.
- composition in addition to the above-mentioned components, conventionally known fillers or reinforcing agents (carbon black, silica, graphite, clay, talc, diatomaceous earth, barium sulfate, titanium oxide, wollastonite etc.), plastic An agent, a lubricant, a processing aid, a pigment and the like can be appropriately blended.
- conventionally known fillers or reinforcing agents carbon black, silica, graphite, clay, talc, diatomaceous earth, barium sulfate, titanium oxide, wollastonite etc.
- plastic An agent a lubricant, a processing aid, a pigment and the like can be appropriately blended.
- Vulcanization is carried out by mixing the above respective components by mixing methods generally used such as roll mixing, kneader mixing, Banbury mixing, solution mixing and the like, followed by heating. Vulcanization is generally performed by primary vulcanization performed at about 100 to 250 ° C. for about 1 to 120 minutes and secondary vulcanization performed at about 150 to 300 ° C. for 0 to 30 hours, but injection molding is also possible. It is.
- Reference Example 1 (1) In a 1-L four-necked flask equipped with a thermometer and a low-boiling receiver, CF 3 (CF 2) 3 ( CH 2 CF 2) (CF 2 CF 2) 2 (CH 2 CH 2) I (99GC%) 500 g (0.78 mol) and 181 g (1.56 mol) of triethyl phosphite P (OC 2 H 5 ) 3 were charged and stirred at 155 ° C. At this time, in order to remove the by-product ethyl iodide from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 91 g (0.78 mol) of triethyl phosphite was added four times at a time, and the mixture was stirred for a total of 18 hours. .
- the reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C and an overhead temperature of 150 to 155 ° C, the distilled fraction is washed with water, and the purified reaction product (96 GC% ) (Yield 78%) was obtained.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 107 g (0.92 mol) of triethyl phosphite was added once at a time for 4 times and stirred for a total of 18 hours. .
- the reaction mixture is subjected to simple distillation under reduced pressure under the conditions of internal pressure 0.2 kPa, internal temperature 145-155 ° C., overhead temperature 138-142 ° C., the distilled fraction is washed with water, and the purified reaction product (98 GC% ) (Yield 79%) was obtained.
- reaction solution was taken for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then triethyl phosphite was further added to 88 g (0.76 mol) at a time for 4 times, and stirred for a total of 18 hours. .
- the reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C and an overhead temperature of 150 to 155 ° C, the distilled fraction is washed with water, and the purified reaction product (96 GC% ) (Yield 77%) was obtained.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 104 g (0.90 mol) of triethyl phosphite was added once at a time for 4 times and stirred for a total of 18 hours. .
- reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of internal pressure 0.2 kPa, internal temperature 145 to 155 ° C., overhead temperature 138 to 141 ° C., and the distilled fraction is washed with water to obtain a purified reaction product (97 GC% ) (Yield 78%) was obtained.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 104 g (0.90 mol) of triethyl phosphite was added once at a time for 4 times and stirred for a total of 18 hours. .
- reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of internal pressure 0.2 kPa, internal temperature 145 to 155 ° C., overhead temperature 140 to 142 ° C., and the distilled fraction is washed with water to obtain a purified reaction product (97 GC% ) (Yield 79%) was obtained.
- reaction solution was fractionated and subjected to gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then triethyl phosphite was further added once at 130 g (1.12 mol) four times and stirred for a total of 18 hours .
- the reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 130 to 140 ° C., and an overhead temperature of 128 to 131 ° C., and the distilled fraction is washed with water to obtain a purified reaction product (98 GC% ) (Yield 79%) was obtained.
- the emulsifier aqueous solution I was added little by little to water, and the surface tension of the aqueous solution was measured.
- the critical micelle concentration [CMC] was 0.8% by weight, and the surface tension at a concentration of 2.0% by weight was 17 mN / m.
- the surface tension was measured by the maximum bubble method at 20 ° C. using a dynamic surface tension meter made by SITA.
- Reference Examples 8 to 12 In Reference Example 7, the amount of water and the concentration of 1.4% by weight aqueous ammonia solution were respectively changed to predetermined amounts, and instead of polyfluoroalkyl phosphonic acid [IIa], the same amount (5 g) of poly obtained in Reference Examples 2 to 6 Using fluoroalkylphosphonic acids [IIb] to [IIf], their aqueous solutions (active ingredient concentration: 7.0% by weight) were obtained [Emulsifier aqueous solutions II to VI].
- Reference Example 13 In Reference Example 7, the amount of water is changed to 66.4 g, and 5 g of pentadecafluorooctanoic acid ammonium salt C 7 F 15 COONH 4 (DIEMCO product F top EF 204) instead of polyfluoroalkyl phosphonic acid [IIa] and aqueous ammonia solution. Using (11.6 mmol), an aqueous solution thereof (active ingredient concentration 7.0% by weight) was obtained [Emulsifier aqueous solution VII].
- Example 1 In a 10 L stainless steel pressure reactor equipped with a stirrer, Water 2911g Emulsifier aqueous solution I 472 g NaOH 1.3 g Ethyl malonate 12.0 g After replacing the interior space with nitrogen gas, Fluorinated vinylidene [VdF] 435 g (83 mol%) Tetrafluoroethylene [TFE] 45 g (6 mol%) Hexafluoropropylene [HFP] 135 g (11 mol%) When the mixed gas having the mixed composition was charged as an initial charge gas (total 615 g) and the internal temperature of the reactor was raised to 80 ° C., the internal pressure became about 2.4 MPa ⁇ G.
- VdF Fluorinated vinylidene
- TFE Tetrafluoroethylene
- HFP Hexafluoropropylene
- Emulsion A solid content concentration 45.2% by weight
- 6420 g total charge Recovery rate 96.3%) was obtained for the amount of 6663.8 g).
- the average particle size of the emulsion A was measured by a dynamic light scattering method using a micro drag particle size distribution analyzer UPA150 manufactured by Nikkiso Co., Ltd., and it was 115 nm.
- UPA150 micro drag particle size distribution analyzer
- the average particle diameter of the aqueous dispersion after passing the aqueous dispersion 10 times through a 325 mesh metal sieve is 125 nm (9% increase) Values were obtained and confirmed to be stable emulsions.
- the obtained emulsion A is added dropwise with stirring to a 0.5 wt% aqueous calcium chloride solution, the coagulated product is separated by filtration, sufficiently washed with ion-exchanged water, filtered and dried to obtain a white powder.
- 1995 g (95% of conversion) of the fluorocopolymer of the shape of a circle were obtained.
- Example 2 Comparative Example 2
- the same amount (472 g) of each aqueous emulsifier solution II to VII was used.
- the recovery amount, the recovery rate, the solid content concentration and the various average particle sizes, and the measurement at the time of the increase were performed in the same manner as in Example 1.
- the results obtained are shown in Table 2 below.
- the results of Example 1 are also shown.
- Example 7 In a 10 L stainless steel pressure reactor with a stirrer, Ion-exchanged water 4500 g Emulsifier aqueous solution I 250 g Na 2 HPO 4 ⁇ 12 H 2 O 15 g Ethyl malonate 1.8 g After replacing the interior space with nitrogen gas, 180 g (69 mol%) of fluorinated vinylidene [VdF] 126 g (31 mol%) of tetrafluoroethylene [TFE] When the mixed gas having the mixed composition was charged as an initial charge gas (total 306 g) and the internal temperature of the reactor was raised to 80 ° C., the internal pressure became about 2.1 MPa ⁇ G.
- Emulsion G solid content concentration 23.2% by weight 6200 g (total charge Recovery rate 96.0%) was obtained.
- the analysis was performed by SIC Labchat 180, using a melting point (DSC 220C type manufactured by Seiko Instruments Inc.), from 30 ° C to 10 ° C / min. Is heated to 30 ° C. at a cooling rate of 10 ° C./min, and temperature rising and cooling are repeated with a temperature program in which the temperature is raised again to 250 ° C. at a temperature rising rate of 10 ° C./min. The temperature at the peak top was measured at 140 ° C.
- Example 8 In a 10 L stainless steel pressure reactor with a stirrer, Ion-exchanged water 4950g Emulsifier aqueous solution I 720 g Na 2 HPO 4 ⁇ 12H 2 O 3.4 g 5 g of methanol After replacing the interior space with nitrogen gas, 130 g (52 mol%) of tetrafluoroethylene [TFE] 260 g (48 mol%) of perfluoro (ethyl vinyl ether) [FEVE] When the mixed gas having the mixed composition was charged as an initial charged gas (total 390 g) and the internal temperature of the reactor was raised to 80 ° C., the internal pressure became about 2.1 MPa ⁇ G.
- Example 9 In a 10 L stainless steel pressure reactor with a stirrer, Ion-exchanged water 4835 g Emulsifier aqueous solution I 285 g Na 2 HPO 4 ⁇ 12 H 2 O 20 g Ethyl malonate 2.6 g 1,4-diiodoperfluorobutane I (CF 2 ) 4 I 20 g After replacing the interior space with nitrogen gas, Fluorinated vinylidene [VdF] 183 g (32 mol%) 105 g (12 mol%) of tetrafluoroethylene [TFE] 750 g (56 mol%) of hexafluoropropylene [HFP] When the mixed gas having the mixed composition was charged as an initial charge gas (total 1038 g) and the internal temperature of the reactor was raised to 70 ° C., the internal pressure became about 3.1 MPa ⁇ G.
- Example 3 Average particle size Example 7
- Example 8 Example 9 Initial (nm) 120 109 125 Room temperature, 1 month (nm) 122 110 125 Same growth rate (%) 2 1 0 40 ° C, 1 month (nm) 125 110 126 Same growth rate (%) 4 1 1 After passing through a sieve (nm) 130 120 133 Same growth rate (%) 8 10 6
- Reference Example 14 100 parts by weight of the terpolymer obtained in Example 9 MT carbon black 20 20 ZnO 5 ⁇ Triallyl isocyanurate (Japan Chemical Products TAIC M60) 5 Organic peroxides (NOF Corporation perhexa 25B) 3.5 ⁇
- the above components were kneaded using an 8-inch open roll, and the kneaded product was press vulcanized at 180 ° C. for 10 minutes and then oven vulcanized (secondary vulcanizing) at 230 ° C. for 22 hours.
- the properties of the vulcanized product were measured, and the following values were obtained.
- the compression set was measured for P-24 O-ring in accordance with ASTM Method B. 100% modulus 4.3 MPa Elongation at break 220% Strength at break 18.2 MPa Compression set 150 ° C, 70 hours 9% 200 ° C, 70 hours 23% 230 ° C, 70 hours 40%
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Abstract
Description
F(CF2CF2)nCH2CH2SO3M (M:1価カチオン)
で表わされ、集合数nが2~8で、平均値が2~6のものと集合数nが2~6のものとの混合物を分散剤として使用することが記載されている。しかしながら、含フッ素界面活性剤としてこのパーフルオロアルキルエタンスルホン酸(塩)を用いた場合には、重合反応時に連鎖移動を起こすため、得られるポリマーが低分子量化するのを避けることができない。
Rf(CH2)mR′fCOOM
Rf:C3~C8のパーフルオロアルキル基またはパーフルオロアル
コキシル基
R′f:C1~C4のパーフルオロアルキレン基
M:NH4、Li、Na、K、H
m:1~3
で表わされる化合物を用いることが、特許文献2で提案されている。しかしながら、この化合物をフッ素系モノマーの乳化重合の乳化剤として用いた場合には、モノマーの乳化性、ラテックスの安定性の点でPFOAよりも劣るばかりではなく、フッ化ビニリデンの単独重合および共重合においては、モノマーであるフッ化ビニリデンのミセル溶解性が低いため重合速度が非常に遅くなり、さらに得られるポリマーラテックスの安定性も悪く、重合反応中に析出物がみられる場合もある。
CF3(CF2)7CH2CH2P(O)(OC2H5)2
が、この種の用途に好んで使用されている(特許文献4~7参照)。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OM1)(OM2) 〔I〕
(ここで、M1は水素原子、アルカリ金属、アンモニウム塩基または有機アミン塩基であり、M2はアルカリ金属、アンモニウム塩基または有機アミン塩基であり、nは1~6の整数、aは1~4の整数、bは1~3の整数、cは1~3の整数である)で表わされるポリフルオロアルキルホスホン酸塩を乳化剤として、含フッ素ポリマーを分散させた含フッ素ポリマー水性分散液によって達成される。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔II〕
(ここで、nは1~6の整数、aは1~4の整数、bは1~3の整数、cは1~3の整数である)で表わされ、この化合物は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OR)2 〔III〕
(ここで、Rは炭素数1~4のアルキル基である)で表わされるポリフルオロアルキルホスホン酸ジエステルを加水分解反応させることによって製造される。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cI 〔IV〕
とトリアルキルホスファイトP(OR)3を反応させることにより得られる。ポリフルオロアルキルアイオダイド〔IV〕は、公知の化合物であり、特許文献8~9に記載されている。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OM1)(OM2) 〔I〕
は、ポリフルオロアルキルホスホン酸
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔II〕
に、アルカリ金属水酸化物水溶液、アンモニア水溶液または有機アミンを反応させることにより得られる。
VdF単独重合体
TFE単独重合体
VdF-TFE共重合体
VdF-HFP共重合体
VdF-TFE-FMVE3元共重合体
VdF-TFE-HFP3元共重合体
VdF-TFE-CTFE3元共重合体
VdF-CTFE共重合体
VdF-TFE-P 3元共重合体
TFE-P共重合体
TFE-E共重合体
TFE-CTFE共重合体
TFE-HFP共重合体
TFE-FMVE共重合体
TFE-FPVE共重合体
TFE-FMVE-FPVE3元共重合体
TFE-FEVE-FPVE3元共重合体
VdF-TFE-FMVE3元共重合体
好ましくはVdF-HFP共重合体、VdF-TFE-FMVE3元共重合体、VdF-TFE-HFP3元共重合体あるいはTFE-FMVE共重合体が用いられる。
注) E:エチレン
P:プロピレン
FMVE:パーフルオロ(メチルビニルエーテル)
FEVE:パーフルオロ(エチルビニルエーテル)
FPVE:パーフルオロ(プロピルビニルエーテル)
CR1R2=CR3XまたはCR1R2=CR3(R4-X)
R1,R2,R3:同一または互いに異なる基であり、H、F、Cl、炭素数1
~10のアルキル基、フルオロアルキル基であり、これら
の基はエーテル結合を含んでいてもよい
R4:炭素数1~10のアルキル基、フルオロアルキル基であり、
これらの基はエーテル結合を含んでいてもよい
X:Br、I
で表される化合物であってもよい。
BrRf-O-CF=CF2
BrRf:臭素基含有パーフルオロアルキル基
かかる臭素基含有パーフルオロビニルエーテルとしては、例えば CF2BrCF2OCF=CF2、CF2Br(CF2)2OCF=CF2、CF2Br(CF2)3OCF=CF2、CF3CFBr(CF2)2OCF=CF2、CF2Br(CF2)4OCF=CF2等が用いられる。
IRf-O-CF=CF2
IRf:ヨウ素基含有パーフルオロアルキル基
で表わされるヨウ素基含有パーフルオロビニルエーテルが用いられ、好ましくはパーフルオロ(2-ヨードエチルビニルエーテル)が用いられる。
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)I (99GC%)
500g(0.78モル)およびトリエチルホスファイトP(OC2H5)3 181g(1.56モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に91g(0.78モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2 (96GC%)
300g(0.44モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分276gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物242g(0.41モル、収率92%)を得た。
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2 〔IIa〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)I (99GC%)
500g(0.92モル)およびトリエチルホスファイトP(OC2H5)3 213g(1.84モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に107g(0.92モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2 (96GC%)
300g(0.53モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分287gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物240g(0.49モル、収率93%)を得た。
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2 〔IIb〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)I (97GC%)
500g(0.76モル)およびトリエチルホスファイトP(OC2H5)3 176g(1.52モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に88g(0.76モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)2 (96GC%)
300g(0.44モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分276gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物237g(0.40モル、収率90%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OH)2 〔IIc〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)I (97GC%)
500g(0.90モル)およびトリエチルホスファイトP(OC2H5)3 208g(1.80モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に104g(0.90モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2 (95GC%)
300g(0.52モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分271gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物235g(0.48モル、収率92%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2 〔IId〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2I (97GC%)
500g(0.88モル)およびトリエチルホスファイトP(OC2H5)3 204g(1.76モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に104g(0.90モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OCH2CH3)2 (97GC%)
300g(0.51モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分269gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物240g(0.46モル、収率90%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OH)2 〔IIe〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)I (98GC%)
500g(1.12モル)およびトリエチルホスファイトP(OC2H5)3 259g(2.24モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に130g(1.12モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2 (94GC%)
300g(0.63モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分262gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物229g(0.59モル、収率93%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2 〔IIf〕
攪拌装置および滴下装置を備えた容量200mlに反応装置内に、40℃に加熱された水53.2gを保温しながら仕込み、参考例1で得られたポリフルオロアルキルホスホン酸〔IIa〕5g(8.4ミリモル)を加えた後、濃度1.4重量%のアンモニア水溶液15.4g(12.7ミリモル)を加え、1時間攪拌を続けて中和反応を行った。これにより、pH8のポリフルオロアルキルホスホン酸アンモニウム塩の水溶液(有効成分濃度7.0重量%)が得られた〔乳化剤水溶液I〕。
参考例7において、ポリフルオロアルキルホスホン酸〔IIa〕に、アンモニア水溶液を加えることなく1時間攪拌した場合には、添加したポリフルオロアルキルホスホン酸〔IIa〕は水に溶解せずに分離し、水溶液は得られなかった。
参考例7において、水量および濃度1.4重量%アンモニア水溶液量をそれぞれ所定量に変更し、またポリフルオロアルキルホスホン酸〔IIa〕の代りに同量(5g)の参考例2~6で得られたポリフルオロアルキルホスホン酸〔IIb〕~〔IIf〕をそれぞれ用い、それらの水溶液(有効成分濃度7.0重量%)を得た〔乳化剤水溶液II~VI〕。
参考例7において、水量を66.4gに変更し、またポリフルオロアルキルホスホン酸〔IIa〕およびアンモニア水溶液の代りに、ペンタデカフルオロオクタン酸アンモニウム塩C7F15COONH4(ジエムコ製品エフトップEF204)5g(11.6ミリモル)を用い、それの水溶液(有効成分濃度7.0重量%)を得た〔乳化剤水溶液VII〕。
攪拌機を備えた内容積10Lのステンレス鋼製圧力反応器に、
水 2911g
乳化剤水溶液I 472g
NaOH 1.3g
マロン酸エチル 12.0g
を仕込み、内部空間を窒素ガスで置換した後、
フッ素ビニリデン〔VdF〕 435g(83モル%)
テトラフルオロエチレン〔TFE〕 45g( 6モル%)
ヘキサフルオロプロピレン〔HFP〕 135g(11モル%)
の混合組成を有する混合ガスを初期仕込みガス(合計615g)として仕込み、反応器の内温を80℃に昇温させると、内圧は約2.4MPa・Gとなった。
増加率=(試験後-初期)/初期×100(%)
実施例1において、乳化剤水溶液Iの代りに、それぞれ同量(472g)の乳化剤水溶液II~VIIが用いられた。得られたエマルジョンB~Fおよびaについて、回収量、回収率、固形分濃度および各種平均粒子径、その増加時の測定を、実施例1と同様に行った。得られた結果は、次の表2に示される。なお、実施例1についての結果も、併記されている。
攪拌機を有する内容積10Lのステンレス鋼製圧力反応器に、
イオン交換水 4500g
乳化剤水溶液I 250g
Na2HPO4・12H2O 15g
マロン酸エチル 1.8g
を仕込み、内部空間を窒素ガスで置換した後、
フッ素ビニリデン〔VdF〕 180g(69モル%)
テトラフルオロエチレン〔TFE〕 126g(31モル%)
の混合組成を有する混合ガスを初期仕込みガス(合計306g)として仕込み、反応器の内温を80℃に昇温させると、内圧は約2.1MPa・Gとなった。
攪拌機を有する内容積10Lのステンレス鋼製圧力反応器に、
イオン交換水 4950g
乳化剤水溶液I 720g
Na2HPO4・12H2O 3.4g
メタノール 5g
を仕込み、内部空間を窒素ガスで置換した後、
テトラフルオロエチレン〔TFE〕 130g(52モル%)
パーフルオロ(エチルビニルエーテル)〔FEVE〕 260g(48モル%)
の混合組成を有する混合ガスを初期仕込みガス(合計390g)として仕込み、反応器の内温を80℃に昇温させると、内圧は約2.1MPa・Gとなった。
攪拌機を有する内容積10Lのステンレス鋼製圧力反応器に、
イオン交換水 4835g
乳化剤水溶液I 285g
Na2HPO4・12H2O 20g
マロン酸エチル 2.6g
1,4-ジヨードパーフルオロブタンI(CF2)4I 20g
を仕込み、内部空間を窒素ガスで置換した後、
フッ素ビニリデン〔VdF〕 183g(32モル%)
テトラフルオロエチレン〔TFE〕 105g(12モル%)
ヘキサフルオロプロピレン〔HFP〕 750g(56モル%)
の混合組成を有する混合ガスを初期仕込みガス(合計1038g)として仕込み、反応器の内温を70℃に昇温させると、内圧は約3.1MPa・Gとなった。
表3
平均粒子径 実施例7 実施例8 実施例9
初期 (nm) 120 109 125
室温、1ヶ月 (nm) 122 110 125
同増加率 (%) 2 1 0
40℃、1ヶ月 (nm) 125 110 126
同増加率 (%) 4 1 1
ふるい通過後 (nm) 130 120 133
同増加率 (%) 8 10 6
実施例9で得られた3元共重合体 100重量部
MTカーボンブラック 20 〃
ZnO 5 〃
トリアリルイソシアヌレート(日本化成製品TAIC M60) 5 〃
有機過酸化物(日本油脂製品パーヘキサ25B) 3.5 〃
以上の各成分を8インチオープンロールを用いて混練し、混練物を180℃で10分間プレス加硫し、次いで230℃で22時間オーブン加硫(二次加硫)した。
100%モジュラス 4.3MPa
破断時伸び 220%
破断時強度 18.2MPa
圧縮永久歪
150℃、70時間 9%
200℃、70時間 23%
230℃、70時間 40%
Claims (6)
- 一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OM1)(OM2) 〔I〕
(ここで、M1は水素原子、アルカリ金属、アンモニウム塩基または有機アミン塩基であり、M2はアルカリ金属、アンモニウム塩基または有機アミン塩基であり、nは1~6の整数、aは1~4の整数、bは1~3の整数、cは1~3の整数である)で表わされるポリフルオロアルキルホスホン酸塩を乳化剤として、含フッ素ポリマーを分散させた含フッ素ポリマー水性分散液。 - ポリフルオロアルキルホスホン酸塩がアンモニウム塩として用いられた請求項1記載の含フッ素ポリマー水性分散液。
- 一般式〔I〕で表わされるポリフルオロアルキルホスホン酸塩乳化剤の水溶液の存在下で、含フッ素モノマーを乳化重合させて得られた請求項1記載の含フッ素ポリマー水性分散液。
- 請求項3記載の含フッ素ポリマー水性分散液を凝析して得られた含フッ素ポリマー。
- 含フッ素ポリマー水性分散液を塩析して得られた請求項4記載の含フッ素ポリマー。
- ポリマー分子中に含臭素または含ヨウ素単量体化合物、あるいは含ヨウ素臭素化合物に由来する臭素基および/またはヨウ素基を架橋性基として有する請求項4または5記載の含フッ素ポリマー。
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