Patent Application
20060194703
The present invention relates to a fluoropolymer liquid composition.
Fluoropolymers having sulfonic acid groups and/or carboxyl groups which may be in the form of salts (hereinafter sometimes referred to as “acid/acid salt groups”) have an established use as materials of ion exchange membranes for use in electrolytic soda processes, water electrolysis processes and so forth and, in recent years, they have attracted attention as materials for the manufacture of various sensor protecting membranes, gas dehumidifying device membranes and, in particular, proton conductive membranes and membrane/electrode assemblies [MEA] for solid polymer fuel cells, among others.
In these fields of application, the use has been contemplated of such acid/acid salt group-containing fluoropolymers in the form of films/membranes molded by cast film formation or by impregnation of porous supports therewith, for instance, and it is desirable that thin and compact films/membranes or large-area films/membranes be obtained.
As the method of obtaining membranous moldings of a sulfonic acid group-based acid/acid salt group-containing fluoropolymer, there is available a method which comprises forming membranous moldings from a fluoropolymer powder obtained by coagulation of an aqueous dispersion of an —SO2F group-containing fluoropolymer, followed by drying or from pellets further obtained from this powder and then hydrolyzing the membranous moldings as they are to thereby convert the —SO2F group to the sulfonic acid group.
However, this method has a problem in that it cannot give thin films/membranes since it is unfeasible for cast film formation or impregnation of porous supports and in that it is also difficult to obtain compact films/membranes.
As a method for solving this problem, there is known a method which comprises preparing an organosol by fluoropolymer transfer from an aqueous dispersion of an —SO2F group-containing fluoropolymer to an organic solvent, forming membranous moldings using this organosol and hydrolyzing the membranous moldings as they are to thereby convert the —SO2F group to the sulfonic acid group or a salt thereof (cf. e.g. Japanese Kokai Publication S57-115424 and Japanese Kokai Publication S57-115425).
However, this method has a problem in that the organosol is poor in film/membrane-forming property, and the document cited above has no description about the use of a film-forming auxiliary.
There is known dispersion which comprises a sulfonic acid salt group-containing, highly fluorinated ion exchange polymer particles of which about 25% by mass have a particle diameter of 2 to 30 nm (cf. e.g. Japanese Kohyo Publication 2001-504872). However, the dispersion described in this document tends to become highly viscous and has a problem in that the productivity in manufacturing films/membranes by cast film formation is low.
A method of obtaining membranous moldings of a sulfonic acid salt group-containing fluoropolymer is known which comprises subjecting a solution or aqueous dispersion of a fluoropolymer obtained by polymerizing a fluorine-containing monomer having such sulfonic acid salt group to ultrafiltration, adding such a cationophilic substance as polyethylene glycol as a film-forming auxiliary and forming the resulting composition into films/membranes by cast film formation (cf. e.g. Japanese Kokai Publication 2001-226425).
In cases where the cationophilic substance needs to be removed from the membranous moldings after formation thereof, this method is disadvantageous in that it is necessary to heat the moldings to the thermal decomposition temperature of the cationophilic substance which is a high molecular substance.
In view of the foregoing, it is an object of the present invention to provide a fluoropolymer liquid composition which is excellent in film/membrane-forming properties and can give acid/acid salt group-containing, i.e. sulfonic acid group- and/or carboxyl group-containing, fluoropolymer films/membranes.
The invention provides a fluoropolymer liquid composition comprising a fluoropolymer and a film-forming auxiliary,
The present invention also provides a method of producing an organosol,
The invention further provides a film/membrane obtainable by cast film formation using the above-defined fluoropolymer liquid composition.
The invention further provides a film/membrane obtainable by impregnating a porous support with the above-defined fluoropolymer liquid composition, followed by removal of the liquid medium.
The invention further provides an active substance-immobilized material comprising a fluoropolymer and an active substance, which is obtainable by applying, to a substrate, a liquid composition comprising said active substance and the above-defined fluoropolymer liquid composition.
The invention further provides an electrolyte membrane comprising the above-defined active substance-immobilized material.
The invention further provides a membrane/electrode assembly which comprises the above-defined electrolyte membrane.
The invention still further provides a solid polymer electrolyte fuel cell which comprises the above-defined film/membrane, the above-defined active substance-immobilized material, the above-defined electrolyte membrane and/or the above-defined membrane/electrode assembly.
In the following, the present invention is described in detail.
The fluoropolymer liquid composition of the invention comprises a fluoropolymer and a film-forming auxiliary.
The fluoropolymer liquid composition of the invention is judiciously used in manufacturing films/membranes by cast film formation, namely by applying the fluoropolymer liquid composition of the invention to a substrate or base material, followed by drying the same at ordinary temperature and/or with heating and, if necessary further followed by immersion in water, or in manufacturing films/membranes by impregnating porous supports with that composition.
The fluoropolymer liquid composition of the invention generally occurs as a liquid composition and is a fluoropolymer dispersion composition-comprising fluoropolymer fine particles of a fluoropolymer as dispersed in a dispersion medium comprising an aqueous dispersion medium, an organic dispersion medium, etc. The “fluoropolymer liquid composition” so referred to herein includes, within the meaning thereof, not only the above-mentioned liquid composition but also a composition resulting from partial gelation of the above-mentioned composition.
The fluoropolymer mentioned above comprises acid/acid salt fluorovinyl ether units represented by the above general formula (I). The “acid/acid salt fluorovinyl ether units” constitute a part of the molecular structure of the fluoropolymer and are moieties derived from the fluorovinyl-ether derivative or acid salt fluorovinyl-ether derivative to be described later herein. The “acid/acid salt fluorovinyl ether units” are acid group-containing acid fluorovinyl ether units or acid salt group-containing acid salt fluorovinyl ether units. The “acid group” so referred to herein includes, within the meaning thereof, a sulfonic acid group, a group represented by —SO2X1 in which X1 is —NR5R6, among the groups represented by A1 in the above general formula (I), and a carboxyl group, and the “acid salt group” includes, within the meaning thereof, a sulfonic acid group in the form of a salt and a carboxyl group in the form of a salt. The above-mentioned acid salt group may be in an ionized form depending on the pH, among others, of the fluoropolymer liquid composition.
The above-mentioned acid group is preferably a sulfonic acid group, and the above-mentioned acid salt group is preferably a sulfonic acid group in the form of an alkali metal salt or an alkaline earth metal salt.
The acid/acid salt fluorovinyl ether units may be derived from one single monomer or two or more monomers.
The fluoropolymer may also be one in each molecule of which acid fluorovinyl ether units and acid salt fluorovinyl ether units coexist.
The above-mentioned fluoropolymer may also comprise a combination of a fluoropolymer comprising acid fluorovinyl ether units and a fluoropolymer comprising acid salt fluorovinyl ether units and, in the case of combined use, each of the fluoropolymer fine particles, which are to be mentioned later herein, may also be one in which a fluoropolymer comprising acid fluorovinyl ether units and a fluoropolymer comprising acid salt fluorovinyl ether units coexist.
As regards the above-mentioned acid/acid salt fluorovinyl ether units, n in the general formula (I) represents an integer of 0 to 3. The integer n is preferably 0 or 1, more preferably 0. The symbol m in the general formula (I) represents an integer of 1 to 5. The integer m is preferably 2.
Y1 in the general formula (I) represents a halogen atom or a perfluoroalkyl group, and n atoms/groups of Y1 may be the same or different. Y2 in the general formula (I) represents a halogen atom, and m atoms of Y2 may be the same or different. The halogen atom represented by Y1 is not particularly restricted but may be a fluorine, chlorine, bromine or iodine atom; preferably it is a fluorine or chlorine atom. The perfluoroalkyl group is not particularly restricted but includes, among others, trifluoromethyl and pentafluoroethyl. As the halogen atom Y2, there may be mentioned the same ones as the halogen atoms represented by Y1. Referring to the above general formula (I), the above Y1 is preferably a trifluoromethyl group, and the above Y2 is preferably a fluorine atom.
In the above general formula (I), A1 represents —SO2X1 or —COOZ1. X1 represents —OH, —ONR1R2R3R4, —NR5R6 or —OM11/L, and R1, R2, R3 and R4 may be the same or different and each represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms. The alkyl group containing 1 to 4 carbon atoms is not particularly restricted but may be a methyl, ethyl, propyl or butyl group. R5 and R6 are the same or different and each represents a hydrogen atom, an alkali metal, an alkyl group or a sulfonyl-containing group. The alkali metal represented by R5 and/or R6 is not particularly restricted but may be, for example, Li, Na, K or Cs. The alkyl group represented by R5 and/or R6 is not particularly restricted but may be, for example, an alkyl group containing 1 to 4 carbon atoms. The alkyl group represented by R5 and/or R6 may be substituted by a halogen atom or atoms. The sulfonyl-containing group is a sulfonyl-containing, fluorine-containing alkyl group, for example a fluorine-containing alkylsulfonyl group, which may have a substituent at the terminal thereof. As the fluorine-containing alkylsulfonyl group, there may be mentioned —SO2Rf1Q (in which Rf1 represents a fluorine-containing alkylene group and Q represents an organic group) and the like. The organic group is, for example, —SO2F and, when the group X1 is —NR5R6, —SO2X1 represented by Al in the general formula (I) may be such an unlimited chain as —SO2(NR5SO2Rf1SO2)kNR5SO2— (k representing an integer of not smaller than 1).
Z1 represents a hydrogen atom, NR7 R8R9R10 or -M21/L, and R7, R8, R9 and R10 may be the same or different and each represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms. The alkyl group containing 1 to 4 carbon atoms as represented by R7, R8, R9 and/or R10 is not particularly restricted but includes the same ones as the alkyl groups containing 1 to 4 carbon atoms as represented by R1, R2, R3 and/or R4. M1 and M2 each represents a metal whose valence is L, and said metal whose valance is L is a metal belonging to the group 1, 2, 4, 8, 11, 12 or 13 of the periodic table. The metal whose valence is L is not particularly restricted but includes, for example, Li, Na, K and Cs as the metal of group 1 of the periodic table, Mg and Ca as the metal of group 2 of the periodic table, Al as the metal of group 4 of the periodic table, Fe as the metal of group 8 of the periodic table, Cu and Ag as the metal of group 11 of the periodic table, Zn as the metal of group 12 of the period table, and Zr as the metal of group 13 of the periodic table. Preferably, the above-mentioned group A1 is —SO2X1.
Preferred as the acid/acid salt fluorovinyl ether units in the fluoropolymer are those in which, in the general-formula (I), Y1 is a trifluoromethyl group, Y2 is a fluorine atom, n is 0 or 1 and m is 2. More preferred are those in which, in the general formula (I), Y1 is a trifluoromethyl group, Y2 is a fluorine atom, n is 0 and m is 2.
The fluoropolymer is preferably a binary or multinary copolymer comprising the acid/acid salt fluorovinyl ether units and ethylenic monomer-derived ethylenic monomer units.
The ethylenic monomer has a vinyl group whose hydrogen atoms may optionally be substituted either partly or wholly by a fluorine atom or atoms. The “ethylenic monomer” so referred to herein does not include those fluorovinyl-ether derivatives or acid salt fluorovinyl-ether derivatives which are to be mentioned later herein.
As the ethylenic monomer, there may be mentioned, for example, haloethylenic monomers represented by the general formula:
CF2═CF—Rf2
The ethylenic monomer may also be a copolymerizable monomer other than the above-mentioned haloethylenic monomer or hydrogen-containing fluoro-ethylenic monomer. The other copolymerizable monomer is not particularly restricted provided that it can provide the fluoropolymer with one or more of various functions; thus, it can be appropriately selected from among various copolymerizable monomers so as to answer the intended purpose, for example the control of the rate of polymerization, the control of the polymer composition, the control of the mechanical properties, such as elastic modulus, or the introduction of crosslinking sites. As such monomers, there may be mentioned monomers having two unsaturated bonds, for example perfluoro-divinyl ether, and cyano group-containing monomers. The content of the ethylenic monomer units derived from the other copolymerizable monomer in fluoropolymer is preferably within the range within which the fundamental performance characteristics of that polymer will not be impaired.
The ethylenic monomer units may be derived from one single or two or more ethylenic monomer species.
The ethylenic monomer preferably comprises at least one monomer selected from the group consisting of CF2═CF2, CH2═CF2, CF2═CFCl, CF2═CFH, CH2═CFH, CF2═CFCF3, and fluorovinyl ethers represented by CF2═CF—O—Rf5 (in which Rf5 represents a fluoroalkyl group containing 1 to 9 carbon atoms or a fluoro-polyether group containing 1 to 9 carbon atoms). Rf5 in the fluorovinyl ether is preferably a perfluoroalkyl group containing 1 to 3 carbon atoms.
The above-mentioned ethylenic monomer is preferably a perhalo-ethylenic monomer, in particular perfluoro-. ethylenic monomer, and more preferably is CF2═CF2.
The content of the acid/acid salt fluorovinyl ether units in the fluoropolymer is preferably 10 to 20 mole percent. When it is lower than 10 mole percent, the proton transport and other performance characteristics of the film/membrane obtained from the resulting fluoropolymer liquid composition may be deteriorated in some instances and, when it exceeds 20 mole percent, the mechanical strength of the film/membrane may become insufficient in certain cases. The above-mentioned “content of the acid/acid salt fluorovinyl ether units” is the ratio of the number of moles of the monomer or monomers from which the acid/acid salt fluorovinyl ether units are derived relative to the number of moles of the monomers from which all monomer units in the fluoropolymer molecule are derived. The “all monomer units” so referred to above include all monomer-derived units from the viewpoint of the molecular structure of the fluoropolymer. Therefore, the “monomers from which all monomer units are derived” correspond to the whole amount of the monomers constituting the fluoropolymer. The above-mentioned acid/acid salt fluorovinyl ether unit content is the value obtained by infrared spectrometric analysis [IR] or by NMR spectrometry in molten state at 300° C.
The fluoropolymer preferably amounts to 1 to 60% by mass of the fluoropolymer liquid composition. When the amount is smaller than 1% by mass, each single application of the fluoropolymer liquid composition in manufacturing film/membranes therefrom will give only a little film/membrane thickness, so that a plurality of applications will often be required to attain the desired film/membrane thickness. When it exceeds 60% by mass, the fluoropolymer liquid composition tends to gelate, hence it may become difficult to obtain uniform films/membranes. A more preferred lower limit is 5% by mass, and a more preferred upper limit is 15% by mass.
The fluoropolymer liquid composition according to the invention comprises a film-forming auxiliary as well as the above-mentioned fluoropolymer.
The film-forming auxiliary is one compatible with water. The term “water” in the phrase “compatible with water” may be any liquid that is generally recognized as “water” in the field to which the present invention relates. Thus, for example, it may be “water” in a mixture with a water-soluble organic solvent or the like, or deionized water, for instance. Pure water is preferred, however. The film-forming auxiliary may be one completely miscible with water at any mixing ratio upon mixing with water or one at least partly compatible with water.
The phrase “compatible with water” as used herein means that the auxiliary shows solubility, in water, of not lower than 1% by mass.
The film-forming auxiliary has a boiling point exceeding 100° C. but not higher than 300° C. When the boiling point is 100° C. or lower, it is generally equal to or lower than the boiling point of water, so that, in preparing the fluoropolymer liquid composition according to the invention by the organosol producing method (to be described later herein) which comprises incorporating the film-forming auxiliary into fluoropolymer aqueous dispersion comprising the fluoropolymer fine particles (to be described later herein) comprising the fluoropolymer as dispersed in an aqueous dispersion medium, it becomes impossible to remove the aqueous dispersion medium alone while the film-forming auxiliary is retained. When the boiling point is higher than 300° C., it is difficult to remove the film-forming auxiliary in cases where it is necessary to remove the film-forming auxiliary from the film/membrane formed using the resulting liquid composition. A preferred lower limit to the boiling point of the film-forming auxiliary is 150° C., and a preferred upper limit is 250° C.
The film-forming auxiliary is an organic liquid. The term “organic liquid” as used herein means an organic compound which occurs as a liquid at ordinary temperature of about 20° C. The organic liquid is not particularly restricted but may be any of those which are compatible with water and have a boiling point exceeding 100° C. but not higher than 300° C. Preferred are those having the ability to swell or partly dissolve the surface of the fluoropolymer fine particles and, as the organic liquids having such ability, there may be mentioned, for example, phosphoric acid esters, cyclic amides or cyclic-amide derivatives, imidazolidinone or imidazolidinone derivatives, ethylene oxide oligomer monohydroxy ethers, dimethyl sulfoxide [DMSO], dimethylformamide [DMF], 1,4-dioxane, trioxane, isophorone, cyclohexanone, sulfolane; and glycerol derivatives containing one or two hydroxyl groups within the molecule, for example glycerol dimethyl ether.
The above-mentioned phosphoric acid esters are not particularly restricted but include, among others, phosphoric triesters derived from phosphoric acid and alcohols containing 1 to 5 carbon atoms, for example trimethyl phosphate and triethyl phosphate.
The cyclic amides or cyclic-amide derivatives are not particularly restricted but include, among others, pyrrolidone and derivatives thereof resulting from substitution of an alkyl group(s) containing 1 to 5 carbon atoms for a hydrogen atom(s) thereof, for example 2-methylpyrrolidone.
The imidazolidinone or imidazolidinone derivatives are not particularly restricted but include, among others, imidazolidinone and derivatives thereof resulting from substitution of an alkyl group(s) containing 1 to 5 carbon atoms for a hydrogen atom(s) thereof, for example 3,4-dimethylimidazolidinone.
The ethylene oxide oligomer monohydroxy ethers are not particularly restricted but molecules resulting from coupling, via an ether bond, of one alkyl group containing 1 to 10 carbon atoms to an adduct formed by 2 to 10 ethylene oxide molecules. The number of moles of addition of ethylene oxide is a mean value for the set of all ethylene oxide oligomer monohydroxy ether molecules.
The ethylene oxide oligomer monohydroxy ethers include, among others, diethylene glycol monoalkyl ethers and triethylene glycol monoalkyl ethers and, as such ethers, there may be mentioned diethylene glycol monomethyl ether and triethylene glycol monomethyl ether.
The “film-forming auxiliary” as used herein does not include, within the meaning thereof, those “lower alcohols” which are to be mentioned later herein, among the organic liquids which are compatible with water and having a boiling point within the range specified above. The film-forming auxiliary may comprise one single species or two or more species.
Phosphoric acid esters, cyclic amides or cyclic-amide derivatives and ethylene oxide oligomer monohydroxy ethers are preferred as the organic liquids. Among them, phosphoric acid esters are more preferred, phosphoric acid triesters are still more preferred, and triethyl phosphate is most preferred.
Preferably, the fluoropolymer liquid composition according to the invention further comprises a lower alcohol as well as the fluoropolymer and film-forming auxiliary.
The lower alcohol can be used in adjusting the surface tension of the fluoropolymer liquid composition.
The lower alcohol so referred to herein is a monoalcohol containing not more than 5 carbon atoms. The monoalcohol containing not more than 5 carbon atoms is not particularly restricted but includes, among others, straight or branched alkanols containing 1 to 5 carbon atoms, which may optionally be substituted by a fluorine atom or atoms. The alkanols preferably contain 1 to 3 carbon atoms. As such alkanols, there may be mentioned, for example, methanol, ethanol, propanol, isopropanol, and tetrafluoropropanol species such as 2,2,3,3-tetrafluoropropanol.
The lower alkanols may be used singly or two or more of them may be used in combination.
The fluoropolymer liquid composition according to the invention is a fluoropolymer dispersion composition comprising fluoropolymer fine particles comprising a fluoropolymer, and a film-forming auxiliary. The “fluoropolymer dispersion composition” so referred to herein also includes, within the meaning thereof, those dispersions resulting from dispersion of the above-mentioned fluoropolymer fine particles as the dispersoid in a dispersion medium comprising an aqueous dispersion medium and an organic dispersion medium, among others, in which the fluoropolymer fine particles have been partly dissolved. In cases where the fluoropolymer liquid composition according to the invention further comprises the above-mentioned lower alcohol, the fluoropolymer dispersion composition comprises the lower alcohol in the dispersion medium.
Since the fluoropolymer liquid composition according to the invention occurs as the fluoropolymer dispersion composition mentioned above and contains the film-forming auxiliary mentioned above, it is expected that, in the step of film/membrane molding, the film-forming auxiliary adsorbed on the surface of the fluoropolymer fine particles will swell or partially dissolve the particles, thereby making the fluoropolymer fine particles compatible and easy to fuse with one another.
While the interaction between the film-forming auxiliary and fluoropolymer fine particles cannot be observed by the eye when the composition is in liquid form before film/membrane molding, a photograph of the film/membrane obtained as taken by using an atomic force microscope [AFM] shows swelling of the polymer particles and fusion of the polymer particles, as shown in
In the case of the prior fluoropolymer solution, not a dispersion, the film-forming auxiliary functions merely as a drying retardant in the step of film/membrane molding and, although it tends to reduce the occurrence of cracking due to stress relaxation as a result of surface drying retardation, there is a problem, namely, the polymer particles are not fused together, so that the cracking resistance of the resulting film/membrane surface is unsatisfactory and the film/membrane is poor in strength and other physical characteristics.
The fluoropolymer fine particles comprise not less than 25% by mass of those fluoropolymer fine particles which are substantially spherical.
The phrase “comprising not less than 25% by mass of those fluoropolymer fine particles which are substantially spherical” as used herein means that not less than 25% by mass of the fluoropolymer fine particles are spherical fluoropolymer fine particles.
The particle shape of the fluoropolymer fine particles can be judged by taking the aspect ratio as a measure.
The term “substantially spherical” as used herein means that the aspect ratio is not higher than 3. Generally, the shape comes nearer and nearer to spherical as the aspect ratio approaches 1. The aspect ratio of the fluoropolymer fine particles is preferably not higher than 3. A more preferred upper limit is 2, and a still more preferred upper limit is 1.5.
Generally, if polymer fine particles are anisotropic in particle shape, a dispersion of the polymer fine particles will tend to show a high viscosity and, if the polymer fine particle dispersion is high in viscosity, it will be unfavorably difficult to increase the polymer fine particles concentration in the dispersion.
When the above-mentioned fluoropolymer fine particles comprise not less than 25% by mass of those fluoropolymer fine particles which are substantially spherical, it is possible to lower the viscosity of the fluoropolymer dispersion composition as compared with the case of a composition containing no substantially spherical fluoropolymer fine particles and, further, it is possible to increase the solid matter concentration of the fluoropolymer dispersion composition and, therefore, it is possible to realize high levels of productivity in film/membrane manufacture by cast film formation or other film/membrane manufacturing techniques. On the other hand, spherical particles tend to cause cracking in film/membrane manufacture by cast film formation or other film/membrane manufacturing techniques since they show only weak interparticle interactions. The present invention has made it possible to prevent cracking by using the above-mentioned film-forming auxiliary.
The fluoropolymer fine particles preferably comprise not less than 50% by mass of spherical fluoropolymer fine particles.
The fluoropolymer dispersion composition whose spherical fluoropolymer fine particle content is within the above-specified range can be readily obtained by preparing it from a dispersion obtained by emulsion polymerization. Even a dispersion composition whose spherical fluoropolymer fine particle content is 90% by mass or higher can be obtained from a dispersion obtained by emulsion polymerization. The above-mentioned fluoropolymer dispersion composition can also be prepared by adjusting a composition having a relatively high content of spherical fluoropolymer fine particles by incorporating therewith-fine particles not substantially spherical in shape among the fluoropolymer fine particles so that the dispersion composition may have the desired performance characteristics.
The mass proportion of the spherical fluoropolymer fine particles is the value obtained by converting the proportion of spherical fluorine-containing fine particles contained in an image of fluoropolymer fine particles as obtained by using a scanning or transmission microscope, an atomic force microscope or the like to the mass of spherical fluoropolymer fine particles.
The fluoropolymer fine particles preferably have an average particle diameter of not smaller than 10 nm. When the diameter is smaller than 10 nm, the fluoropolymer dispersion composition may cover active sites and will fail to give good battery characteristics in some of the cases where the dispersion composition is used as an electrode material for solid polymer fuel cells.
When the average particle diameter is within the above range, an upper limit may be set at 300 nm, for instance, considering the stability of the fluoropolymer dispersion composition and the ease of preparation of the fluoropolymer precursor which is to be described later herein. Average particle diameters exceeding 300 nm, however, will not greatly influence the battery characteristics.
The fluoropolymer fine particles preferably have an average particle diameter of 10 to 300 nm. A more preferred lower limit to the average particle diameter is 30 nm, and a more preferred upper limit is 160 nm.
The above-mentioned aspect ratio and average particle diameter can be determined by observing the fluoropolymer fine particles using a scanning or transmission microscope, an atomic force microscope or the like, measuring the major and minor axes of at least 20 fine particles on the image obtained and calculating the major-to-minor axis length ratio (major axis/minor axis) as the aspect ratio and the mean of the major and minor axis lengths as the average particle diameter to be further described later herein, respectively.
The above-mentioned fluoropolymer dispersion composition preferably comprises at least 25% by mass of those spherical fluorine-containing fine particles which have an average particle diameter of not smaller than 10 nm among the fluoropolymer fine particles.
More preferably, the fluoropolymer dispersion composition comprises at least 25% by mass of those spherical fluorine-containing fine particles which have an average particle diameter of 10 to 300 nm among the fluoropolymer fine particles.
Still more preferably, the fluoropolymer dispersion composition comprises at least 25% by mass of those spherical fluorine-containing fine particles which have an average particle diameter of 30 to 160 nm among the fluoropolymer fine particles.
The fluoropolymer liquid composition according to the invention is preferably a dispersion obtained by incorporating a film-forming auxiliary into fluoropolymer aqueous dispersion in which fluoropolymer fine particles are dispersed in an aqueous dispersion medium. Since the “dispersion obtained by incorporating a film-forming auxiliary” is obtained by incorporating a film-forming auxiliary into fluoropolymer aqueous dispersion comprising fluoropolymer fine particles dispersed in an aqueous dispersion medium, the aqueous dispersion medium in the above-mentioned fluoropolymer aqueous dispersion and the film-forming auxiliary incorporated in the fluoropolymer aqueous dispersion, as they are, serve as the dispersion medium in the above-mentioned “dispersion obtained by incorporating a film-forming auxiliary”. Since the above-mentioned “dispersion obtained by incorporating a film-forming auxiliary” comprises a film-forming auxiliary compatible with water, as described hereinabove, the aqueous dispersion medium and the film-forming auxiliary generally form a uniform liquid. In the above-mentioned “dispersion obtained by incorporating a film-forming auxiliary”, there are dispersed the above-mentioned fluoropolymer fine particles in such dispersion medium.
In the above-mentioned “dispersion obtained by incorporating a film-forming auxiliary”, the film-forming auxiliary preferably amounts to 10 to 99% by mass relative to the total mass of the film-forming auxiliary and aqueous dispersion medium. At levels lower than 10% by mass, the film/membrane-forming property of the resulting fluoropolymer liquid composition may possible become insufficient.
In cases where the fluoropolymer liquid composition according to the invention further comprises a lower alcohol, the above-mentioned “dispersion obtained by incorporating a film-forming auxiliary” is preferably one obtained by incorporating the film-forming auxiliary and lower alcohol into fluoropolymer aqueous dispersion comprising fluoropolymer fine particles dispersed in an aqueous dispersion medium, and the above-mentioned aqueous dispersion medium, film-forming auxiliary and lower alcohol generally constitute a uniform liquid to serve as the dispersion medium in the “dispersion obtained by incorporating the film-forming auxiliary”.
The term “fluoropolymer aqueous dispersion” as used herein means a dispersion of fluoropolymer fine particles dispersed in an aqueous dispersion medium as prepared prior to incorporation of the film-forming auxiliary. The concentration of the fluoropolymer fine particles in the fluoropolymer aqueous dispersion is preferably 2 to 60% by mass. A more preferred upper limit is 30% by mass.
The aqueous dispersion medium in the above-mentioned fluoropolymer aqueous dispersion and the aqueous dispersion medium in the above-mentioned “dispersion obtained by incorporating a film-forming auxiliary” are only required to comprise water, hence they may comprise a water-soluble organic solvent as well as water.
The above-mentioned fluoropolymer dispersion composition is preferably an organosol comprising fluoropolymer fine particles dispersed in an organic medium. The “organosol” so referred to herein is a sol comprising fluoropolymer fine particles and an organic medium in which the fluoropolymer fine particles are dispersed in the organic medium. The organosol is preferably one obtained by removing the aqueous dispersion medium from the above-mentioned “dispersion obtained by incorporating the film-forming auxiliary”.
The organic medium comprises the film-forming auxiliary in the organosol obtained by removing the aqueous medium from the “dispersion obtained by incorporating the film-forming auxiliary”. The organic medium in the organosol further contains water or does not contain water, and the water content is preferably not higher than 10% by mass relative to the organic medium. A more preferred upper limit is 5% by mass. The organic medium is preferably a water-free one since the organosol obtained can form films/membranes excellent in uniformity. In cases where the fluoropolymer liquid composition according to the invention further comprises a lower alcohol, the above-mentioned organic medium comprises the film-forming auxiliary and the lower alcohol.
The fluoropolymer liquid composition according to the invention may contain an additive or additives generally used in liquid compositions, for example a stabilizer and the like. When the fluoropolymer liquid composition according to the invention is a fluoropolymer dispersion composition comprising fluoropolymer fine particles dispersed in a dispersion medium comprising an aqueous dispersion medium, it may further comprise a surfactant and the like generally used in aqueous dispersions.
Preferred as the fluoropolymer liquid composition according to the invention is the above-mentioned organosol in which the content of water is not higher than 10% by mass relative to the organic medium, since such organosol is excellent in film/membrane-forming property.
The fluoropolymer liquid composition according to the invention can be prepared by using any of the conventional methods, for instance.
The level of addition of the film-forming auxiliary is preferably 0.1 to 100 parts by mass relative to each part by mass of the fluoropolymer. At levels lower than 0.1 part by mass, the film/membrane-forming property of the resulting fluoropolymer liquid composition may possibly be insufficient in forming films/membranes using the composition. At levels exceeding 100 parts by mass, the effects producible will no more correspond to the addition level and this is unfavorable from the economical viewpoint. A more preferred lower limit is 0.5 part by mass, and a more preferred upper limit is 20 parts by mass.
The level of addition of the film-forming auxiliary can be adequately selected according to the acid group/acid salt group content of the fluoropolymer and the film/membrane molding conditions.
In cases where the fluoropolymer is a fluoropolymer having a relatively high acid group/acid salt group content, the fluoropolymer liquid composition obtained even at a relatively low addition level will have good film/membrane-forming property and it is preferred that the level of addition of the film-forming auxiliary be low so that the load on the environment may also be reduced; levels of 0.1 to 1 part by mass per part by mass of the fluoropolymer are preferred. The phrase “fluoropolymer having a relatively high acid group/acid salt group content” as used herein means a fluoropolymer such that the molecular weight per acid group/acid salt group is lower than 900.
In cases where the fluoropolymer is a fluoropolymer having a relatively low acid group/acid salt group content, a relatively high film-forming auxiliary addition level is required so that uniform films/membranes may be obtained using the resulting fluoropolymer liquid composition, and levels of 3 to 20 parts by mass per part by mass of the fluoropolymer are preferred. The phrase “fluoropolymer having a relatively low acid group/acid salt group content” as used herein means a fluoropolymer such that the molecular weight per acid group/acid salt group is not lower than 900.
From the industrial productivity viewpoint, it is preferred that the film-forming auxiliary addition level be relatively low; thus, levels of 0.1 to 1 part by mass per part by mass of the fluoropolymer are preferred.
Considering the film/membrane-forming property and the uniformity and other physical properties of the films/membranes obtained, however, it is preferred that the level of addition of the film-forming auxiliary be relatively high; thus, levels of 3 to 20 parts by mass per part by mass of the fluoropolymer are preferred.
The fluoropolymer liquid composition according to the invention may sometimes gelate upon incorporation of the film-forming auxiliary. However, the gel can be again converted to a sol by dilution with an aqueous medium such as water.
In cases where the fluoropolymer liquid composition according to the invention further contains a lower alcohol, the lower alcohol is incorporated at levels of 0.5 to 5 parts by mass per part by mass of the fluoropolymer. In forming films/membranes using the fluoropolymer liquid composition according to the invention, the addition of the lower alcohol at levels given above can lower the surface tension of the fluoropolymer liquid composition, making it possible to form uniform films/membranes.
In cases where the fluoropolymer liquid composition according to the invention further comprise a lower alcohol, the order of addition of the film-forming auxiliary and lower alcohol is not particularly restricted. Thus, the lower alcohol may be added after addition of the film-forming auxiliary, or the film-forming auxiliary may be added after addition of the lower alcohol.
In cases where the fluoropolymer liquid composition according to the invention occurs as an organosol comprising fluoropolymer fine particles dispersed in an organic medium, the organosol is preferably one obtained by the production method given below.
Thus, the method of producing organosols according to the invention is a method for obtaining fluoropolymer dispersion compositions comprising fluoropolymer fine particles dispersed in an organic medium from fluoropolymer aqueous dispersion comprising fluoropolymer fine particles dispersed in an aqueous medium which method comprises incorporating the film-forming auxiliary into the fluoropolymer aqueous dispersion, followed by water evaporation.
The term “water evaporation” used herein means evaporation of the water in the aqueous medium in the dispersion obtained by incorporating the film-forming auxiliary into the fluoropolymer aqueous dispersion. The water evaporation can be carried out using an evaporator, and the evaporator is not particularly restricted but may be, for example, a rotary evaporator. Although the water evaporation may be carried out at room temperature, it is preferred that the composition comprising the fluoropolymer aqueous dispersion and the film-forming auxiliary be heated at 50 to 300° C. If necessary, the evaporation may be carried out under reduced pressure. By heating at the above temperature, it is possible to remove the water lower in boiling point than the film-forming auxiliary from the “dispersion obtained by incorporating the film-forming auxiliary” which comprises the fluoropolymer fine particles dispersed in the dispersion medium composed of the aqueous medium and film-forming auxiliary while the film-forming auxiliary is retained.
The fluoropolymer liquid composition according to the invention, which is obtained by incorporating the film-forming auxiliary into the fluoropolymer, is preferably one in which the fluoropolymer is obtained by the method described below.
Thus, the fluoropolymer is preferably one obtained by emulsion polymerization of a fluorovinyl-ether derivative represented by the general formula (II):
CF2═CF—O—(CF2CFY1—O)n—(CFY2)m-A2 (II)
The halogen atom represented by X2 is not particularly restricted but may be any of fluorine, chlorine, bromine and iodine atoms. A fluorine or chlorine atom is preferred, however.
The alkoxy group containing 1 to 4 carbon atoms as represented by Z2 is not particularly restricted but, preferably is a n-alkoxy group, more preferably a methoxy group. The group —SO2X2 is preferably —SO2F, and the group —COZ2 is preferably —COOCH3. In the above general formula (II), A2 is preferably —SO2X2.
Y1, Y2, n and m in the above general formula (II) are respectively the same as Y1, Y2, n and m in the general formula (I) given hereinabove. Y1, Y2, n and m in the general formula (I) representing the acid/acid salt fluorovinyl ether unit mentioned above are derived from Y1, Y2, n and m in the general formula (II) representing the fluorovinyl-ether derivative.
The emulsion polymer dispersion obtained by emulsion polymerization of the above-mentioned fluorovinyl-ether derivative contains precursor fluoropolymer fine particles comprising a fluoropolymer precursor. The term “fluoropolymer precursor” as used herein means a polymer giving the above-mentioned fluoropolymer upon hydrolysis treatment, as described later herein.
The fluoropolymer precursor comprises fluorovinyl-ether derivative units derived from the above-mentioned fluorovinyl-ether derivative and has —SO2X2 and/or —COZ2 groups. The fluoropolymer precursor may be one obtained by emulsion polymerization of one or two or more fluorovinyl-ether derivatives.
The emulsion polymerization is generally carried out in an aqueous reaction medium. The term “aqueous reaction medium” as used herein means a medium in which the emulsion polymerization is carried out and which comprises water. The aqueous reaction medium is only required to comprise water, hence it may comprise a water-soluble organic solvent as well as water; one containing no water-soluble organic solvent is preferred, however. The aqueous reaction medium may contain one or more of those additives and emulsifying agents which are generally used in aqueous dispersions, for example surfactants, stabilizers, and existing emulsifiers to be described later herein. The aqueous reaction medium does not include, within the meaning thereof, such monomer(s) as the fluorovinyl-ether derivative(s) occurring in the reaction system in which the emulsion polymerization is carried out or the polymer formed by the emulsion polymerization. After the above-mentioned emulsion polymerization, the aqueous reaction medium serves as a dispersion medium (aqueous dispersion medium) in the emulsion polymer dispersion and can be used as it is as an aqueous medium in the hydrolysis treatment to be mentioned later herein.
In the above emulsion polymerization, the method of emulsification may be one comprising carrying out the emulsification using any of those conventional emulsifiers generally used in emulsion polymerization (hereinafter referred to as “existing emulsifiers”), for example ammonium perfluorooctanoate [C7F15COONH4], or one comprising causing emulsification by using an agent not belonging to the category of existing emulsifiers but having emulsifying activity (hereinafter such agent is referred to as “emulsifying agent”) and causing the same to bind to the polymer to thereby provide the polymer with emulsifying activity, or one comprising carrying out the emulsification by using both an existing emulsifier and such an emulsifying agent as defined above. As such emulsifying agent, there may be mentioned, among others, compounds having sulfonic acid groups in salt form. In the emulsion polymerization, the existing emulsifier and/or the emulsifying agent is generally used in an amount of 0.01 to 10% by mass relative to the aqueous reaction medium.
The above-mentioned emulsifying agent may be, for example, an acid salt fluorovinyl-ether derivative represented by the general formula (III):
CF2═CF—O—(CF2CFY1—O)n—(CFY2)m-A3 (III)
The alkyl group containing 1 to 4 carbon atoms as represented by R1, R2, R3 and/or R4 is not particularly restricted but may be any of methyl, ethyl, propyl and butyl groups. The alkali metal M3 is not particularly restricted but includes, for example, Li, Na, K, Cs, etc. The alkaline earth metal M4 is not particularly restricted but includes, for example, Mg, Ca, etc.
The alkyl group containing 1 to 4 carbon atoms as represented by R7, R8, R9 and/or R10 is not particularly restricted but includes the same ones as the alkyl groups containing 1 to 4 carbon atoms mentioned above referring to R1, R2, R3 and R4. The alkali metal M5 is not particularly restricted but includes the same ones as the above-mentioned alkali metals represented by M3. The alkaline earth metal M6 is not particularly restricted but includes, for example, the same ones as the alkaline earth metals mentioned above referring to M4.
The acid salt fluorovinyl-ether derivative is preferably one represented by the general formula (III) in which A3 is —SO3X3.
The above-mentioned acid salt fluorovinyl-ether derivative and the above-mentioned fluorovinyl-ether derivative are common with the above-mentioned ethylenic monomer in that they can have a vinyl group whose hydrogen atoms may be wholly substituted by fluorine atoms but differ from the ethylenic monomer giving the ethylenic monomer units mentioned above in that they give the above-mentioned acid/acid salt fluorovinyl ether units in the fluoropolymer upon hydrolysis treatment following emulsion polymerization.
When the above-mentioned acid salt fluorovinyl-ether derivative is used, emulsification can be effected even if the aqueous reaction medium contains no existing emulsifier, so that, unlike the prior art, it is not necessary to remove any existing emulsifier after emulsion polymerization. The acid salt fluorovinyl-ether derivative shows emulsifying activity in the emulsion polymerization and, further, since it is an ethylenic compound, it is possible to cause it to participate as a monomer in the polymerization reaction to constitute at least a part of the molecular structure of the fluoropolymer precursor. The polymer chain obtained by polymerizing the above-mentioned acid salt fluorovinyl-ether derivative can also have emulsifying activity.
In the above-mentioned emulsion polymerization, it is preferred that an emulsifying agent be used, without using any existing emulsifier, since there is no need for emulsifier removal after the polymerization reaction and, further, the agent having emulsifying activity can be used as a monomer. Under certain polymerization conditions, the above emulsion polymerization may result in a decreased number of fluoropolymer precursor particles with an increased particle size, which in turn may increase the load on the ultrafiltration membrane when the treatment for removing low-molecular-weight substances, which is to be described later herein, is carried out in the manner of ultrafiltration and, further, which may render the product films/membranes not uniform in the step of film/membrane molding. In such cases, existing emulsifiers are preferably used since those inconveniences can be easily avoided with them.
The above emulsion polymerization is preferably carried out using existing emulsifiers.
The above emulsion polymerization can be carried out in the conventional manner except that the above-mentioned emulsifying agent can be used.
The emulsion polymerization may also be carried out in the manner of the so-called “seed polymerization” which comprises diluting the above-mentioned dispersion obtained by polymerization using the above-mentioned existing emulsifier and/or emulsifying agent in an amount larger than 0.01 to 10% by mass relative to the aqueous reaction medium and then further continuing the polymerization so that the number of precursor fluoropolymer fine particles in the emulsion polymer dispersion obtained may be increased.
In preparing the fluoropolymer liquid composition according to the invention, the above-mentioned emulsion polymer dispersion comprising precursor fluoropolymer fine particles may be one obtained by carrying out the emulsion polymerization in the simultaneous presence of a fluorovinyl-ether derivative represented by the above general formula (II) and an acid salt fluorovinyl-ether derivative represented by the above general formula (III). The precursor fluoropolymer fine particles, which have the hydrophobic —SO2X2 and/or —COZ2 groups coming from the fluorovinyl-ether derivative and the hydrophilic —SO3X3 and/or —COOZ3 groups coming from the acid salt fluorovinyl-ether derivative, can take a core/shell structure with the fluorovinyl-ether derivative-derived polymer chain(s) forming the core and the acid salt fluorovinyl-ether derivative-derived polymer chain(s) forming the shell.
The emulsion polymer dispersion comprising the precursor fluoropolymer fine particles may be one obtained by carrying out the emulsion polymerization in the simultaneous presence of an acid salt fluorovinyl ether unit-based polymer obtained by polymerizing the above-mentioned acid salt fluorovinyl-ether derivative and the above-mentioned fluorovinyl-ether derivative. The precursor fluoropolymer fine particles obtained by this method comprise seed polymers.
In cases where the fine particles comprising the fluoropolymer precursor have or comprise the above-mentioned core/shell structure or seed polymers, the above-mentioned acid salt fluorovinyl-ether-derivative and the polymer chains comprising the acid salt fluorovinyl-ether derivative have emulsifying activity and, therefore, it is not necessary to add, in the step of polymerization, any of the emulsifiers generally used in the conventional emulsion polymerization and there is no need for emulsifier removal in a subsequent step.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer is preferably one obtained by subjecting the above-mentioned emulsion polymer dispersion to hydrolysis treatment. The hydrolysis treatment can be carried out by adding an alkali to the emulsion polymer dispersion.
The alkali to be used in the hydrolysis treatment is not particularly restricted but may be any of those alkalis which are generally used in hydrolysis, including, among others, alkali metal hydroxides and alkaline earth metal hydroxides. As such hydroxides, there may be mentioned, for example, sodium hydroxide, potassium hydroxide and lithium hydroxide.
The above hydrolysis treatment converts the —SO2X2 and/or —COZ2 groups which the above fluoropolymer precursor has to acid salt groups and, therefore, can convert the fluoropolymer precursor to an acid salt fluorovinyl ether unit-based fluoropolymer (hereinafter sometimes referred to as “acid salt fluoropolymer”).
In cases where the fluoropolymer precursor has —SO2X2 groups (in which X2 is as defined above, namely represents a halogen atom), the precursor is generally unstable and readily coagulates upon addition of an acid. However, an alkali is added in the above hydrolysis treatment, so that, unless the alkali is added abruptly, the fluoropolymer precursor can be maintained stably in a state of dispersion in the aqueous medium without coagulation thereof and the —SO2X2 groups can be quantitatively converted to sulfonic acid salt groups.
The above hydrolysis treatment can convert the above emulsion polymer dispersion to fluoropolymer aqueous dispersion comprising the corresponding acid salt fluoropolymer dispersed in an aqueous dispersion medium.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer may be one obtained by the above-mentioned hydrolysis treatment of the above-mentioned emulsion polymer dispersion, followed by further treatment with an acid, namely acid treatment, according to need.
The acid to be used in the above-mentioned acid treatment is not particularly restricted but may be any of those acids generally used in neutralizing alkalis; thus, it may be a mineral acid, for instance. As the mineral acid, there may be mentioned, for example, hydrochloric acid and sulfuric acid.
The above acid treatment converts the acid salt groups of the above-mentioned acid salt fluoropolymer to the acid groups and thus can convert the acid salt fluoropolymer to the corresponding acid fluorovinyl ether unit-based fluoropolymer (hereinafter sometimes referred to as “acid fluoropolymer”).
The end point of the hydrolysis reaction in the above-mentioned hydrolysis treatment and the end point of the neutralization reaction in the above-mentioned acid treatment can be detected based on the fact that no more alkali or acid is consumed and the pH is stabilized.
The reaction temperature in the hydrolysis treatment and the reaction temperature in the acid treatment are not particularly restricted but may be room temperature. From the reaction rate viewpoint, however, each reaction is preferably carried out at a temperature of 30 to 100° C. The fluoropolymer precursor concentration in carrying out the hydrolysis treatment or the acid salt fluoropolymer concentration in carrying out the acid treatment is not particularly restricted but, when it is 5 to 15% by mass relative to the aqueous medium, the viscosity of the emulsion polymer dispersion comprising the aqueous medium and fluoropolymer precursor or the viscosity of the fluoropolymer aqueous dispersion comprising the aqueous medium and acid salt fluoropolymer falls within a preferred range and the particles comprising the fluoropolymer precursor or the particles comprising the acid salt fluoropolymer show a uniform distribution, so that the hydrolysis treatment or acid treatment can be allowed to proceed smoothly.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer is preferably one obtained by subjecting the above-mentioned emulsion polymer dispersion to hydrolysis treatment, if necessary followed by acid treatment, and further followed by treatment for removing low-molecular-weight substances (hereinafter sometimes referred to as treatment for removing low-molecular-weight substances). The low-molecular-weight substances include the monomer(s) remaining after the emulsion polymerization, polymerization initiator residues, unnecessary low-molecular-weight polymer molecules, or substances formed upon hydrolysis treatment of the fluoropolymer precursor and, when the residues of the emulsifier used in the emulsion polymerization remain, they can also be removed.
The treatment for removing low-molecular-weight substances is not particularly restricted but includes, among others, centrifugation, electrophoresis, and ultrafiltration. The ultrafiltration method is preferably used, however. The ultrafiltration method is not particularly restricted but may be any of those methods of removing low-molecular-weight substances which use an ultrafiltration apparatus having an ultrafiltration membrane, including the centrifugal ultrafiltration method and circulating ultrafiltration method, among others. Suitably usable as the ultrafiltration membrane-containing ultrafiltration apparatus are commercial ones and, for use in laboratories, there may be mentioned, for example, Centriprep (trademark; product of Amicon), Millitan (trademark; product of Millipore) and Pellicon (trademark; product of Millipore). In the above ultrafiltration step, the fluoropolymer obtained can also be concentrated.
The above treatment for removing low-molecular-weight substances may be carried out after the hydrolysis treatment and, when the hydrolysis treatment is further followed by acid treatment, it may be carried out after the acid treatment.
In preparing the fluoropolymer liquid composition according to the invention, the above-mentioned hydrolysis treatment and acid treatment can be carried out in an aqueous dispersion. In this case, the hydrolysis treatment is preferably carried out in an aqueous medium, and the acid treatment is preferably carried out in an aqueous dispersion medium. The aqueous medium is only required to comprise water, hence may comprise a water-soluble organic solvent as well as water.
When, in preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer is one obtained by emulsion polymerization, the emulsion polymerization and hydrolysis treatment and, further, the acid treatment to be carried out according to need can all be carried out in an aqueous dispersion.
After the hydrolysis treatment, the aqueous medium in the hydrolysis treatment can be used, as it is, as the aqueous dispersion medium in the fluoropolymer aqueous dispersion. The aqueous dispersion medium in the acid treatment can be used, as it is, as the aqueous dispersion medium in the fluoropolymer aqueous dispersion.
In the process for preparing the fluoropolymer liquid composition according to the invention, the above-mentioned aqueous medium is the dispersion medium in the above-mentioned emulsion polymer dispersion and the dispersion medium in the aqueous dispersion in which the above-mentioned hydrolysis treatment is carried out, the above-mentioned aqueous dispersion medium is the dispersion medium in the fluoropolymer aqueous dispersion obtained after the above-mentioned hydrolysis treatment, the dispersion medium in the aqueous dispersion in which the above-mentioned acid treatment is carried out, and the dispersion medium in the fluoropolymer aqueous dispersion obtained after the above-mentioned hydrolysis treatment and acid treatment, and the above-mentioned aqueous reaction medium is the dispersion medium in the aqueous dispersion system in which the emulsion polymerization is carried out and, in this respect, the above-mentioned aqueous medium, the above-mentioned aqueous dispersion medium and the above-mentioned aqueous reaction medium conceptually differ from one another.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer may be one obtained by subjecting the above-mentioned acid salt fluorovinyl-ether derivative to emulsion polymerization substantially without using the above-mentioned fluorovinyl-ether derivative. The phrase “substantially without using” as used herein means that in the case of this fluoropolymer, for instance, the content of acid salt fluorovinyl ether units derived from the above-mentioned fluorovinyl-ether derivative among the total number of moles of the monomers from which the fluoropolymer-constituting monomer units are derived is lower than 5 mole percent.
The fluoropolymer obtained by this method has a polymer chain derived from the acid salt fluorovinyl-ether derivative and acid salt fluorovinyl-ether derivative and having emulsifying activity, as described hereinabove, and, therefore, it is no more necessary, in the step of polymerization, to add such an emulsifier as generally used in the conventional emulsion polymerization, hence it is not necessary to remove such emulsifier in a later step.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer may be one obtained by carrying out the copolymerization of the fluorovinyl-ether derivatives in the presence of an iodide compound such as 1,4-diiodoperfluorobutane to give a polymer dispersion comprising a block polymer and subjecting the polymer dispersion obtained to the above-mentioned hydrolysis treatment.
The fluoropolymer obtained by the method comprising subjecting an acid salt fluorovinyl-ether derivative to emulsion polymerization substantially without using any fluorovinyl-ether derivative and the fluoropolymer obtained by carrying out the copolymerization in the presence of an iodine compound each comprises an acid salt fluoropolymer and it may be used as such for the preparation of a fluoropolymer dispersion composition or further subjected to the above-mentioned acid treatment to give a fluoropolymer comprising an acid fluoropolymer, which is to be used for the preparation of a fluoropolymer liquid composition.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer may be one obtained by the method comprising subjecting membranous moldings formed from an —SO2F group-containing, fluoropolymer precursor to hydrolysis in the form of membranous moldings as such to convert the —SO2F groups to sulfonic acid groups or a salt form thereof and dissolving the membranous moldings obtained in a mixed solvent comprising an alcohol, or one obtained by the method comprising dispersing the membranous moldings obtained in water with stirring at a temperature of 220 to 300° C.
In preparing the fluoropolymer liquid composition according to the invention, the fluoropolymer in which, in the general formula (I) given hereinabove, A1 is —SO2X1 in which X1 is NR5R6 may be one obtained by polymerizing an acid fluorovinyl-ether derivative represented by the general formula (IV):
CF2═CF—O—(CF2CFY1—O)n—(CFY2)m—SO2NR5R6 (IV)
The fluoropolymer to be contained in the fluoropolymer liquid composition according to the invention is preferably one obtained by subjecting an emulsion polymer dispersion obtained by emulsion polymerization of a fluorovinyl-ether derivative represented by the general formula (II) given hereinabove to hydrolysis treatment. The above-mentioned fluoropolymer, when obtained by this method comprising carrying out the emulsion polymerization and hydrolysis treatment, is generally obtained in the form of fine particles and is suited for use in preparing the above-mentioned fluoropolymer dispersion comprising the fluoropolymer fine particles and the film-forming auxiliary.
The fluoropolymer liquid composition according to the invention is excellent in film/membrane-forming property, since it comprises an organic liquid which is compatible with water and has a boiling point exceeding 100° C. but not higher than 300° as incorporated therein as the film-forming auxiliary.
The fluoropolymer liquid composition according to the invention comprises the film-forming auxiliary as incorporated therein and, therefore, even the above-mentioned fluoropolymer liquid composition which comprises fluoropolymer fine particles is excellent in film/membrane-forming property since the fluoropolymer fine particles are in a swollen state and the fluoropolymer fine particles partly occur in a mutually fused state. The fluoropolymer liquid composition in which the fluoropolymer fine particles are partly in a mutually fused state, as mentioned above, is therefore excellent in film/membrane-forming property even when the average particle diameter of the fluoropolymer fine particles is as great as 10 to 300 nm.
The film-forming auxiliary which is contained in the fluoropolymer liquid composition according to the invention and has a boiling point within the range specified above remains in the fluoropolymer liquid composition even in the process of film/membrane formation to improve the film/membrane-forming property of the composition and, when it is necessary to remove the film-forming auxiliary from the films/membranes obtained, the removal can be effected with ease by heating.
The fluoropolymer dispersion composition of the invention, which has the above-described constitution, can be adequately used in forming fibers and films/membranes. The “films/membranes” so referred to herein are films/membranes including the so-called thin films/membranes and the term conceptually includes films, sheets and the like as well. The films/membranes may be those obtained, for example, by cast film formation, impregnation, or coating. They do not include substrates, porous supports or the like used in film/membrane formation.
The film/membrane of the present invention is one obtained by cast film formation using the above-mentioned fluoropolymer dispersion composition. The “cast film formation” generally denotes the technique which comprises applying the above-mentioned fluoropolymer liquid composition to the surface of a substrate, drying the coat at ordinary temperature and/or with heating, if necessary immersing the same in water, and peeling the resulting film/membrane from the substrate surface to give a thin film/membrane. The “ordinary temperature” so referred to herein is a temperature of 30° C., and “with heating” herein refers to heating at a temperature of 50 to 80° C. The drying mentioned above, when carried out with heating, is preferably carried out for 30 to 60 minutes.
The above-mentioned substrate to be used in cast film formation is not particularly restricted but includes, among others, glass, stainless steel and so forth. The method of application is not particularly restricted but includes, among others, application by impregnation, spray coating and so forth.
When the film/membrane obtained by the above-mentioned cast film formation is further heated at 150 to 300° C. for 20 to 40 minutes, the film-forming auxiliary can be completely removed from the film/membrane.
The film/membrane of the invention also includes one obtained by impregnating a porous support with the above-mentioned fluoropolymer liquid composition and then removing the liquid medium. The term “liquid medium” as used herein means a solvent capable of dissolving the fluoropolymer and/or a dispersion medium capable of dispersing the fluoropolymer, which occurs as a liquid at ordinary temperature around 20° C. As the solvent capable of dissolving the fluoropolymer and the dispersion medium capable of dispersing the fluoropolymer, there may be mentioned herein the above-mentioned aqueous dispersion medium, film-forming auxiliary, lower alcohol and organic medium, among others.
The above-mentioned porous support is not particularly restricted but may be any one having a porous structure. It may be an organic or inorganic material; thus, it includes, among others, glass wool, ceramics, alumina, polytetrafluoroethylene [PTFE] porous films, carbon, nonwoven fabrics, and various polymer-derived ones. The removal of the liquid medium may be carried out by heating at 50 to 80° C., for instance, or by heating to a temperature not lower than the glass transition point of the fluoropolymer, or by heating to a temperature not lower than the melting point of the fluoropolymer. The temperature not lower than the glass transition temperature of the fluoropolymer is generally a temperature of 150 to 350° C., and the temperature not lower than the melting point of the fluoropolymer is generally a temperature of 200 to 350° C.
The thickness of the film/membrane obtained by cast film formation and the thickness of the film/membrane obtained by impregnating a porous support with the fluoropolymer liquid composition each is preferably 10 to 40 μm. When the thickness is less than 10 μm, the mechanical strength of the film/membrane will be insufficient and, when it exceeds 40 μm, the use of the film/membrane in a solid polymer electrolyte type fuel cell, which is to be mentioned later herein, may result in deteriorated fuel cell performance characteristics.
The active substance-immobilized material of the present invention comprises a fluoropolymer and an active substance and is one obtained by applying a substrate with a liquid composition comprising the above-defined fluoropolymer liquid composition and the active substance. When the above-mentioned liquid composition is applied to the substrate, the fluoropolymer and active substance are immobilized onto the substrate.
The active substance is not particularly restricted but may be any one capable of remaining active in the active substance-immobilized material; it can be appropriately selected according to the intended purpose of the active substance-immobilized material of the invention. In some instances, a catalyst may be adequately used. The catalyst is not particularly restricted but may be any of those generally used as electrode catalysts, including, among others, metals containing platinum, ruthenium or the like.
The substrate which is to be applied with the above-mentioned liquid composition is not particularly restricted but includes, among others, the above-mentioned porous supports, resin moldings, metal sheets and so forth. Preferred are, among others, those electrolyte membranes and porous carbon electrodes which are used in fuel cells etc. The electrolyte membranes preferably comprise fluoropolymer, and it may comprise the above-mentioned fluoropolymer.
The “applying of a substrate with a liquid composition” so referred to above comprises applying the above-mentioned liquid composition to the substrate, drying if necessary, and generally further heating at a temperature not lower than the melting point of the fluoropolymer. The heating conditions are not particularly restricted but may be such that the fluoropolymer and active substance may be immobilized on the substrate; for example, 2 to 30 minutes of heating at 200 to 350° C. is preferred, however.
The electrolyte membrane comprises the above-mentioned active substance-immobilized material. The electrolyte membrane may further comprise some substance other than the active substance-immobilized material in an amount such that the properties of the active substance-immobilized material may not be deteriorated.
The membrane/electrode assembly [MEA] of the present invention comprises the above electrolyte membrane. The membrane/electrode assembly may further comprise some substance other than the electrolyte membrane in an amount such that the properties of the electrolyte membrane may not be deteriorated.
The solid polymer electrolyte fuel cell of the invention comprises the above-mentioned film/membrane, active substance-immobilized material, electrolyte membrane and/or membrane/electrode assembly. As the solid polymer electrolyte fuel cell of the invention, there may be mentioned, for example, one comprising the above-mentioned film/membrane, one comprising the above-mentioned active substance-immobilized material, one comprising the above-mentioned electrolyte membrane, one comprising the above-mentioned membrane/electrode assembly, and one comprising the above-mentioned film/membrane and active substance-immobilized material, among others.
The solid polymer electrolyte fuel cell may also be one further comprising such constituent components as solid polymer electrolyte fuel cell constituent gases.
In each of the above-mentioned fluoropolymer liquid composition, the above-mentioned film/membrane obtained by cast film formation, the above-mentioned film/membrane obtained by impregnating a porous support with the fluoropolymer liquid composition, and the above-mentioned active substance-immobilized material, electrolyte membrane, membrane/electrode assembly or solid polymer electrolyte fuel cell, use is made of a fluoropolymer having sulfonic acid and/or carboxylic acid groups which may occur in salt form, preferably a fluoropolymer having sulfonic acid groups which may occur in salt form.
The following examples illustrate the present invention in further detail. These examples are, however, by no means limitative of the scope of the present invention.
(1) An emulsion polymer dispersion (200 ml) containing a copolymer obtained by emulsion polymerization of CF2═CF2 and CF2═CFOCF2CF2SO2F and having an EW value (polymer weight [g] equivalent to ion exchange capacity for exchanging 1 mole of ions) of 710 was 3-fold diluted with pure water, and a 10% (by mass) aqueous solution of sodium hydroxide was added dropwise to the dilution with stirring at 80° C. while maintaining the pH at 9 to 12, to carry out the hydrolysis of —SO2F. After 2 hours, at the time point at which the reaction had proceeded to an extent of about 80%, the rate of consumption of sodium hydroxide decreased as compared with the initial stage, so that the aqueous solution of sodium hydroxide was added until the expected equivalent consumption, followed by standing in an oven maintained at 80° C. After confirming that the mixture was almost neutral, an amount of the aqueous solution of sodium hydroxide corresponding to 20% of the expected consumption was further added and the resultant mixture was allowed to stand in the same oven. After 14 hours, after confirming that the pH was stable without further consumption of sodium hydroxide, the excess of sodium hydroxide was neutralized with hydrochloric acid, and the resultant mixture was purified and concentrated using an ultrafilter (trademark: Pellicon Unit; product of Millipore; molecular weight cut-off: 10000) until the filtrate showed an electric conductivity not higher than 0.01 S (siemens) to give 150 ml of fluoropolymer aqueous dispersion with a fluoropolymer fine particle concentration of 26% by mass.
This fluoropolymer aqueous dispersion was very stable and, even after 1 month of standing, no settlement of the fluoropolymer fine particles was observed by the eye.
(2) Triethyl phosphate (1.2 ml) and 0.5 ml of isopropanol were compounded with 1 ml of the fluoropolymer aqueous dispersion obtained in (1). A viscous fluoropolymer dispersion composition was obtained which was slightly more turbid than the emulsion polymer dispersion obtained in (1). A portion of the fluoropolymer dispersion composition obtained was collected and measured for fluoropolymer concentration by the dry weight method; the concentration was 10% by mass.
(3) The fluoropolymer dispersion composition obtained in (2) was applied onto a glass sheet, and the whole was allowed to stand in an oven maintained at 80° C. for 30 minutes to form a transparent membrane. Immersion, together with the glass plate, in pure water easily resulted in peeling off of the membrane to give a thin membrane with a thickness of 10 μm.
(4) The emulsion polymer dispersion, fluoropolymer aqueous dispersion and fluoropolymer dispersion composition obtained as described above in (1) and (2) were each applied onto a silicon wafer and, after drying at room temperature (20° C.), each coat film formed was observed under an atomic force microscope [AFM]. The photograph, taken by using the AEM, of the coat film formed by the emulsion polymer dispersion is shown in
As can be seen in
A porous membrane made of polytetrafluoroethylene [PTFE] (product of Daikin Industries) was impregnated with the fluoropolymer dispersion composition obtained in Example 1 (2), the whole was allowed to stand in an oven maintained at 80° C. for 30 minutes to give a transparent membrane with a thickness of 15 μm.
A 5-ml portion of the fluoropolymer aqueous dispersion obtained in Example 1 (1) was two-fold diluted with pure water, and 10 ml of triethyl phosphate was compounded with the dilution with stirring. Water evaporation was caused by heating at 40° C. in a rotary evaporator to give an organosol with the triethyl phosphate as the dispersion medium.
In the same manner as in Example 1 (3), a thin membrane was formed from the organosol obtained and peeled off from the glass sheet, whereupon a thin membrane with a thickness of 10 μm was obtained.
Using the fluoropolymer aqueous dispersion obtained in Example 1 (1) alone, a membrane was formed in the same manner as in Example 1 (3).
The transparent membrane obtained showed cracking and was not a continuous membrane. When immersed in pure water, it was redispersed.
A composition was obtained in the same manner as in Example 1 except that ethanol was used in lieu of triethyl phosphate, and a membrane was formed using the composition obtained.
The membrane obtained showed cracking and, when immersed in pure water, it was redispersed.
While the triethyl phosphate-containing, fluoropolymer liquid compositions as obtained in Examples 1 to 3 all could give membranes, the compositions of Comparative Examples 1 and 2 as used without incorporation of triethyl phosphate failed to give continuous membranes similar to those obtained in Examples 1 to 3.
The fluoropolymer liquid composition according to the invention, which has the constitution described hereinabove, is excellent in film/membrane-forming property and can give acid/acid salt group-containing, namely sulfonic acid group- and/or carboxyl group-containing, fluoropolymer film/membranes.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2003-056184 | Mar 2003 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP04/02609 | 3/3/2004 | WO | 9/2/2005 |
