WO2022270477A1 - 化合物、重合性組成物、重合体及び重合膜 - Google Patents
化合物、重合性組成物、重合体及び重合膜 Download PDFInfo
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- WO2022270477A1 WO2022270477A1 PCT/JP2022/024583 JP2022024583W WO2022270477A1 WO 2022270477 A1 WO2022270477 A1 WO 2022270477A1 JP 2022024583 W JP2022024583 W JP 2022024583W WO 2022270477 A1 WO2022270477 A1 WO 2022270477A1
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- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940006487 lithium cation Drugs 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003266 membrane potential measurement method Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RUEPJNWQHNUKIG-UHFFFAOYSA-M sodium 2,4-bis(ethenyl)benzenesulfonate Chemical compound [Na]OS(=O)(=O)C1=CC=C(C=C)C=C1C=C RUEPJNWQHNUKIG-UHFFFAOYSA-M 0.000 description 1
- OIIWPAYIXDCDNL-UHFFFAOYSA-M sodium 3-(trimethylsilyl)propionate Chemical compound [Na+].C[Si](C)(C)CCC([O-])=O OIIWPAYIXDCDNL-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 229920001567 vinyl ester resin Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/21—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
-
- 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
- C08F12/00—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 an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/30—Sulfur
-
- 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
- C08F12/00—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 an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- 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
- C08F12/00—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 an aromatic carbocyclic ring
- C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on 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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
Definitions
- the present invention relates to a compound, a polymerizable composition containing this compound, a polymer of the compound, and a polymer film containing this polymer.
- Functional polymers and the like are used in various technical fields such as ion exchange membranes, reverse osmosis membranes, forward osmosis membranes, gas separation membranes and other polymeric functional membranes, and electrochemical devices.
- functional polymers it is necessary to research and develop polymers that can express the properties required for each product's application and function, and monomers that form such polymers.
- Polymers, monomers, etc. having chemical structures are being investigated.
- Patent Document 1 discloses that, in a lithographic printing plate, a phenyl group of styrene and a phenyl group of benzenesulfonic acid are used as a polymerizable compound forming an intermediate layer provided between a support and a photosensitive layer.
- Patent Document 2 discloses a styrene compound incorporating a salicylic acid unit as a polymerizable monomer for constituting a charge control agent used in a developer carrier equipped in an image forming apparatus.
- a polymerizable compound is disclosed in which a phenyl group of styrene and salicylic acid are bonded via a sulfonic acid amide bond such that the phenolic hydroxyl group is at the para position.
- Patent Document 3 a compound (reactive organic dye) in which an ⁇ -bromostyrene skeleton and a water-soluble organic dye residue such as anthraquinone are bonded via a group containing a sulfonic acid amide bond is disclosed as a water-soluble dye.
- a compound (reactive organic dye) in which an ⁇ -bromostyrene skeleton and a water-soluble organic dye residue such as anthraquinone are bonded via a group containing a sulfonic acid amide bond is disclosed as a water-soluble dye.
- An object of the present invention is to provide a compound exhibiting alkali resistance and a polymerizable composition containing this compound.
- Another object of the present invention is to provide an acid-resistant and alkali-resistant polymer having a component derived from the above compound, and a polymer film containing the polymer and exhibiting acid-resistant and alkali-resistant properties. do.
- the present inventor considers the monomer forming the polymer to be a compound having a chemical structure in which a sulfonic acid group-containing benzene ring is introduced at the para-position to the benzene ring of a styrene compound via a sulfonic acid amide bond. It was found that this monomer exhibits acid resistance. As a result of further investigation, it was found that homopolymerization or copolymerization of this monomer results in a polymer exhibiting acid resistance and alkali resistance. The present invention has been completed based on these findings.
- R1 represents a hydrogen atom or a lower alkyl group.
- R2 represents an alkyl group, alkenyl group, aryl group, halogen atom, hydroxyl group or amino group.
- R 3 is an alkyl group, an alkenyl group, an aryl group, a halogen atom, an amino group, a carboxy group, or a group having a —SO 3 ⁇ M + group , an alkyl group, an alkenyl group, an aryl group, an oxygen atom, —SO 3 - indicates a group combining an M + group or an arylsulfonylamino group.
- R4 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, an amino group or a carboxy group, an alkyl group, an alkenyl group, an aryl group, an oxygen atom , a -SO3- M + group or an arylsulfonylamino group; represents a group in which M + denotes H + , Li + , Na + , K + , Cs + or an ammonium salt.
- k is an integer of 0 to 4, and when k is an integer of 2 or more, a plurality of R 2 may be the same or different, and may be linked together to form a ring.
- n is an integer of 0 to 4, and when n is an integer of 2 or more, a plurality of R 3 may be the same or different, and may be linked together to form a ring.
- m is an integer of 0 to 4, and when m is an integer of 2 or more, multiple —SO 3 ⁇ M + groups may be the same or different. However, n and m satisfy 1 ⁇ n+m ⁇ 4. Also, when m is 0, at least one R 3 is a group having a —SO 3 ⁇ M + group.
- R 1A represents a hydrogen atom or a methyl group.
- R 3 , R 4 and M + have the same meanings as R 3 , R 4 and M + in general formula (I).
- m is 1 or 2 and n is an integer of 0-2.
- ⁇ 7> A polymerizable composition containing the compound according to any one of ⁇ 1> to ⁇ 6> above.
- ⁇ 8> A polymer having a component derived from the compound according to any one of ⁇ 1> to ⁇ 6> above.
- ⁇ 9> A polymer film containing the polymer according to ⁇ 8> above.
- the present invention can provide a compound exhibiting alkali resistance and a polymerizable composition containing this compound.
- the present invention can provide a polymer having a component derived from the above compound and exhibiting acid resistance and alkali resistance, and a polymer film containing this polymer and exhibiting acid resistance and alkali resistance.
- FIG. 1 is a schematic diagram of a channel of an apparatus for measuring the water permeability of a polymer membrane.
- FIG. 2 is a 1 H-NMR (400 MHz, D 2 O) chart of exemplary compound (1) synthesized in Examples.
- FIG. 3 is a 1 H-NMR (400 MHz, D 2 O) chart of exemplary compound (2) synthesized in Examples.
- FIG. 4 is a 1 H-NMR (400 MHz, D 2 O) chart of exemplary compound (8) synthesized in Examples.
- a numerical range represented using "-" means a range including the numerical values described before and after "-" as lower and upper limits.
- the upper and lower limits forming the numerical range are defined as a specific numerical range. are not limited to the specific combinations described in , and the numerical values of the upper and lower limits forming each numerical range can be appropriately combined.
- the term "dissociative group” refers to a group that can be reversibly decomposed into its component atoms, ions, atomic groups, and the like.
- the expression of a compound is used to include the compound itself, its salt, and its ion.
- it is meant to include derivatives in which a part is changed, such as by introducing a substituent, to the extent that the effects of the present invention are not impaired.
- (meth)acrylamide means at least one of acrylamide and methacrylamide, or acrylamide and methacrylamide
- (Meth)acrylate” represents at least one of acrylate and methacrylate, or acrylate and methacrylate, respectively.
- the geometrical isomers which are the substitution modes of the double bond in each general formula, are either the E isomer or the Z isomer unless otherwise specified. or a mixture thereof.
- the compound represented by each general formula has an ethylenic double bond as a linking group or the like, the ethylenic double bond may be polymerized in the polymer of this compound.
- substituents, linking groups, etc. for which substitution or non-substitution is not specified are intended to mean that the group may have an appropriate substituent. Therefore, in the present invention, even when the YYY group is simply described, this YYY group includes not only the embodiment having no substituent but also the embodiment having a substituent. This also applies to compounds that are not specified as substituted or unsubstituted. In the present invention, even if not otherwise specified, when a plurality of substituents and the like are adjacent, they may be connected to each other or condensed to form a ring.
- the compound of the present invention is a polymerizable compound having a chemical structure in which a benzene ring containing a sulfonic acid group is introduced via a sulfonic acid amide bond at the para-position to the benzene ring of a styrene compound, and is called a styrene sulfonamide compound. be able to.
- the compound of the present invention is specifically represented by the following general formula (I). This compound exhibits excellent alkali resistance and also exhibits water solubility.
- the term "alkali resistance” refers to the property that a compound, polymer, polymer film, etc.
- Acid resistance refers to the property that a polymer, polymer film, etc. is resistant to hydrolysis reaction in an acidic environment (property capable of suppressing the progression of decomposition).
- Partial decomposition of the polymer or the like is unavoidable due to the strength of the acid, the prolonged exposure period to the acidic environment, etc., but in the present invention, at least the tests in the examples described later show a passing level.
- styrene ethylenic double bond
- the compound of the present invention exhibiting the above properties can be homopolymerized or copolymerized to form a polymer exhibiting excellent acid resistance and alkali resistance, taking advantage of the above properties of the compound, as described later. Therefore, the compound of the present invention can be used in a wide range of applications, and is particularly suitable as a compound for polymers constituting polymer films.
- R 1 represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group that can be taken as R 1 is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
- a lower alkyl group may be straight, branched or cyclic. Examples of lower alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl and the like.
- R 1 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
- R2 represents an alkyl group, alkenyl group, aryl group, halogen atom, hydroxyl group or amino group.
- the alkyl group that can be taken as R 2 may be linear, branched or cyclic.
- the number of carbon atoms constituting the alkyl group is not particularly limited, and is, for example, preferably 1-10, more preferably 1-5, and particularly preferably 1-3.
- Examples of alkyl groups that can be taken as R 2 include methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-octyl, 2-ethylhexyl, n-decyl and n-hexadecyl.
- the alkenyl group that can be taken as R 2 may be linear, branched or cyclic.
- the number of carbon atoms constituting the alkenyl group is not particularly limited, and is, for example, preferably 2-10, more preferably 2-6, and particularly preferably 2-5.
- Aryl groups that can be taken as R 2 include aromatic hydrocarbon ring groups and aromatic heterocyclic groups, and may be monocyclic or condensed ring.
- the aromatic hydrocarbon ring group is not particularly limited, but preferably has 6 to 14 carbon atoms.
- Examples of aromatic hydrocarbon ring groups include phenyl and naphthyl.
- a nitrogen atom, an oxygen atom, and a sulfur atom are preferable as the ring-constituting heteroatom that constitutes the aromatic heterocyclic group.
- the number of ring members of the monocyclic aromatic heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
- aromatic heterocyclic groups include nitrogen-containing heterocyclic groups such as pyrrole rings and pyridine rings, furan ring groups, thiophene ring groups, and benzothiazole ring groups.
- a halogen atom that can be taken as R 2 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- Amino groups that can be used as R 2 include unsubstituted amino groups (—NH 2 ) and mono- or di-alkyl or arylamino groups substituted with alkyl or aryl groups.
- the alkyl group and aryl group are not particularly limited, but include, for example, the aforementioned alkyl group and aryl group that can be taken as R 2 .
- the group that can be taken as R 2 is preferably an alkenyl group, more preferably a vinyl group or isopropenyl.
- the position of the benzene ring to which R 2 is bonded is not particularly limited, and relative to the ring-constituting carbon atom to which the ethylenic double bond (vinyl group having R 1 ) is bonded It may be at the 2nd position (ortho position) or 3rd position (meta position), but preferably at the 3rd position.
- R 3 is an alkyl group, an alkenyl group, an aryl group, a halogen atom, an amino group, a carboxy group, a group having a —SO 3 ⁇ M + group , an alkyl group, an alkenyl group, an aryl group, an oxygen atom, —SO Denotes a group combining a 3 ⁇ M + group or an arylsulfonylamino group. However, when m, which will be described later, is 0, at least one of n R 3 is a group having a —SO 3 ⁇ M + group.
- the alkyl group, alkenyl group, aryl group, halogen atom and amino group that can be taken as R 3 have the same meanings as the alkyl group, alkenyl group, aryl group, halogen atom and amino group that can be taken as R 2 .
- a group having a —SO 3 ⁇ M + group that can be used as R 3 is a group that introduces a —SO 3 ⁇ M + group into the benzene ring in general formula (I) via a linking group.
- the linking group is not particularly limited and can be selected as appropriate, and preferably includes an alkylene group, an alkenylene group, an arylene group, and the like. These groups include groups obtained by removing one hydrogen atom from each of the alkyl groups, alkenyl groups, and aryl groups that can be taken as R 2 , respectively.
- the above combined groups that can be taken as R 3 are optionally two or more groups selected from the group consisting of alkyl groups, alkenyl groups, aryl groups, oxygen atoms, —SO 3 ⁇ M + groups and arylsulfonylamino groups.
- a group formed by combining may be used.
- the alkyl group, alkenyl group, and aryl group forming a combined group have the same meanings as the alkyl group, alkenyl group, and aryl group that can be taken as R 2 .
- the aryl group constituting the arylsulfonylamino group has the same definition as the aryl group that can be taken as R 2 , preferably an aromatic hydrocarbon ring group, more preferably a benzene ring group.
- the number of groups to be combined in the combined groups is not particularly limited, but for example, it is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 6, 2 ⁇ 4 is particularly preferred.
- the group to be combined is not particularly limited, but a combination containing an alkenyl group and a —SO 3 ⁇ M + group or an arylsulfonylamino group is preferable, and a combined group that can be taken as R 4 described later can also be adopted.
- Examples of the combined group include a group in which a vinyl group and a —SO 3 ⁇ M + group are combined, a group in which a vinyl group and a phenylsulfonylamino group are combined (a nitrogen atom of a phenylsulfonylamino group and benzene ring) is preferred.
- R 3 is preferably an alkyl group, an alkenyl group, or a combination of the above groups, more preferably a combination of the above groups.
- n which will be described later, is an integer of 1 or more, the position of the benzene ring to which R 3 is bonded is not particularly limited, and the 2-position (ortho-position) or 3-position ( meta position) is also acceptable.
- R 4 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, an amino group or a carboxy group, an alkyl group, an alkenyl group, an aryl group, an oxygen atom, -SO 3 - Denotes a group combining an M + group or an arylsulfonylamino group.
- the alkyl group, alkenyl group, aryl group, halogen atom and amino group that can be taken as R4 have the same meanings as the alkyl group, alkenyl group, aryl group, halogen atom and amino group that can be taken as R2 .
- the alkyl group, alkenyl group and aryl group forming the above combined groups that can be taken as R 4 have the same meanings as the alkyl group, alkenyl group and aryl group that can be taken as R 2 .
- the arylsulfonylamino group has the same definition as the arylsulfonylamino group constituting the above combined group that can be taken as R3.
- the combined groups that can be taken as R 4 are optionally two or more groups selected from the group consisting of alkyl groups, alkenyl groups, aryl groups, oxygen atoms, —SO 3 ⁇ M + groups and arylsulfonylamino groups.
- a group formed by combining may be used.
- the number of groups to be combined is not particularly limited. It is particularly preferred to have The groups to be combined are not particularly limited, but a combination containing an alkenyl group and an arylsulfonylamino group is preferred, and a combination further containing an aryl group and a —SO 3 ⁇ M + group is more preferred.
- Combined groups include, for example, p-vinyl-substituted phenylsulfonylamino groups and groups containing p-vinyl-substituted phenylsulfonylamino groups.
- Specific examples of the p-vinyl-substituted phenylsulfonylamino group include "p-vinyl-substituted phenylsulfonylamino group”.
- Examples of the group containing a p-vinyl-substituted phenylsulfonylamino group include groups containing a p-vinyl-substituted phenylsulfonylamino group and a linking group (for example, L A or L B described later), which are specifically described later. Examples thereof include a "p-vinyl-substituted phenylsulfonylamino group containing L A or L B " bonded to the second benzene ring from the left in the chemical formula represented by general formula (V) or (VI).
- R 4 is preferably a hydrogen atom, an alkyl group, an alkenyl group, or a combination of the above groups, more preferably a combination of the above groups.
- M + forming a —SO 3 ⁇ M + group represents H + , Li + , Na + , K + , Cs + or an ammonium salt.
- Ammonium salts that can be used as M + are not particularly limited and include NH 4 + or organic ammonium salts having at least one organic group. Examples of the organic group constituting the organic ammonium salt include an alkyl group and an aryl group, with an alkyl group being preferred. Although the alkyl group is not particularly limited, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
- the aryl group is not particularly limited and includes, for example, aryl groups that can be taken as R 2 .
- the number (series) of organic groups possessed by the organic ammonium salt may be 1 or more (secondary to quaternary ammonium salts), but is 3 (tertiary ammonium salts) or 4 (quaternary ammonium salts). is preferred. When two or more organic groups are used, the organic groups may be the same or different.
- a tertiary alkylammonium salt or a quaternary alkylammonium salt is preferable as the organic ammonium salt.
- the position of the benzene ring to which the —SO 3 ⁇ M + group is bonded is not particularly limited, and may be the 2-position (ortho-position) with respect to the carbon atom to which the sulfonylamino group is bonded. Although it may be at the 3rd position (meta position), it is preferably at the 3rd position.
- R 1 to R 4 can be combined as appropriate, and preferred combinations of R 1 to R 4 include combinations of preferred groups that can be taken as R 1 to R 4 Specific examples include combinations of exemplary compounds described later.
- k is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1.
- n is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1;
- m is an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2;
- n and m satisfy 1 ⁇ n+m ⁇ 4, preferably 1 ⁇ n+m ⁇ 2.
- a plurality of R 2 and R 3 may be the same or different, and may be linked to each other to form a ring.
- a vinyl group having a —SO 3 ⁇ M + group as R 3 and a vinyl group are bonded to adjacent ring-constituting carbon atoms, and the two vinyl groups are linked to form benzene It forms a ring (naphthalene ring) condensed with a ring.
- m is an integer of 2 or more, multiple —SO 3 ⁇ M + groups may be the same or different.
- the compound represented by formula (I) may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound.
- the "monofunctional polymerizable compound” means a compound having one ethylenic double bond present in the molecular structure, for example, the above formula (I) or the following (II) Among the compounds represented, compounds having no ethylenic double bond (alkenyl group) as R 2 to R 4 are exemplified.
- the term “polyfunctional polymerizable compound” means a compound having two or more ethylenic double bonds present in its molecular structure, and the groups represented by R 2 to R 4 etc.
- the compound represented by the general formula (I) is preferably a monofunctional polymerizable compound from the viewpoint of water permeability when used in a polymer film. Polyfunctional polymerizable compounds are preferred from the viewpoint of improving acid resistance and alkali resistance.
- the compound represented by the above general formula (I) is preferably represented by the following general formula (II).
- R 1A represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- R 3 , R 4 and M + have the same meanings and preferred ranges as R 3 , R 4 and M + in formula (I) above.
- the bonding positions of R 3 and —SO 3 ⁇ M + groups on the benzene ring are also the same as in the above general formula (I).
- Preferred combinations of R 1A , R 2A , R 3 and R 4 are R 1 to Same as R4 combination.
- m is 1 or 2;
- n is an integer of 0 to 2, preferably 0 or 1;
- the compound represented by the above general formula (I) is a compound represented by the following general formula (III).
- the compound represented by the general formula (III) is a compound in which a p-vinyl-substituted phenylsulfonylamino group among the above combined groups is applied as R 4 in the above general formula (I), and is a polyfunctional polymerizable compound. and preferably a bifunctional polymerizable compound or a tetrafunctional polymerizable compound.
- R 1 to R 3 , M + , k, m and n have the same meanings as R 1 to R 3 , M + , k, m and n in general formula (I) above, The preferred range is also the same.
- the bonding positions of the benzene rings of R 2 , R 3 and —SO 3 ⁇ M + groups are also the same as in the above general formula (I).
- Preferred combinations of R 1 to R 3 are the same as the combinations of R 1 to R 3 in general formula (I) above.
- the compound represented by the above general formula (I) is a compound represented by the following general formula (V).
- the compound represented by the general formula ( V ) is a compound in which a group obtained by combining a p-vinyl-substituted phenylsulfonylamino group and LA among the above combined groups is applied as R 4 in the above general formula (I). is.
- This compound is a polyfunctional polymerizable compound, preferably a bifunctional polymerizable compound or a tetrafunctional polymerizable compound.
- R 1 to R 3 , M + , k, m and n have the same meanings as R 1 to R 3 , M + , k, m and n in general formula (I) above; The preferred range is also the same.
- the bonding positions of the benzene rings of R 2 , R 3 and —SO 3 ⁇ M + groups are also the same as in the above general formula (I).
- Preferred combinations of R 1 to R 3 are the same as the combinations of R 1 to R 3 in general formula (I) above.
- LA represents a single bond or a divalent linking group.
- a divalent linking group that can be used as L A is not particularly limited and can be appropriately selected, and preferably includes an oxygen atom (--O-- group), an alkylene group, an alkenylene group, an arylene group, and the like.
- these groups include groups obtained by removing one hydrogen atom from each of the alkyl groups, alkenyl groups, and aryl groups that can be taken as R 2 above.
- LA is preferably a single bond, an alkenylene group or an oxygen atom, more preferably a single bond or an alkenylene group.
- the compound represented by any one of the general formulas (I) to (III), particularly the compound represented by the general formula (II), is preferably a compound represented by the following general formula (IV).
- the compound represented by the general formula (IV) is a compound in which the p-vinyl-substituted phenylsulfonylamino group among the above combined groups is applied as R 4 in the above general formula (II).
- This compound is a polyfunctional polymerizable compound, preferably a bifunctional polymerizable compound or a tetrafunctional polymerizable compound.
- R 1A , R 2A , R 3 , M + , m and n have the same meanings as R 1A , R 2A , R 3 , M + , m and n in general formula (II) above. and the preferred ranges are also the same.
- the bonding positions of the benzene rings of R 2A , R 3 and —SO 3 ⁇ M + groups are also the same as in the above general formula (II).
- Preferred combinations of R 1A , R 2A and R 3 are the same as the combinations of R 1A , R 2A and R 3 in the general formula (II).
- the compound represented by general formula (I), (II) or (V), particularly the compound represented by general formula (II), is more preferably a compound represented by general formula (VI) below. It is a mode.
- the compound represented by the general formula (VI) is a compound in which a group obtained by combining a p-vinyl-substituted phenylsulfonylamino group and L B among the above combined groups is applied as R 4 in the above general formula (II). is.
- This compound is a polyfunctional polymerizable compound, preferably a bifunctional polymerizable compound or a tetrafunctional polymerizable compound.
- R 1A , R 2A , R 3 , M + , m and n have the same meanings as R 1A , R 2A , R 3 , M + , m and n in general formula (II). , and the preferred ranges are also the same.
- the bonding positions of the benzene rings of R 2A , R 3 and —SO 3 ⁇ M + groups are also the same as in the above general formula (II).
- Preferred combinations of R 1A , R 2A and R 3 are the same as the combinations of R 1A , R 2A and R 3 in the general formula (II).
- the compound represented by general formula (III) or (IV) has an asymmetrical structure with respect to the benzene ring (the benzene ring to which the —SO 3 ⁇ M ⁇ + group can be bonded) located in the center of each formula. symmetrical structure is preferred.
- the compound represented by general formula ( V ) or (VI) may have an asymmetrical structure with respect to the linking group LA or LB, but preferably has a symmetrical structure.
- the compound of the present invention can be synthesized by a known synthesis method, and further by a method according to the synthesis method shown in the examples described later.
- the polymerizable composition of the present invention contains (A) at least one compound represented by the general formula (I) as an essential component, optionally containing (B) another copolymerizable compound, (C) polymerization initiation (D) a co-sensitizer, (E) a polymerization inhibitor, (F) a solvent, and (G) an alkali metal compound.
- compound (A) the compound represented by the general formula (I) (hereinafter sometimes referred to as compound (A)) contained in the polymerizable composition is not particularly limited, and the compound represented by each of the above general formulas It can be selected as appropriate.
- the number of types of compound (A) contained in the polymerizable composition is not particularly limited as long as it is one or more, but is preferably two or more, and can be, for example, five or less.
- the compound (A) may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound.
- the polymerizable composition contains two or more compounds (A)
- two or more of the compounds represented by the above general formulas can be appropriately combined. A combination with is preferred.
- the total content of the compound (A) in the polymerizable composition is not particularly limited, for example, it is preferably 5 to 95% by mass, preferably 5 to 60% by mass, based on the total mass of the polymerizable composition. is more preferable, 10 to 40% by mass is more preferable, and 15 to 30% by mass is also preferable.
- the content of the monofunctional polymerizable compound is not particularly limited.
- water permeability can be improved without significantly impairing the effect of improving resistance and alkali resistance, for example, in the total weight of the polymerizable composition, it is preferably more than 0% by mass and 90% by mass or less, 1 to 20 % by mass is more preferred, and 3 to 10% by mass is even more preferred.
- the content of the polyfunctional polymerizable compound is not particularly limited, but the effect of improving acid resistance and alkali resistance while maintaining water permeability when made into a polymer is high, for example, the total amount of the polymerizable composition It is preferably more than 0% by mass and 95% by mass or less, more preferably 5 to 60% by mass, and even more preferably 15 to 25% by mass.
- the polymerizable composition of the present invention may contain, in addition to the compound (A), other copolymerizable compounds copolymerizable with the compound (A) as components forming a polymer.
- "Another polymerizable compound” is a polymerizable compound different in chemical structure from the compound (A). This polymerizable compound may be a polyfunctional polymerizable compound, but is preferably a monofunctional polymerizable compound.
- Examples of such other polymerizable compounds include acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl ester compounds, vinyl ether compounds, aromatic vinyl compounds such as styrene compounds, allyl compounds, acrylic Known polymerizable compounds such as acids, methacrylic acid, acrylonitrile, maleic anhydride, and maleic acid imide can be used. By copolymerizing such a polymerizable compound, it is possible to improve various physical properties such as film formability, film strength, hydrophilicity, hydrophobicity, solubility, reactivity and stability.
- (meth)acrylamide compounds those having no ester bond, (meth)acrylamide compounds, vinyl ether compounds, aromatic vinyl compounds, N-vinyl compounds (with amide polymerizable monomer), allyl compounds are preferred, and (meth)acrylamide compounds are particularly preferred.
- the (meth)acrylamide compound is preferably a compound represented by the following general formula (B).
- R 10 represents a hydrogen atom or methyl.
- R 11 represents a hydrogen atom or a substituted or unsubstituted alkyl group
- R 12 represents a substituted or unsubstituted alkyl group.
- R 11 and R 12 may combine with each other to form a ring.
- R 10 is preferably a hydrogen atom.
- the number of carbon atoms in the alkyl group for R 11 and R 12 is preferably 1-18, more preferably 1-12, and particularly preferably 1-6.
- the alkyl group is preferably a linear or branched alkyl group, and may have a substituent.
- the substituents that the alkyl group may have are not particularly limited, and examples thereof include a hydroxy group, a sulfo group or a salt thereof, a carboxy group or a salt thereof, a phosphoric acid group or a salt thereof, an onio group (ammonio, pyridinio, sulfonio, etc.), halogen atoms, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups (including amino groups, alkylamino groups, arylamino groups, heterocyclic amino groups ), amide group, sulfonamide group, carbamoyl group, sulfamoyl group, acyl group, cyano group and the like.
- the substituent of this alkyl group is given a function, especially in order to give the function of a polymer film. Therefore, among the above substituents, a dissociative group and a polar substituent are preferred, and a dissociative group is particularly preferred.
- the dissociative group is preferably a hydroxy group (especially a phenolic or enolic hydroxy group), a sulfo group or a salt thereof, a carboxy group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfo group or a salt thereof is more preferred.
- the counter cations for the sulfo group, carboxy group, etc. are preferably organic base ions such as N-methylmorpholinyl and pyridinium, and cations of alkali metal atoms such as lithium cation, potassium cation and sodium cation.
- the other copolymerizable compound is preferably a monofunctional polymerizable compound, and is particularly preferably used in combination with a polyfunctional polymerizable compound represented by any one of general formulas (III) to (VI).
- the total content of other copolymerizable compounds in the polymerizable composition is not particularly limited, for example, the total weight of the polymerizable composition, preferably 0 to 90% by mass, 0 to 60% by mass more preferably 3 to 15% by mass.
- the polymerizable composition of the present invention may contain various components such as additives and solvents in addition to the polymerizable compounds described above.
- the polymerizable composition may contain one or more of various components.
- Various components will be briefly described below, but for details thereof, the contents described in JP 2014-171951 A can be referred to as appropriate, and the contents thereof are incorporated as part of the description of the present specification.
- the polymerizable composition of the invention preferably contains a polymerization initiator.
- the polymerization initiator is not particularly limited, but a photopolymerization initiator capable of polymerizing a polymerizable compound by energy ray irradiation is preferable.
- photopolymerization initiators include aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, Metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, alkylamine compounds and the like can be mentioned.
- a water-soluble polymerization initiator is preferably used in the present invention.
- the fact that the polymerization initiator is water-soluble means that it dissolves in distilled water at 25° C. in an amount of 0.5 mass % or more.
- the water-soluble photopolymerization initiator is more preferably soluble in distilled water at 25° C. in an amount of 1% by mass or more, particularly preferably 3% by mass or more.
- the content of the polymerization initiator in the polymerizable composition is not particularly limited.
- the total weight of the polymerizable composition is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. , more preferably 0.3 to 2 parts by mass.
- the polymerizable composition of the present invention may contain, as a co-sensitizer, a known compound having actions such as further improving sensitivity or suppressing inhibition of polymerization by oxygen.
- co-sensitizers include amine compounds, thiol and sulfide compounds, amino acid compounds, organometallic compounds, hydrogen donors, sulfur compounds, phosphorus compounds, Si—H and Ge—H compounds.
- the content of the co-sensitizer in the polymerizable composition is not particularly limited. Parts by weight are more preferred, and 0.10 to 1.00 parts by weight is even more preferred.
- the polymerizable composition of the present invention preferably contains a polymerization inhibitor.
- a polymerization inhibitor known polymerization inhibitors can be used, including phenol compounds, hydroquinone compounds, amine compounds, mercapto compounds and the like.
- the content of the polymerization inhibitor in the polymerizable composition is not particularly limited.
- the total weight of the polymerizable composition is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass. , 0.01 to 0.5 parts by mass is more preferable.
- the polymerizable composition of the invention may contain at least one of water and an organic solvent as a solvent.
- the content of the solvent in the polymerizable composition is not particularly limited, and is usually the balance of the polymerizable composition, for example, the total weight of the polymerizable composition, preferably 5 to 90% by mass. , more preferably 30 to 85% by mass, and even more preferably 50 to 80% by mass.
- the polymerizable composition contains a solvent, the polymerization reaction proceeds uniformly and smoothly. Moreover, when the porous support is impregnated with the polymerizable composition, the impregnation can be performed smoothly.
- the organic solvent to be used preferably has a solubility in water of 5% by mass or more, and more preferably one that is freely mixed with water. For this reason, solvents selected from water-soluble solvents are preferred.
- the water-soluble solvent is not particularly limited, but is preferably an alcohol solvent, an aprotic polar solvent such as an ether solvent, an amide solvent, a ketone solvent, a sulfoxide solvent, a sulfone solvent, a nitrile solvent, or an organic phosphorus solvent.
- the polymerizable composition of the present invention may contain an alkali metal compound in order to improve the solubility of (B) other polymerizable compounds, particularly compounds having a (meth)acrylamide structure.
- the alkali metal compound is also preferably used to neutralize the composition, composition solution mixture.
- the alkali metal compound lithium, sodium and potassium hydroxide salts, chloride salts, nitrates and the like are preferable.
- lithium compounds are more preferable, and specific examples include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoro borate, lithium hexafluorophosphate, and lithium hexafluoroarsenate.
- the alkali metal compound may be a hydrate.
- the content of the alkali metal compound in the polymerizable compound is not particularly limited. 0.5 to 5 parts by mass is more preferable.
- the polymerizable composition of the present invention can also contain various polymer compounds for the purpose of improving the physical properties of the polymer film.
- Polymer compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, and rubber resins. , waxes, and other natural resins can be used.
- the polymerizable composition of the present invention may also contain nonionic surfactants, cationic surfactants, organic fluoro compounds, etc. for the purpose of improving the liquid properties of the polymerizable composition. Furthermore, for example, a viscosity improver, a surface tension modifier, and a preservative may be contained.
- the polymerizable composition of the present invention can be prepared by mixing each of the above components by a conventional method.
- the polymerizable composition of the present invention can be suitably used as a material for forming the polymer film of the present invention, which will be described later.
- the polymer (polymer) of the present invention has at least one component [A] derived from the compound (A) represented by the above general formula (I), and contains at least one compound (A). It is synthesized through a polymerization reaction.
- the polymer of the present invention exhibits high acid resistance and alkali resistance due to the compound (A) and can be used in a wide range of applications, and is particularly suitable as a polymer constituting a polymer film.
- the polymer of the present invention preferably has two or more constituent components [A], and may also have a constituent component derived from a monofunctional polymerizable compound and a constituent component derived from a polyfunctional polymerizable compound. preferable.
- the component [A] is incorporated in the polymer as at least one component derived from a monofunctional polymerizable compound and a component derived from a polyfunctional polymerizable compound, and the polyfunctional polymerization It is preferably incorporated into the polymer as one of the structural components derived from the polar compound.
- This component [A] may be incorporated into the polymer as either a component derived from a monofunctional polymerizable compound or a component derived from a polyfunctional polymerizable compound.
- the constituent component derived from a compound other than the compound (A), which may be contained in the polymer of the present invention, is not particularly limited.
- Constituent component [B] is included, and it is preferable to have constituent component [B] as a constituent component derived from a monofunctional polymerizable compound.
- the mode of bonding of the constituent components is not particularly limited. may be linked.
- the component [A] derived from the compound (A), which the polymer of the present invention has, is a component obtained by polymerizing the compound represented by any one of the general formulas (I) to (VI), It exhibits high acid and alkali resistance.
- Component [A] is specifically represented by the following general formula (IP).
- the constituent represented by general formula (IP) is a constituent derived from the compound represented by general formula (I), and in general formula (IP), R 1 to R 3 , M + , k, m and n have the same meanings as R 1 to R 3 , M + , k, m and n in formula (I) above, and the preferred ranges are also the same.
- the constituent represented by the above general formula (IP) is preferably represented by the following general formula (IIP).
- the constituent represented by general formula (IIP) is a constituent derived from the compound represented by general formula (II), and in general formula (IIP), R 1A , R 2A , R 3 and R 4 , M + , m and n have the same meanings and preferred ranges as R 1A , R 2A , R 3 , R 4 , M + , m and n in the general formula (II).
- the component represented by the above general formula (IP) is a component represented by the following general formula (IIP).
- the constituent represented by the general formula (IIP) is a constituent derived from the compound represented by the general formula (III), and in the general formula (IIP), R 1 to R 3 , M + , k, m and n have the same meanings as R 1 to R 3 , M + , k, m and n in general formula (IP) above, and the preferred ranges are also the same.
- the constituent represented by the above general formula (IP) is a constituent represented by the following general formula (VP).
- the constituent represented by the general formula (VP) is a constituent derived from the compound represented by the general formula (V), and in the general formula (VP), R 1 to R 3 , M + , k, m and n have the same meanings as R 1 to R 3 , M + , k, m and n in general formula (IP) above, and the preferred ranges are also the same.
- the constituent represented by any one of the general formulas (IP) to (IIP), particularly the constituent represented by the general formula (IIP), is a constituent represented by the following general formula (IVP).
- the constituent represented by the general formula (IVP) is a constituent derived from the compound represented by the general formula (IV), and in the general formula (IVP), R 1A , R 2A , R 3 , M + , m and n have the same meanings and preferred ranges as R 1A , R 2A , R 3 , M + , m and n in the general formula (IIP).
- the constituent represented by the general formula (IP), (IIP) or (VP), particularly the constituent represented by the general formula (IIP), is a constituent represented by the following general formula (VIP).
- the constituent represented by the general formula (VIP) is a constituent derived from the compound represented by the general formula (VI), and in the general formula (VIP), R 1A , R 2A , R 3 , M + , m and n have the same meanings and preferred ranges as R 1A , R 2A , R 3 , M + , m and n in formula (IIP).
- the component [A] represented by each general formula above has an alkenyl group (ethylenic double bond) as a group represented by a symbol such as R 2 to R 4 , L A , or LB in each formula above. If so, the alkenyl group may or may not be polymerized.
- the polymer of the present invention may have a component represented by the following formula (PB) as (B) a component [B] derived from another copolymerizable compound.
- R 10 , R 11 and R 12 have the same meanings as R 10 , R 11 and R 12 in general formula (B) above, and their preferred ranges are also the same.
- the content of the component [A] derived from the compound (A) and the component [B] derived from another copolymerizable compound depends on the polymerization reactivity of each compound. Although not determined unconditionally, for example, it can be in the same range as the content (mass ratio) of each compound in the polymerizable composition of the present invention to be used.
- the polymer of the present invention Since the polymer of the present invention has a component derived from the compound (A) of the present invention, it exhibits excellent acid resistance and alkali resistance.
- the average mass molecular weight of the polymer of the present invention is not particularly limited, but when it contains a component derived from a polyfunctional polymerizable compound, it is usually several hundred thousand or more because three-dimensional crosslinks are formed, practically unmeasurable. generally regarded as infinity.
- the method for synthesizing the polymer of the present invention is not particularly limited, and the polymer can be synthesized according to an appropriate method.
- the polymer of the present invention can also be polymerized continuously or simultaneously with the production of the polymer film in the production of the polymer film, which will be described later.
- the polymer film of the present invention contains at least one polymer of the present invention.
- the content of the polymer in the polymer film of the present invention is not particularly limited, but is preferably 20 to 98% by mass, more preferably 50 to 95% by mass, based on the total mass of the polymer film.
- the lower limit may be 70% by mass or 80% by mass.
- the polymer membrane of the present invention (hereinafter also simply referred to as membrane) can be used in a wide range of applications, such as ion exchange, selective permeation of ions, proton conduction, fuel cells, protein aggregates or virus removal, and the like. can be used to do
- preferred embodiments of the present invention will be described by taking as an example the case where the polymer membrane of the present invention has a function as a cation exchange membrane.
- the thickness of the film is not particularly limited, it is preferably 150 ⁇ m or less, more preferably 5 to 150 ⁇ m, still more preferably 10 to 130 ⁇ m.
- the thickness of the polymerizable membrane including the porous support which will be described later, is set within the above range, including the porous support.
- the thickness of the film referred to here is the thickness of the film when the film is impregnated with a 0.5 M NaCl aqueous solution and saturated.
- the permselectivity for cations such as Na + is not particularly limited. greater than, most preferably greater than 0.96.
- the permselectivity of the membrane preferably has a high value even after the membrane is treated with acid and alkali, for example, preferably 0.85 or more (Evaluation Criteria C) in Examples described later.
- the water permeability of the membrane is preferably 14 ⁇ 10 ⁇ 5 mL/m 2 /Pa/hr or less, more preferably 12 ⁇ 10 ⁇ 5 mL/m 2 /Pa/hr or less, and 10 ⁇ 10 ⁇ 5 mL/m 2 /Pa/hr or less. -5 mL/m 2 /Pa/hr or less is most preferable. It is preferable that the water permeability of the membrane is maintained at the above value even after the film is treated with acid and alkali and does not significantly decrease.
- the water absorption of the film is not particularly limited, but is preferably less than 70%, more preferably less than 50%, and particularly preferably less than 40%, based on the weight of the dry film.
- the ion exchange capacity of the membrane is not particularly limited, e.g., preferably 0.5 meq/meq, relative to the total dry mass of the membrane and the porous support and any porous reinforcing material remaining in contact with the resulting membrane. g or more, more preferably 0.8 meq/g or more, and particularly preferably 1.2 meq/g or more.
- the bursting strength, electrical resistance (membrane resistance), and swelling rate in water (rate of dimensional change due to swelling) of the membrane are not particularly limited and can be appropriately set.
- the polymer membrane of the present invention has sulfonic acid groups (SO 3 ⁇ ) and can be used, for example, as an electrolyte membrane (ion exchange membrane) to exchange the cation Na + in water containing salts such as NaCl. can do.
- An ideal ion exchange membrane has low membrane resistance, low permeability and high transport number (cation/anion exchange separation selectivity). Generally, the higher the charge density per unit structural molecular weight, the lower the membrane resistance and the higher the transport number, and the higher the crosslink density, the lower the water permeability.
- the polymer film of the present invention contains a polymer having a component derived from the compound represented by general formula (I). Therefore, it exhibits high acid resistance and alkali resistance attributed to the compound represented by general formula (I).
- a porous support is preferably used for the polymer membrane of the present invention in order to obtain a membrane having good mechanical strength.
- This porous support functions as a support (reinforcing material) for the polymer membrane by being coated and/or impregnated with the polymerizable composition and then subjected to a curing reaction.
- a porous support is not particularly limited, and examples thereof include synthetic woven fabrics or synthetic nonwoven fabrics, sponge-like films, films having fine through holes, and paper.
- the content described in JP-A-2014-171951 can be referred to as appropriate, and the content thereof is incorporated as a part of the description of the present specification.
- the polymer film of the present invention may contain various components in addition to the polymer.
- Various components that may be contained in the polymer film are not particularly limited, but are the same as those in the polymerizable composition of the present invention.
- (C) polymerization initiators, (E) components that can be decomposed during polymerization such as polymerization inhibitors, and (F) volatile components such as solvents must be contained as their residues (decomposition products).
- the method for producing the polymer film of the present invention is not particularly limited.
- it can be produced by curing the polymerizable composition of the present invention (polymerizing the compound of the present invention). More specifically, it can be formed by coating the surface of the porous support with the polymerizable composition of the present invention or by impregnating the pores of the porous support, followed by a curing reaction, that is, a polymerization reaction.
- the polymer membrane of the present invention can also be formed by coating the surface of a porous support with the polymerizable composition of the present invention, impregnating the pores of the porous support, and then performing a curing reaction.
- a method of irradiating the porous support coated with the polymerizable composition with actinic radiation eg, ultraviolet rays, electron beams
- actinic radiation eg, ultraviolet rays, electron beams
- the conditions for forming the polymer film are not particularly limited, but the temperature is, for example, preferably -30 to 100°C, more preferably -10 to 80°C, and particularly preferably 5 to 60°C.
- the contents described in JP-A-2014-171951 can be referred to as appropriate, and the contents thereof are incorporated as part of the description of the present specification.
- the polymer membrane of the present invention is preferably a composite membrane combined with a porous support, and used in various modules and devices. For example, it can be used in a separation membrane module or an ion exchange device having means for ion exchange, desalting, and purification. Moreover, it can be suitably used as a fuel cell.
- the polymer membrane of the present invention can be suitably used after being modularized. Examples of modules include spiral type, hollow fiber type, pleated type, tubular type, plate & frame type, stack type, and the like.
- the polymer membrane of the present invention is particularly suitable for use in ion exchange, but in addition to ion exchange, it can also be suitably used in, for example, proton conducting membranes for fuel cells and protein/virus removal.
- Example 1 1. Synthesis of Compound Represented by General Formula (I) [Synthesis Example 1] Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized according to the following synthesis scheme.
- the aqueous layer was extracted with 300 mL of ethyl acetate, combined with the organic layer, and separated and washed three times with 500 mL of water.
- the obtained organic layer was dried with magnesium sulfate, and then the solvent was distilled off to obtain 58.6 g of styrenesulfonyl chloride containing 8% ethyl acetate.
- the obtained styrenesulfonyl chloride was identified by nuclear magnetic resonance spectroscopy ( 1 H-NMR).
- 1 H-NMR 400 MHz, CDCL 3 ): ⁇ 8.0 (2H), ⁇ 7.6 (2H), ⁇ 6.8 (1H), ⁇ 6.0 (1H), ⁇ 5.5 (1H)
- the aqueous layer was extracted with 300 mL of ethyl acetate, combined with the organic layer, and separated and washed three times with 500 mL of water. After filtering the organic layer through celite/silica gel, the resulting organic layer was dried over magnesium sulfate, and the solvent was distilled off to obtain 27.2 g of 2,4-containing 31.2% ethyl acetate. Divinylbenzenesulfonyl chloride was obtained. 2,4-divinylbenzenesulfonyl chloride was identified by nuclear magnetic resonance spectroscopy ( 1 H-NMR).
- Comparative Compounds As comparative compounds, the following comparative compounds (1) and (2) were used. The following comparative compound (2) was prepared with reference to JP-T-2014-526959.
- the peak used as a reference for calculating the decomposition rate is the hydrogen atom appearing at the chemical shift ⁇ of 7.3 ppm in Exemplified Compound (1). did.
- the alkali resistance (alkali stability) of each exemplified compound was evaluated according to which of the following evaluation criteria the calculated decomposition rate was included in. Table 1 shows the results. In this test, the lower the decomposition rate, the better the alkali resistance, and the evaluation standard "B" or higher is the acceptable level.
- the comparative compounds (1) and (2) show a high hydrolysis reaction in an alkaline environment and show a high decomposition rate, whereas the exemplary compounds corresponding to the compounds of the present invention It can be seen that both exhibit high alkali resistance even in an alkaline environment.
- Example 2 Preparation of cation films 100 to 108
- Each composition (coating solution) 100 to 108 having the composition shown in Table 2 below was prepared, and each composition was applied to an aluminum plate using a 150 ⁇ m wire-wound rod, manually about 5 m / It was applied at a speed of min.
- a nonwoven fabric (FO-2223-10 (trade name), thickness 100 ⁇ m, manufactured by Freudenberg) was placed on the coating liquid applied to the aluminum plate to impregnate the nonwoven fabric with the coating liquid. Excess coating liquid not impregnated into the nonwoven fabric was removed using a rod without wire winding. The temperature of the coating solution during coating was about 40°C.
- Comparative Example 2- which was prepared by changing the composition of Example 2-1 to the composition shown in Table 2 below.
- Cation membranes c100 and c101 of Comparative Examples 2-1 and 2-2 were prepared in the same manner as in Example 2-1 except that compositions c100 and c101 of 1 and 2-2 were used.
- Genorad 16 (trade name): manufactured by Rahn AG (polymerization initiator)
- Darocur 1173 (trade name): 2-hydroxy-2-methylpropiophenone, manufactured by Ciba Specialty Chemicals Tego Glide 432 (trade name): polyether siloxane copolymer, manufactured by Evonik Industries
- Permselectivity was calculated by measuring membrane potential (V) by static membrane potential measurement. Two electrolytic cells (cells) are separated by a membrane to be measured. The membrane was equilibrated in 0.05 M NaCl aqueous solution for about 16 hours before measurement. After that, aqueous NaCl solutions with different concentrations were respectively poured into the electrolytic cell on opposite sides of the membrane to be measured. 100 mL of 0.05 M NaCl aqueous solution was poured into one of the cells. Also, 100 mL of 0.5 M NaCl aqueous solution was poured into the other cell.
- the cation membranes 100 to 108 produced in Examples 2-1 to 2-9 had the same selective permeability and water permeability as the cation membranes c100 and c101 produced in Comparative Examples 2-1 and 2-2. , and had sufficient performance as a cation membrane.
- Example 3 Production of Acid and Alkaline Treated Membranes 200-207, c200 and c201
- Each of the cation membranes 100-104, 106-108, c100 and c101 produced in Example 2 was immersed in 4 M hydrochloric acid water at 25° C. for 6 hours. rice field.
- the acid-treated cationic membrane was then removed from the 4M aqueous hydrochloric acid and held in a 0.1M NaCl solution at 25° C. for at least 12 hours.
- the cationic membrane was taken out from the NaCl solution and immersed in a 1 M sodium hydroxide aqueous solution at 25° C. for 6 hours.
- the alkali-treated cation membrane was removed from the aqueous sodium hydroxide solution and stored (immersed) in a 0.1 M NaCl solution at 25° C. for at least 12 hours.
- acid-treated and alkali-treated cationic membranes (acid- and alkali-treated membranes) 200 to 207, c200 and c201 were produced.
- ⁇ Selective permeability (transference number) test> The permselectivity (transportation number) was measured in the same manner as ⁇ permselectivity (transportation number) test> in Example 2 using the acid- and alkali-treated membranes 200 to 207, c200 and c201.
- the permselectivity (transportation number) of the acid- and alkali-treated membranes was evaluated according to which of the following evaluation criteria the measured transference number was included. In this test, the higher the transference number of the acid- and alkali-treated membrane, the higher the cation membrane's resistance to acidic and alkaline environments. can.
- ⁇ Water Permeability (mL/m 2 /Pa/hr) Test> Using the acid and alkali treated membranes 200 to 207, c200 and c201, in the same manner as ⁇ water permeability (mL/m 2 /Pa/hr) test> in Example 2, the water permeability (mL/m 2 /Pa/ hr) was measured. The rate of change in water permeability of the acid- and alkali-treated membranes relative to the cation membranes 100 to 104, 106 to 108, c100 and c101 produced in Example 2 was calculated from the following formula.
- the acid resistance and alkali resistance of the acid- and alkali-treated film were evaluated according to which of the following evaluation criteria the measured rate of change was included.
- the smaller the rate of change in water permeability the higher the acid resistance and alkali resistance of the cationic membrane produced in Example 2 (the membrane is stable against acids and alkalis).
- Alkali-treated membranes can maintain excellent permeability even in acidic and alkaline environments.
- Amount of change in permeability (%) [(permeability of cationic membrane-permeability of acid and alkali treated membrane)/permeability of cationic membrane] ⁇ 100 - Evaluation criteria - A: Less than 10% B: 10% or more and less than 20% C: 20% or more and less than 30% D: 30% or more
- the cation membranes c100 and c101 produced in Comparative Examples 3-1 and 3-2 were subjected to acid treatment and alkali treatment (assuming alkali-treated membranes c200 and c201), and the permselectivity has decreased significantly, and the permeability has increased significantly. This is probably because the polymer constituting the cationic membrane underwent a hydrolysis reaction during acid treatment or alkali treatment.
- Membrane 2 Arrows indicating the penetration of water in the feed solution through the membrane into the draw solution 3
- Feed solution flow path 4
- Draw solution flow path 5
- Direction of liquid travel 10
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Abstract
Description
例えば、特許文献1には、平版印刷版において、支持体と感光層との間に設けられる中間層を形成する重合性化合物として、例えば、スチレンのフェニル基とベンゼンスルホン酸のフェニル基とを、スルホン酸基がパラ位となるように、スルホン酸アミド結合で結合した化合物が記載されている。また、特許文献2には、画像形成装置に装備される現像剤担持体に用いる電荷制御剤を構成するための重合性単量体として、サリチル酸ユニットを組み込んだスチレン化合物、より具体的には、スチレンのフェニル基とサリチル酸とを、フェノール性水酸基がパラ位となるように、スルホン酸アミド結合で結合した重合性化合物が記載されている。更に、特許文献3には、水溶性染料として、α-ブロモスチレン骨格と、アントラキノン等の水溶性有機染料残基とを、スルホン酸アミド結合を含む基で結合した化合物(反応性有機染料)が記載されている。
しかし、従来の機能性重合体、特に特許文献1~3に記載の重合体及び単量体については、酸耐性及びアルカリ耐性の発現若しくは向上については何ら検討されていない。
本発明は、アルカリ耐性を示す化合物、及びこの化合物を含む重合性組成物を提供することを課題とする。また、本発明は、上記化合物に由来する構成成分を有し、酸耐性及びアルカリ耐性を示す重合体、並びにこの重合体を含み、酸耐性及びアルカリ耐性を示す重合膜を提供することを課題とする。
<1>下記一般式(I)で表される化合物。
R1は水素原子又は低級アルキル基を示す。
R2はアルキル基、アルケニル基、アリール基、ハロゲン原子、水酸基又はアミノ基を示す。
R3はアルキル基、アルケニル基、アリール基、ハロゲン原子、アミノ基、カルボキシ基、若しくは-SO3 -M+基を有する基、又は、アルキル基、アルケニル基、アリール基、酸素原子、-SO3 -M+基若しくはアリールスルホニルアミノ基を組み合わせた基を示す。
R4は水素原子、アルキル基、アルケニル基、アリール基、ハロゲン原子、アミノ基若しくはカルボキシ基、又は、アルキル基、アルケニル基、アリール基、酸素原子、-SO3 -M+基若しくはアリールスルホニルアミノ基を組み合わせた基を示す。
M+はH+、Li+、Na+、K+、Cs+又はアンモニウム塩を示す。
kは0~4の整数であり、kが2以上の整数である場合、複数存在するR2は互いに同じでも異なっていてもよく、互いに連結して環を形成してもよい。
nは0~4の整数であり、nが2以上の整数である場合、複数存在するR3は互いに同じでも異なっていてもよく、互いに連結して環を形成してもよい。
mは0~4の整数であり、mが2以上の整数である場合、複数存在する-SO3 -M+基は互いに同じでも異なっていてもよい。
ただし、nとmは1≦n+m≦4を満たす。またmが0である場合、少なくとも1つのR3は-SO3 -M+基を有する基である。
R1Aは水素原子又はメチル基を示す。
R2Aは水素原子、-CH=CH2又は-C(CH3)=CH2を示す。
R3、R4及びM+は一般式(I)のR3、R4及びM+と同じ意味を持つ。
mは1又は2であり、nは0~2の整数である。
<8>上記<1>~<6>のいずれか1つに記載の化合物に由来する構成成分を有する重合体。
<9>上記<8>に記載の重合体を含む重合膜。
本発明の上記及び他の特徴及び利点は、適宜に添付の図面を参照して、下記の記載からより明らかになるであろう。
本発明において、化合物の表示(例えば、化合物と末尾に付して呼ぶとき)については、この化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、本発明の効果を損なわない範囲で、置換基を導入する等一部を変化させた誘導体を含む意味である。
本発明において、「(メタ)アクリル」等の記載は、-C(=O)CH=CH2及び-C(=O)C(CH3)=CH2、又は-C(=O)CH=CH2と-C(=O)C(CH3)=CH2の少なくとも一方を意味するものであり、「(メタ)アクリルアミド」は、アクリルアミド及びメタクリルアミド、又はアクリルアミドとメタクリルアミドの少なくとも一方を、「(メタ)アクリレート」は、アクリレート及びメタクリレート、又はアクリレートとメタクリレートの少なくとも一方を、それぞれ表す。
また、各一般式において、特に断りがない限り、複数存在する同一符号の基がある場合、これらは互いに同一であっても異なってもよく、同じく、複数の部分構造の繰り返しがある場合は、これらの繰り返しが同一の繰り返しでも、また規定する範囲で異なった繰り返しの混合の両方を意味するものである。
更に、各一般式における二重結合の置換様式である幾何異性体は、表示の都合上、異性体の一方を記載したとしても、特段の断りがない限り、E体であってもZ体であっても、これらの混合物であっても構わない。更に、各一般式で表される化合物において、連結基等としてエチレン性二重結合を有する場合、この化合物の重合体において、エチレン性二重結合は重合していてもよい。
本発明において、特に断らない場合であっても、複数の置換基等が隣接するときにはそれらが互いに連結したり縮環したりして環を形成していてもよい意味である。
本発明の化合物は、スチレン化合物のベンゼン環に対して、そのパラ位にスルホン酸アミド結合を介してスルホン酸基含有ベンゼン環を導入した化学構造を有する重合性化合物であり、スチレンスルホンアミド化合物ということができる。本発明の化合物は、具体的には下記一般式(I)で表される。この化合物は、優れたアルカリ耐性を発現し、更に水溶性をも示す。
本発明において、アルカリ耐性とは、化合物、重合体、重合膜等がアルカリ性環境下において加水分解反応を受けにくい特性(分解進行を抑制できる特性)をいう。アルカリ性の強度、アルカリ性環境下への暴露期間の長期化等により、化合物等の一部分解は避けられないが、本発明においては、少なくとも、後述する実施例における試験で合格レベルにある。
また、酸耐性とは、重合体、重合膜等が酸性環境下において加水分解反応を受けにくい特性(分解進行を抑制できる特性)をいう。酸性の強度、酸性環境下への暴露期間の長期化等により、重合体等の一部分解は避けられないが、本発明においては、少なくとも、後述する実施例における試験で合格レベルにある。なお、本発明の化合物は、酸性環境下ではスチレン(エチレン性二重結合)が重合しやすいが、その他の化学構造部分は酸耐性を示す。
上記特性を示す本発明の化合物は、後述するように、単独重合若しくは共重合することにより、化合物の上記特性を活かして、優れた酸耐性及びアルカリ耐性を発現する重合体を形成できる。そのため、本発明の化合物は、広範な用途に用いることができ、特に重合膜を構成する重合体用化合物として好適である。
R1としてとりうる低級アルキル基は、炭素数が1~4のアルキル基であり、好ましくは炭素数が1~3のアルキル基である。低級アルキル基は、直鎖、分岐若しくは環状鎖のいずれであってもよい。低級アルキル基としては、例えば、メチル、エチル、n-プロピル、iso-プロピル、n-ブチル、tert-ブチル等が挙げられる。
R1は、水素原子又はメチル基が好ましく、水素原子がより好ましい。
R2としてとりうるアルキル基は、直鎖、分岐若しくは環状鎖のいずれであってもよい。アルキル基を構成する炭素数は、特に制限されず、例えば、1~10であることが好ましく、1~5であることがより好ましく、1~3であることが特に好ましい。R2としてとりうるアルキル基としては、例えば、メチル、エチル、n-プロピル、iso-プロピル、n-ブチル、tert-ブチル、n-オクチル、2-エチルヘキシル、n-デシル、n-ヘキサデシル等が挙げられる。
R2としてとりうるアルケニル基は、直鎖、分岐若しくは環状鎖のいずれであってもよい。アルケニル基を構成する炭素数は、特に制限されず、例えば、2~10であることが好ましく、2~6であることがより好ましく、2~5であることが特に好ましい。R2としてとりうるアルケニル基としては、例えば、ビニル(-CH=CH2)、2-プロペニル(-CH2-CH=CH2)、イソプロペニル(-CH(CH3)=CH2)、ブテニル、ヘキセニル等が挙げられる。中でもビニル基又はイソプロペニルが好ましい。
芳香族複素環基を構成する環構成ヘテロ原子としては、窒素原子、酸素原子、硫黄原子が好ましい。また、単環の芳香族複素環基の環員数としては5員環又は6員環が好ましい。芳香族複素環基としては、例えば、ピロール環、ピリジン環等の含窒素複素環からなる基、フラン環基、チオフェン環基、ベンゾチアゾール環基等が挙げられる。
R2としてとりうるアミノ基としては、無置換アミノ基(-NH2)、アルキル基若しくはアリール基で置換されたモノ若しくはジ-アルキル若しくはアリールアミノ基を含む。アルキル基及びアリール基としては、特に制限されないが、例えば、上述の、R2としてとりうるアルキル基及びアリール基が挙げられる。
後述するkが1以上の整数である場合、R2が結合するベンゼン環の位置は特に制限されず、エチレン性二重結合(R1を有するビニル基)が結合する環構成炭素原子に対して2位(オルト位)でも3位(メタ位)でもよいが、3位であることが好ましい。
R3としてとりうる、アルキル基、アルケニル基、アリール基、ハロゲン原子及びアミノ基は、それぞれ、R2としてとりうる、アルキル基、アルケニル基、アリール基、ハロゲン原子及びアミノ基と同じ意味である。
R3としてとりうる、-SO3 -M+基を有する基としては、連結基を介して-SO3 -M+基を一般式(I)中のベンゼン環に導入する基であればよい。連結基としては、特に制限されず、適宜に選択できるが、アルキレン基、アルケニレン基、アリーレン基等が好適に挙げられる。これらの基としては、それぞれ、R2としてとりうる、アルキル基、アルケニル基又はアリール基のそれぞれから更に水素原子を1つ除去した基が挙げられる。
組み合わせた基を形成する、アルキル基、アルケニル基、アリール基は、それぞれ、R2としてとりうる、アルキル基、アルケニル基、アリール基と同じ意味である。また、アリールスルホニルアミノ基を構成するアリール基は、R2としてとりうるアリール基と同義であり、芳香族炭化水素環基が好ましく、ベンゼン環基がより好ましい。
組み合わせた基において組み合わせる基の数は、特に制限されないが、例えば、2~10個であることが好ましく、2~8個であることがより好ましく、2~6個であることが更に好ましく、2~4個であることが特に好ましい。組み合わせる基は、特に制限されないが、アルケニル基と-SO3 -M+基又はアリールスルホニルアミノ基とを含む組み合わせが好ましく、後述するR4としてとりうる組み合わせた基を採ることもできる。
上記組み合わせた基としては、ビニル基と-SO3 -M+基とを組み合わせた基、ビニル基とフェニルスルホニルアミノ基とを組み合わせた基(フェニルスルホニルアミノ基の窒素原子で一般式(I)中のベンゼン環と結合する)が好ましい。
後述するnが1以上の整数である場合、R3が結合するベンゼン環の位置は特に制限されず、スルホニルアミノ基が結合する環構成炭素原子に対して2位(オルト位)でも3位(メタ位)でもよい。
R4としてとりうる、アルキル基、アルケニル基、アリール基、ハロゲン原子及びアミノ基は、それぞれ、R2としてとりうる、アルキル基、アルケニル基、アリール基、ハロゲン原子及びアミノ基と同じ意味である。
R4としてとりうる上記組み合わせた基を形成する、アルキル基、アルケニル基、アリール基は、それぞれ、R2としてとりうる、アルキル基、アルケニル基、アリール基と同じ意味である。また、アリールスルホニルアミノ基は、R3としてとりうる上記組み合わせた基を構成するアリールスルホニルアミノ基と同義である。
p-ビニル置換フェニルスルホニルアミノ基としては、具体的には、後述する一般式(III)若しくは(IV)で表される化学式における中央のベンゼン環に結合している「p-ビニル置換フェニルスルホニルアミノ基」が挙げられる。p-ビニル置換フェニルスルホニルアミノ基を含む基としては、p-ビニル置換フェニルスルホニルアミノ基と連結基(例えば後述するLA若しくはLB)とを含む基が挙げられ、具体的には、後述する一般式(V)若しくは(VI)で表される化学式における左から2つ目のベンゼン環に結合している「LA若しくはLBを含むp-ビニル置換フェニルスルホニルアミノ基」が挙げられる。
M+としてとりうるアンモニウム塩としては、特に制限されず、NH4 +又は少なくとも1つの有機基を有する有機アンモニウム塩が挙げられる。有機アンモニウム塩を構成する有機基としては、アルキル基、アリール基等が挙げられ、アルキル基が好ましい。アルキル基としては、特に限定されないが、炭素数1~18のアルキル基が好ましく、炭素数1~6のアルキル基がより好ましい。アリール基としては、特に限定されず、例えば、R2としてとりうるアリール基が挙げられる。有機アンモニウム塩が有する有機基の数(級数)は、1個以上(2~4級アンモニウム塩)であればよいが、3個(3級アンモニウム塩)又は4個(4級アンモニウム塩)であることが好ましい。有機基を2個以上する場合、有機基は同一でも異なっていてもよい。有機アンモニウム塩としては3級アルキルアンモニウム塩又は4級アルキルアンモニウム塩が好ましい。
後述するmが1以上の整数である場合、-SO3 -M+基が結合するベンゼン環の位置は特に制限されず、スルホニルアミノ基が結合する炭素原子に対して2位(オルト位)でも3位(メタ位)でもよいが、3位であることが好ましい。
なお、k及びnがそれぞれ2以上の整数である場合、複数存在するR2及びR3は互いに同じでも異なっていてもよく、互いに連結して環を形成してもよい。例えば、後記例示化合物(13)において、R3として-SO3 -M+基を有するビニル基とビニル基とが隣接する環構成炭素原子に結合し、この2つのビニル基が互いに連結してベンゼン環と縮合した環(ナフタレン環)を形成している。また、mが2以上の整数である場合、複数存在する-SO3 -M+基は互いに同じでも異なっていてもよい。
一般式(I)で表される化合物は、重合膜に用いたときの透水性の観点からは単官能重合性化合物であることが好ましく、一方、重合体としたとき若しくは重合膜に用いたときの酸耐性及びアルカリ耐性の改善効果の観点からは多官能重合性化合物であることが好ましい。
mは1又は2である。nは0~2の整数であり、0又は1であることが好ましい。
LAは、単結合又は二価の連結基を示す。LAとしてとりうる二価の連結基は、特に制限されず、適宜に選択できるが、酸素原子(-O-基)、アルキレン基、アルケニレン基、アリーレン基等が好適に挙げられる。これらの基としては、それぞれ、上記R2としてとりうる、アルキル基、アルケニル基又はアリール基のそれぞれから更に水素原子を1つ除去した基が挙げられる。中でも、アルケニレン基又は酸素原子が好ましく、アルケニレン基がより好ましく、-CH=CH-基、-CH(CH3)=CH-基が更に好ましい。LAとしては、単結合、アルケニレン基又は酸素原子が好ましく、単結合又はアルケニレン基がより好ましい。
LBは、単結合、-CH=CH-又は酸素原子を示し、単結合又は-CH=CH-が好ましい。
本発明の重合性組成物は、(A)一般式(I)で表される化合物を必須成分として少なくとも1種含有し、適宜に、(B)他の共重合性化合物、(C)重合開始剤、(D)共増感剤、(E)重合禁止剤、(F)溶媒、及び(G)アルカリ金属化合物等を含有している。
重合性組成物における化合物(A)の総含有量は、特に制限されず、例えば、重合性組成物の全質量中、5~95質量%であることが好ましく、5~60質量%であることがより好ましく、10~40質量%であることが更に好ましく、15~30質量%であることも好ましい。
重合性組成物が化合物(A)のうち単官能重合性化合物と多官能重合性化合物とを含有する場合、単官能重合性化合物の含有量は、特に制限されないが、重合体としたときに酸耐性及びアルカリ耐性の改善効果を大幅に損なうことなく透水性を改善できる点で、例えば、重合性組成物の全質量中、0質量%を超え90質量%以下であることが好ましく、1~20質量%であることがより好ましく、3~10質量%であることが更に好ましい。多官能重合性化合物の含有量は、特に制限されないが、重合体としたときに透水性を維持しながらも酸耐性及びアルカリ耐性の改善効果が高くなる点で、例えば、重合性組成物の全質量中、0質量%を超え95質量%以下であることが好ましく、5~60質量%であることがより好ましく、15~25質量%であることが更に好ましい。
本発明の重合性組成物は、重合体を形成する成分として、上記化合物(A)に加えて、この化合物(A)と共重合しうる他の共重合性化合物を含有していてもよい。
「他の重合性化合物」とは、化合物(A)とは化学構造上異なる重合性化合物である。この重合性化合物は、多官能重合性化合物であってもよいが、単官能重合性化合物であることが好ましい。
このような他の重合性化合物としては、例えば、アクリル酸エステル化合物、メタクリル酸エステル化合物、アクリルアミド化合物、メタクリルアミド化合物、ビニルエステル化合物、ビニルエーテル化合物、スチレン化合物等の芳香族ビニル化合物、アリル化合物、アクリル酸、メタクリル酸、アクリロニトリル、無水マレイン酸、マレイン酸イミド等の公知の重合性化合物が挙げられる。このような重合性化合物を共重合させることで、製膜性、膜強度、親水性、疎水性、溶解性、反応性、安定性等の諸物性を改善することができる。これらの中でも、得られた高分子機能性膜の安定性等の点で、エステル結合を有さないもの、(メタ)アクリルアミド化合物、ビニルエーテル化合物、芳香族ビニル化合物、N-ビニル化合物(アミド結合を有する重合性モノマー)、アリル化合物が好ましく、(メタ)アクリルアミド化合物が特に好ましい。
R10は水素原子が好ましい。
R11及びR12におけるアルキル基の炭素数は、1~18が好ましく、1~12がより好ましく、1~6が特に好ましい。アルキル基は、直鎖若しくは分岐のアルキル基が好ましく、置換基を有していてもよい。
アルキル基が有していてもよい置換基としては、特に制限されないが、例えば、ヒドロキシ基、スルホ基若しくはその塩、カルボキシ基若しくはその塩、リン酸基若しくはその塩、オニオ基(アンモニオ、ピリジニオ、スルホニオ等)、ハロゲン原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アミノ基(アミノ基、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基を含む)、アミド基、スルホンアミド基、カルバモイル基、スルファモイル基、アシル基、シアノ基等が挙げられる。
重合性組成物における他の共重合性化合物の総含有量は、特に制限されず、例えば、重合性組成物の全質量中、0~90質量%であることが好ましく、0~60質量%であることがより好ましく、3~15質量%であることが更に好ましい。
本発明の重合性組成物は、重合開始剤を含有することが好ましい。
重合開始剤は、特に制限されないが、エネルギー線照射で重合性化合物を重合させることが可能な光重合開始剤が好ましい。このような光重合開始剤としては、芳香族ケトン類、アシルホスフィン化合物、芳香族オニウム塩化合物、有機化酸化物、チオ化合物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、アルキルアミン化合物等が挙げられる。
本発明の重合性組成物は、感度を一層向上させる、又は酸素による重合阻害を抑制する等の作用を有する公知の化合物を共増感剤として、含有していてもよい。このような共増感剤の例としては、アミン化合物、チオール及びスルフィド化合物、アミノ酸化合物、有機金属化合物、水素供与体、イオウ化合物、リン化合物、Si-H、Ge-H化合物等が挙げられる。
重合性組成物中における共増感剤の含有量は、特に制限されず、例えば、重合性組成物の全質量中、0.01~3.00質量部か好ましく、0.05~2.00質量部がより好ましく、0.10~1.00質量部が更に好ましい。
本発明の重合性組成物は、塗布安定性の点で、重合禁止剤を含有することも好ましい。
重合禁止剤としては、公知の重合禁止剤が使用でき、フェノール化合物、ハイドロキノン化合物、アミン化合物、メルカプト化合物等が挙げられる。
重合性組成物中における重合禁止剤の含有量は、特に制限されず、例えば、重合性組成物の全質量中、0.01~5質量部か好ましく、0.01~1質量部がより好ましく、0.01~0.5質量部が更に好ましい。
本発明の重合性組成物は、溶媒として水及び有機溶媒の少なくとも1種を含有していてもよい。重合性組成物中における溶媒の含有量は、特に制限されず、通常、重合性組成物の残部とされるが、例えば、重合性組成物の全質量に対して、5~90質量%が好ましく、30~85質量%がより好ましく、50~80質量%が更に好ましい。
重合性組成物が溶媒を含有していると、重合反応が、均一にしかもスムーズに進行する。また、多孔質支持体に重合性組成物を含浸させる場合、スムーズに含浸できる。
有機溶媒は、水に対する溶解度が5質量%以上であるものが好ましく用いられ、更には水に対して自由に混合するものが好ましい。このため、水溶性溶媒から選択される溶媒が好ましい。水溶性溶媒としては、特に限定されないが、アルコール溶媒、非プロトン性極性溶媒であるエーテル溶媒、アミド溶媒、ケトン溶媒、スルホキシド溶媒、スルホン溶媒、ニトリル溶媒、有機リン溶媒が好ましい。
本発明の重合性組成物は、上記(B)他の重合性化合物、特に(メタ)アクリルアミド構造を有する化合物の溶解性を向上させるために、アルカリ金属化合物を含有していてもよい。また、アルカリ金属化合物は、組成物、組成物溶液混合物を中和するために使用することも好ましい。
アルカリ金属化合物としては、リチウム、ナトリウム、カリウムの水酸化物塩、塩化物塩、硝酸塩等が好ましい。中でも、リチウム化合物がより好ましく、その具体例としては、水酸化リチウム、塩化リチウム、臭化リチウム、硝酸リチウム、ヨウ化リチウム、リチウム塩素酸塩、チオシアン酸リチウム、過塩素酸リチウム、リチウム・テトラフルオロボラート、リチウム・ヘキサフルオロホスファート、リチウム・ヘキサフルオロアルセナートが挙げられる。アルカリ金属化合物は水和物であってもよい。
重合性化合物中におけるアルカリ金属化合物の含有量は、特に制限されず、例えば、重合性組成物の全質量中、0.1~20質量部か好ましく、0.1~10質量部がより好ましく、0.5~5質量部が更に好ましい。
本発明の重合性組成物は、重合膜の物性改善を目的として、各種高分子化合物を含有することもできる。高分子化合物としては、アクリル系重合体、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、シェラック、ビニル系樹脂、アクリル系樹脂、ゴム系樹脂、ワックス類、その他の天然樹脂等が使用できる。
また、本発明の重合性組成物は、重合性組成物の液物性改善を目的として、ノニオン性界面活性剤、カチオン性界面活性剤、有機フルオロ化合物等を含有することもできる。
更に、例えば、粘度向上剤、表面張力調整剤、防腐剤を含有してもよい。
本発明の重合性組成物は、後述する本発明の重合膜を形成する材料等として、好適に用いることができる。
本発明の重合体(ポリマー)は、上記一般式(I)で表される化合物(A)に由来する構成成分[A]を少なくとも1種有しており、少なくとも1種の化合物(A)を重合反応させて合成される。本発明の重合体は、化合物(A)による高い酸耐性及びアルカリ耐性を発現して、広範な用途に用いることができ、特に重合膜を構成する重合体として好適である。
本発明の重合体は、構成成分[A]を2種以上有することが好ましく、また、単官能重合性化合物に由来する構成成分と、多官能重合性化合物に由来する構成成分とを有することも好ましい。ここで、構成成分[A]は、単官能重合性化合物に由来する構成成分及び多官能重合性化合物に由来する構成成分のうち少なくとも1種として重合体中に組み込まれていればく、多官能重合性化合物に由来する構成成分の1種として重合体中に組み込まれていることが好ましい。この構成成分[A]は単官能重合性化合物に由来する構成成分及び多官能重合性化合物に由来する構成成分のいずれの構成成分として重合体中に組み込まれていてもよい。
本発明の重合体が有していてもよい、化合物(A)以外の化合物に由来する構成成分としては、特に制限されないが、例えば、上記「(B)他の共重合性化合物」に由来する構成成分[B]が挙げられ、単官能重合性化合物に由来する構成成分として構成成分[B]を有することが好ましい。
本発明の重合体が2種以上の構成成分を有する場合、構成成分の結合の様式は、特に限定されるものでなく、例えば、各構成成分がブロック型に連結していても、ランダム型に連結していてもよい。
本発明の重合体が有する、化合物(A)に由来する構成成分[A]は、上記一般式(I)~(VI)のいずれかで表される化合物を重合反応させた構成成分であり、高い酸耐性及びアルカリ耐性を示す。
構成成分[A]は、具体的には、下記一般式(IP)で表される。一般式(IP)で表される構成成分は、上記一般式(I)で表される化合物に由来する構成成分であり、一般式(IP)において、R1~R3、M+、k、m及びnは上記一般式(I)におけるR1~R3、M+、k、m及びnと同じ意味を持ち、好ましい範囲も同じである。
本発明の重合体は、(B)他の共重合性化合物に由来する構成成分[B]として、下記式(PB)で表される構成成分を有していてもよい。
本発明の重合体の平均質量分子量は、特に制限されないが、多官能重合性化合物に由来する構成成分を含有している場合、通常三次元架橋が形成されているため数十万以上であり、実質的に測定できない。一般的には無限大とみなされる。
本発明の重合体の合成方法は、特に制限されず、適宜の方法に準じて合成することができ、例えば、後述する重合膜の作製における活性放射線を照射する方法等が挙げられる。なお、本発明の重合体は、後述する重合膜の作製において重合膜の作製と連続して又は同時に重合体を重合することもできる。
本発明の重合膜は、本発明の上記重合体を少なくとも1種含有している。
本発明の重合膜における重合体の含有量は、特に制限されないが、例えば、重合膜の全質量中、20~98質量%であることが好ましく、50~95質量%であることがより好ましい。下限値としては、70質量%とすることもでき、80質量%とすることもできる。
本発明の重合膜(以下、単に膜ともいう。)は、広範な用途に用いることができ、例えば、イオン交換、イオンの選択的透過、プロトン伝導、燃料電池、タンパク質凝集物若しくはウイルス除去等を行うために用いることができる。
以下、本発明の好ましい実施形態について、本発明の重合膜がカチオン交換膜としての機能を有する場合を例に挙げて説明する。
膜(カチオン交換膜)において、Na+等のカチオンに対する選択透過性は、特に制限されないが、例えば、好ましくは0.9を超え、より好ましくは0.93を超え、特に好ましくは0.95を超え、最も好ましくは0.96を超える。膜の選択透過性は、膜を酸及びアルカリ処理後にも高い値を有いていることが好ましく、例えば、後述する実施例における0.85以上(評価基準C)であることが好ましい。
膜の透水率は、14×10―5mL/m2/Pa/hr以下であることが好ましく、12×10―5mL/m2/Pa/hr以下であることがより好ましく、10×10―5mL/m2/Pa/hr以下であることが最も好ましい。膜の透水率は、膜を酸及びアルカリ処理後にも上記値を維持して大きく低下しないことが好ましく、例えば、後述する実施例における透水率の変化量が30%未満(評価基準C)以上であることが好ましい。
膜の吸水量は、特に制限されないが、例えば、乾燥膜の質量に対して、好ましくは70%未満、より好ましくは50%未満、特に好ましくは40%未満である。
膜のイオン交換容量は、特に制限されず、例えば、膜ならびに得られる膜と接触し続けている多孔質支持体及び任意の多孔質補強材料の全乾燥質量に対して、好ましくは0.5meq/g以上、より好ましくは0.8meq/g以上、特に好ましくは1.2meq/g以上である。
膜の破裂強度、電気抵抗(膜抵抗)、水中での膨潤率(膨潤による寸法変化率)は、いずれも、特に制限されず、適宜に設定できる。例えば、特開2014-171951号公報に記載の内容を適宜参照することができ、その内容はそのまま本明細書の記載の一部として取り込まれる。
選択透過性は、Membrane Science,319,217~218(2008)、中垣正幸著、膜学実験法,193~195頁(1984)に記載されている方法、より具体的には実施例で説明する方法により、測定することができる。
その上で、本発明の重合膜は、一般式(I)で表される化合物に由来する構成成分を有する重合体を含んでいる。そのため、一般式(I)で表される化合物に起因する高い酸耐性及びアルカリ耐性を示す。
より具体的には、本発明の重合性組成物を多孔質支持体の表面に塗布した後、又は多孔質支持体の孔部に含浸させた後に硬化反応、すなわち重合反応して形成できる。また、本発明の重合膜は、本発明の重合性組成物を多孔質支持体の表面に塗布し、かつ多孔質支持体の孔部に含浸させた後に硬化反応して形成することもできる。
硬化反応を行うに際しては、重合性組成物を塗布した多孔質支持体に活性放射線(例えば、紫外線、電子線)を照射する、又は熱を付与すること方法が挙げられる。重合膜を形成する条件は、特に制限はないが、温度としては、例えば、-30~100℃が好ましく、-10~80℃がより好ましく、5~60℃が特に好ましい。
本発明の重合膜の製造方法の詳細については、特開2014-171951号公報に記載の内容を適宜参照することができ、その内容はそのまま本明細書の記載の一部として取り込まれる。
本発明の重合膜はモジュール化して好適に用いることができる。モジュールの例としては、スパイラル型、中空糸型、プリーツ型、管状型、プレート&フレーム型、スタック型等が挙げられる。
本発明の重合膜は、特にイオン交換に使用することが好適であるが、イオン交換以外にも、例えば、燃料電池用のプロトン伝導膜、タンパク質・ウイルス除去にも好適に用いることができる。
得られたスチレンスルホン酸クロライドを核磁気共鳴スペクトル(1H-NMR)測定して同定した。
1H-NMR(400MHz,CDCL3):δ8.0(2H)、δ7.6(2H)、δ6.8(1H)、δ6.0(1H)、δ5.5(1H)
例示化合物(1)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。得られたチャートを図2に示す。
1H-NMR(400MHz,D2O):δ7.7(4H)、δ7.5(4H)、δ7.3(2H)、δ6.9(2H)、δ6.8(2H)、δ6.7(2H)、δ5.8(2H)、δ5.3(2H)
例示化合物(2)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。得られたチャートを図3に示す。
1H-NMR(400MHz,D2O):δ7.7(4H)、δ7.5(4H)、δ7.4(2H)、δ6.9(2H)、δ6.8(2H)、δ6.7(2H)、δ5.8(2H)、δ5.3(2H)
2,4-ジビニルベンゼンスルホン酸クロライドを核磁気共鳴スペクトル(1H-NMR)測定して同定した。
1H-NMR(400MHz,CDCL3):δ8.0(1H)、δ7.7(1H)、δ7.6(1H)、δ7.5(1H)、δ6.8(1H)、δ6.0(1H)、δ5.9(1H)、δ5.6(1H)、δ5.6(1H)
例示化合物(3)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。
1H-NMR(400MHz,D2O):δ7.7(2H)、δ7.6(2H)、δ7.5(2H)、δ7.3(2H)、δ7.3(2H)、δ6.8(2H)、δ6.8(2H)、δ6.6(2H)、δ5.8(2H)、δ5.6(2H)、δ5.3(4H)
例示化合物(5)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。
1H-NMR(400MHz,D2O):δ7.7(4H)、δ7.5(4H)、δ7.4(4H)、δ7.3(2H)、δ6.9(2H)、δ6.6(2H)、δ5.8(2H)、δ5.2(2H)
例示化合物(8)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。得られたチャートを図4に示す。
1H-NMR(400MHz,D2O):δ7.7(2H)、δ7.6(2H)、δ7.5(2H)、δ7.4(2H)、δ7.4(2H)、δ7.3(2H)、δ7.2(2H)、δ6.8(2H)、δ6.6(2H)、δ5.8(2H)、δ5.6(2H)、δ5.3(4H)
例示化合物(12)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。
1H-NMR(400MHz,D2O):δ7.7(4H)、δ7.5(4H)、δ7.3(2H)、δ6.9(2H)、δ6.8(2H)、δ6.7(2H)、δ5.8(2H)、δ5.3(2H)
例示化合物(16)を核磁気共鳴スペクトル(1H-NMR)測定して同定した。
1H-NMR(400MHz,D2O):δ7.6(2H)、δ7.4(2H)、δ7.2(1H)、δ7.1(2H)、δ6.9(1H)、δ6.6(1H)、δ5.8(1H)、δ5.3(1H)
例示化合物(9)、(11)及び(21)は、それぞれ、上記合成例等に準拠して、合成した。
上記合成例で合成した各例示化合物5mgを、重水(D2O)1mLに溶解させ、そこに内部標準物質としてトリメチルシリルプロピオン酸ナトリウム(d4)を加えた後、室温下で、1H-NMR測定を行った。
その後、測定を行ったサンプルに重水酸化ナトリウム溶液を濃度が1Nとなる量を加えて混合し、1日経過後に室温下で、再度1H-NMR測定を行った。内部標準物質のピーク(0ppm)面積に対する各例示化合物のピークの減少量から、各例示化合物の分解率を算出した。分解率の算出の基準とするピークは例示化合物(1)において化学シフトδ7.3ppmに出現する水素原子とし、例示化合物(1)以外の例示化合物においては上記水素原子に対応する水素原子のピークとした。
算出した分解率が下記評価基準のいずれに含まれるかにより、各例示化合物のアルカリ耐性(アルカリ安定性)を評価した。その結果を表1に示す。
本試験において、分解率が小さいほど、アルカリ耐性に優れることを示し、評価基準「B」以上が合格レベルである。
- 評価基準 -
A:10%未満
B:10%以上20%未満
C:20%以上
1.カチオン膜100~108の作製
下記表2に示す組成の各組成物(塗布液)100~108を調製し、各組成物をアルミニウム板に、150μmのワイヤ巻き棒を用いて、手動で約5m/minの速さで塗布した。続いて、アルミニウム板上に塗布した塗布液上に、不織布(FO-2223-10(商品名)、厚さ100μm、Freudenberg社製)を載置して、不織布内に塗布液を含浸させた。ワイヤの巻いていないロッドを用いて不織布に含浸していない余分な塗布液を除去した。塗布時の塗布液の温度は約40℃であった。次いで、UV露光機(型式Light Hammer 10、D-バルブ、コンベア速度15m/min、100%強度、Fusion UV Systems社製)を用いて、不織布に含浸させた塗布液を硬化(重合)することにより、アルミニウム板上に、不織布と塗布液の硬化物(重合体)とが一体化した膜を作製した(厚さ:130μm)。次いで、作製した膜をアルミニウム板から取り外し、0.1M NaCl溶液中で少なくとも12時間保存した。こうして、各組成物を用いて、実施例2-1~2-9のカチオン膜100~108をそれぞれ作製した。
国際公開第2013/011272号を参照し、それぞれ、実施例2-1の組成物の組成を下記表2に記載の組成に変えて調製した比較例2-1及び2-2の組成物c100及びc101を用いたこと以外は、実施例2-1と同様にして比較例2-1及び2-2のカチオン膜c100及びc101をそれぞれ作製した。
表2における化合物は以下の通りである。
Genorad 16((商品名)):Rahn AG社製(重合開始剤)
Darocur 1173(商品名):2-ヒドロキシ-2-メチルプロピオフェノン、チバ・スペシャリティ・ケミカルズ社製
Tego Glide 432(商品名):ポリエーテルシロキサンコポリマー、Evonik industries社製
上記のようにして作製したカチオン膜100~108、c100及びc101について、下記特性を評価した。
選択透過性は、静的膜電位測定により膜電位(V)を測定し、算出した。2つの電解槽(cell)は、測定対象の膜により隔てられている。測定前に、膜を0.05M NaCl水溶液中で約16時間平衡化した。その後、異なる濃度のNaCl水溶液を、測定対象の膜の相対する側の電解槽に、それぞれ、注いだ。
一方のcellに0.05M NaCl水溶液を100mL注いだ。また、他方のcellに0.5M NaCl水溶液100mLを注いだ。
恒温水槽により、cell中のNaCl水溶液の温度を25℃に安定化してから、両液を膜面に向かって流しながら、両電解槽とAg/AgCl参照電極(Metrohm社製)を、塩橋で接続して膜電位(V)を測定し、下記式(A)により輸率tを算出した。
なお、膜の有効面積は1cm2であった。
t=(a+b)/2b 式(A)
上記式(A)における各符号の詳細を以下に示す。
a:膜電位(V)
b:0.5915log(f1c1/f2c2)(V)
f1、f2:両cellのNaCl活量係数
c1、c2:両cellのNaCl濃度(M)
膜の透水率を図1に示す流路10を有する装置により測定した。図1において、符号1は膜を表し、符号3及び4は、それぞれ、フィード溶液(純水)及びドロー溶液(3M NaCl)の流路を表す。また、符号2の矢印はフィード溶液から分離された水の流れを示す。
フィード溶液400mLとドロー溶液400mLとを、膜を介して接触させ(膜接触面積18cm2)、各液はペリスタポンプを用いて符号5の矢印の向きに流速0.11cm/秒で流した。フィード溶液中の水が膜を介してドロー溶液に浸透する速度を、フィード液とドロー液の質量をリアルタイムで測定することによって解析し、透水率を求めた。
1.酸及びアルカリ処理膜200~207、c200及びc201の作製
実施例2で作製した各カチオン膜100~104、106~108、c100及びc101を、それぞれ、4Mの塩酸水に25℃で6時間浸漬させた。次いで、4M塩酸水から酸処理したカチオン膜を取り出して、0.1MのNaCl溶液中に25℃で少なくとも12時間保持した。次いで、NaCl溶液からカチオン膜を取り出して、1Mの水酸化ナトリウム水溶液に25℃で6時間浸漬させた。その後、水酸化ナトリウム水溶液からアルカリ処理したカチオン膜を取り出して、0.1MのNaCl溶液中に25℃で少なくとも12時間保存(浸漬)した。こうして、酸処理及びアルカリ処理したカチオン膜(酸及びアルカリ処理膜)200~207、c200及びc201を作製した。
上記のようにして作製した酸及びアルカリ処理膜200~207、c200及びc201について、選択透過性及び透水率を評価した。結果を表3に示す。
酸及びアルカリ処理膜200~207、c200及びc201を用いて、実施例2における<選択透過性(輸率)試験>と同様にして、選択透過性(輸率)を測定した。測定された輸率が下記評価基準のいずれに含まれるかにより、酸及びアルカリ処理膜の選択透過性(輸率)を評価した。
本試験において、酸及びアルカリ処理膜の輸率が大きいほど、カチオン膜が酸性環境下及びアルカリ性環境下においても高い耐性を示すことを意味し、これら環境下においても初期の優れた輸率を維持できる。
- 評価基準 -
A:0.95以上
B:0.95未満0.90以上
C:0.90未満0.85以上
D:0.85未満
酸及びアルカリ処理膜200~207、c200及びc201を用いて、実施例2における<透水率(mL/m2/Pa/hr)試験>と同様にして、透水率(mL/m2/Pa/hr)を測定した。
実施例2で作製したカチオン膜100~104、106~108、c100及びc101に対する酸及びアルカリ処理膜の透水率の変化率を下記式から算出した。測定された変化率が下記評価基準のいずれに含まれるかにより、酸及びアルカリ処理膜の酸耐性及びアルカリ耐性を評価した。
本試験において、透水率の変化率が小さいほど、実施例2で作製したカチオン膜が高い酸耐性及びアルカリ耐性を示す(酸及びアルカリに対して安定な膜である)ことを意味し、酸及びアルカリ処理膜が酸性環境下及びアルカリ性環境下においても優れた透水率を維持できる。
透水率の変化量(%)=
[(カチオン膜の透水率-酸及びアルカリ処理膜の透水率)/カチオン膜の透水率]×100
- 評価基準 -
A:10%未満
B:10%以上20%未満
C:20%以上30%未満
D:30%以上
これに対して、実施例2-1~2-5及び2-7~2-9で作製したカチオン膜100~104及び106~108は、いずれも、酸処理及びアルカリ処理を行っても(アルカリ処理膜200~207としても)、選択透過性の低下を抑制しながらも透水率の変化量も小さく、酸耐性及びアルカリ耐性に優れている。これは、カチオン膜100~104及び106~108を構成する本発明の重合体が、少なくとも1種の本発明の化合物に由来する構成成分を含有しており、酸処理又はアルカリ処理において加水分解反応を受けにくく、処理前の状態(重合体の化学構造)を維持できているためと考えられる。特に、本発明の化合物として多官能重合性化合物に由来する構成成分を有していると、またこの構成成分の含有量を単官能重合性化合物に由来する構成成分に対して高めると、選択透過性及び透水率を更に高い水準で両立できることが分かる。
2 フィード溶液中の水が膜を介してドロー溶液に浸透することを示す矢印
3 フィード溶液の流路
4 ドロー溶液の流路
5 液体の進行方向
10 透水率測定装置の流路
Claims (9)
- 下記一般式(I)で表される化合物。
R1は水素原子又は低級アルキル基を示す。
R2はアルキル基、アルケニル基、アリール基、ハロゲン原子、水酸基又はアミノ基を示す。
R3はアルキル基、アルケニル基、アリール基、ハロゲン原子、アミノ基、カルボキシ基、若しくは-SO3 -M+基を有する基、又は、アルキル基、アルケニル基、アリール基、酸素原子、-SO3 -M+基若しくはアリールスルホニルアミノ基を組み合わせた基を示す。
R4は水素原子、アルキル基、アルケニル基、アリール基、ハロゲン原子、アミノ基若しくはカルボキシ基、又は、アルキル基、アルケニル基、アリール基、酸素原子、-SO3 -M+基若しくはアリールスルホニルアミノ基を組み合わせた基を示す。
M+はH+、Li+、Na+、K+、Cs+又はアンモニウム塩を示す。
kは0~4の整数であり、kが2以上の整数である場合、複数存在するR2は互いに同じでも異なっていてもよく、互いに連結して環を形成してもよい。
nは0~4の整数であり、nが2以上の整数である場合、複数存在するR3は互いに同じでも異なっていてもよく、互いに連結して環を形成してもよい。
mは0~4の整数であり、mが2以上の整数である場合、複数存在する-SO3 -M+基は互いに同じでも異なっていてもよい。
ただし、nとmは1≦n+m≦4を満たす。またmが0である場合、少なくとも1つのR3は-SO3 -M+基を有する基である。 - 請求項1~6のいずれか1項に記載の化合物を含有する重合性組成物。
- 請求項1~6のいずれか1項に記載の化合物に由来する構成成分を有する重合体。
- 請求項8に記載の重合体を含む重合膜。
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