Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
  • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
  • C08L71/03—Polyepihalohydrins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
  • Y02C20/00—Capture or disposal of greenhouse gases
  • Y02C20/40—Capture or disposal of greenhouse gases of CO2
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/542—Dye sensitized solar cells

Definitions

• the present invention relates to a polyether compound, and more particularly to a polyether compound having excellent carbon dioxide absorption.
• the polyether compound having a cationic group has ionic conductivity, for example, in an electrochemical device such as a secondary battery, a fuel cell, a dye-sensitized solar cell, and an actuator, ionic conductivity between electrodes It is known to be used as an electrolyte for imparting.
• Patent Document 1 describes a polyalkylene oxide having a side chain having a cation site and a counter ion of the side chain in the main chain of the polyalkylene oxide, and the side chain or the counter ion is liquid crystal. Electrolyte compositions characterized by containing have been proposed.
• An object of the present invention is to provide a polyether compound having excellent carbon dioxide absorption.
• the present inventor has attempted to use a polyether compound having a cationic group as a carbon dioxide absorbent.
• the conventional polyether compound having a cationic group does not have sufficient carbon dioxide absorption. Therefore, as a result of diligent research to achieve the above object, the present inventors have introduced a side chain having a specific imidazolium structure into a polyether compound, and made the counter anion specific. It has been found that a polyether compound having excellent carbon dioxide absorption can be obtained.
• the present invention is an invention completed as a result of such studies.
• the polyether compound contains the repeating unit represented by the general formula (1), and the following general formula (2) is used as at least a part of the repeating unit represented by the general formula (1).
• A represents a monovalent group.
• R 1 represents an alkyl group having 3 or more carbon atoms
• R 2 to R 4 independently represent a hydrogen atom or carbon. Representing an alkyl group of numbers 1 to 8, R 2 and R 3 may be bonded to each other.
• X ⁇ contains any one or more of nitrogen, carbon and oxygen. Represents an anion.
• the proportion of the repeating unit represented by the general formula (2) is 50 mol% or more and 100 mol% or less with respect to the entire repeating unit represented by the general formula (1). Is preferable.
• the polyether compound of the present invention preferably has a number average molecular weight (Mn) of 500 or more and 100,000 or less.
• an ionic composition containing the above-mentioned polyether compound of the present invention and an ionic liquid.
• the content ratio of the ionic liquid is preferably 50 parts by mass or more and 3000 parts by mass or less with respect to 100 parts by mass of the polyether compound.
• a molded product containing the above-mentioned polyether compound of the present invention or the above-mentioned ionic composition of the present invention.
• a polyether compound having excellent carbon dioxide absorption is provided.
• the polyether compound of the present invention is a polyether compound containing a repeating unit represented by the following general formula (1), and has the following general formula (1) as at least a part of the repeating unit represented by the general formula (1). It is characterized by including a repeating unit represented by 2).
• A represents a monovalent group.
• R 1 represents an alkyl group having 3 or more carbon atoms
• R 2 to R 4 independently represent a hydrogen atom or carbon. Representing an alkyl group of numbers 1 to 8, R 2 and R 3 may be bonded to each other.
• X ⁇ contains any one or more of nitrogen, carbon and oxygen. Represents an anion.
• the polyether compound of the present invention comprises, as at least a part of the repeating unit represented by the general formula (1), an oxylan unit containing an imidazolium structure represented by the general formula (2). ..
• the polyether compound of the present invention can be made excellent in carbon dioxide absorption by containing the repeating unit represented by the general formula (2).
• the group represented by R 1 may be an alkyl group having 3 or more carbon atoms and is not particularly limited, but for example, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and the like. Examples thereof include an octyl group, a nonyl group and a decyl group.
• the polyether compounds of the present invention because it can be made more excellent by carbon dioxide adsorbing carbon atoms of the groups represented by R 1, may preferably 4 or more, 12 or less It is preferably 6 or less, more preferably 4 or 6, and most preferably 4.
• the group represented by R 1 is not particularly limited and may be linear or branched.
• the polyether compounds of the present invention, because it can be made more excellent by carbon dioxide adsorptive group represented by R 1 is preferably linear.
• the groups represented by R 2 to R 4 independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
• the alkyl group having 1 to 8 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
• R 2 ⁇ R 4 are each independently, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
• Groups represented by R 2 ⁇ R 4 are in the same repeating unit, all may be the same group, partially or all may be different groups.
• R 2 and R 3 may be bonded to each other, but it is preferable that R 2 and R 3 are not bonded to each other.
• an alkylene group having 1 to 16 carbon atoms is formed.
• the alkylene group having 1 to 16 carbon atoms is not particularly limited, and is, for example, a 1,2-ethylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, or 1,6-. Examples thereof include a hexylene group, a 4-methyl-2,2-pentylene group, a 2,3-dimethyl-2,3-butylene group and the like.
• R 1 ⁇ R 4 are different, may be one containing repeating units represented by the plurality of kinds of general formula (2), R 1 ⁇ R 4 is a single, It may include a repeating unit represented by a single general formula (2).
• the anion represented by X ⁇ means a counter anion having an imidazolium structure.
• the anion represented by X ⁇ may be an anion containing any one or more of nitrogen, carbon, and oxygen, and is not particularly limited, but the polyether compound of the present invention is more excellent in carbon dioxide adsorption. It is preferable that it contains at least carbon because it can be used as a compound. That is, the anion represented by X ⁇ is preferably an organic acid ion.
• the number of atoms constituting the anion represented by X ⁇ is preferably 2 or more, more preferably 4 or more, because the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption. 6 or more is further preferable, 25 or less is preferable, 20 or less is more preferable, 15 or less is further preferable, and 10 or less is particularly preferable.
• anion represented by X ⁇ examples include sulfonylimided ions such as (FSO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 2 N ⁇ , and (CF 3 CF 2 SO 2 ) 2 N ⁇ ; CH 3 COO -, C 3 H 7 COO -, CF 3 COO -, PhCOO - (Ph represents a phenyl group.) a carboxylic oxide ions, such as; B (CN) 4 -, SCN -, (NC) 2 N - etc.
• the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption, so it is preferably an organic acid ion, a sulfonylimided ion, and a carboxylic oxidation. More preferably ones are ion or cyanide ion, (CF 3 SO 2) 2 N -, CH 3 COO - or B (CN) 4 - and still more preferably a.
• all the anions represented by X ⁇ may be the same type of anions, or different types of anions may be mixed. May be good.
• the repeating unit represented by the general formula (1) is a unit (oxylan monomer unit) obtained by ring-opening polymerization of the oxylan structure portion of the compound containing the oxylan structure.
• the polyether compound of the present invention may contain a repeating unit represented by the general formula (1) other than the repeating unit represented by the general formula (2).
• Examples of the repeating unit represented by the general formula (1) other than the repeating unit represented by the general formula (2) include an alkylene oxide monomer such as an ethylene oxide unit, a propylene oxide unit, and a 1,2-butylene oxide unit.
• Epihalohydrin monomer units such as epichlorohydrin units, epibromohydrin units, and epiiodohydrin units; alkenyl group-containing oxylan monomer units such as allylglycidyl ether units; aromatics such as phenylglycidyl ether units ether group-containing oxirane monomer units; glycidyl acrylate units, such as glycidyl methacrylate unit (meth) acryloyl group-containing oxirane monomer units; counter anion (X -) is nitrogen, except that it does not contain any carbon, oxygen
• a unit having the same structure as the repeating unit represented by the general formula (2); and the like can be mentioned.
• Examples of the repeating unit represented by the general formula (1) other than the repeating unit represented by the general formula (2) include an alkylene oxide monomer unit, an epihalohydrin monomer unit, and a (meth) acryloyl group-containing oxylan monomer.
• a unit or a unit having the same structure as the repeating unit represented by the general formula (2) is preferable except that the counter anion (X ⁇ ) does not contain any of nitrogen, carbon and oxygen.
• the polyether compound of the present invention may contain a repeating unit other than the repeating unit represented by the general formula (1).
• the repeating unit other than the repeating unit represented by the general formula (1) include an oxylan monomer unit having two or more substitutions such as a 2,3-butylene oxide unit and an oxylane containing a ring structure such as cyclohexene oxide. Monomer units can be mentioned.
• the polyether compound of the present invention may contain an oxylan monomer unit having a crosslinkable group.
• a crosslinkable composition can be prepared by blending a crosslinking agent, and the crosslinked product obtained by crosslinking the crosslinkable composition contains a crosslinked structure. Since it is a crosslink, it is more excellent in shape retention when it is molded into a predetermined shape.
• the oxylan monomer unit having a crosslinkable group is not particularly limited, and examples thereof include an epihalohydrin monomer unit, an alkenyl group-containing oxylan monomer unit, and a (meth) acryloyl group-containing oxylan monomer unit. ..
• the polyether compound of the present invention may contain two or more kinds of repeating units, and in this case, the distribution mode of the plurality of repeating units is not particularly limited, but has a random distribution. It is preferable to have.
• the chain structure of the polyether compound of the present invention is not particularly limited, and may be a linear structure, or may have a chain structure having branches such as a graft shape and a radial shape.
• the terminal group of the polyether compound of the present invention is not particularly limited and can be any monovalent group.
• Specific examples of the group serving as the terminal group include a hydrogen atom, a halogen group, an alkyl group, a haloalkyl group, a hydroxyl group, an azide group, and a group represented by the following general formula (3).
• R 5 represents an alkyl group having 3 or more carbon atoms
• R 6 to R 8 independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
• R 6 and R 7 represent each other. It may be combined.
• X '- is an anion.
• the number average molecular weight (Mn) of the polyether compound of the present invention is not particularly limited, but is preferably 500 or more and 100,000 or less, and more preferably 1,000 or more and 80,000 or less. By setting the number average molecular weight (Mn) of the polyether compound in the above range, the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption.
• the weight average molecular weight (Mw) of the polyether compound of the present invention is not particularly limited, but is preferably 500 or more and 200,000 or less, and more preferably 1000 or more and 160,000 or less.
• the molecular weight distribution (Mw / Mn) of the polyether compound of the present invention is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 2.0.
• the number of repeating units represented by the general formula (1) is not particularly limited, but the average number per molecule is preferably 5 to 1000, preferably 8 to 800. More preferably.
• the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption.
• the number of repeating units represented by the general formula (2) is not particularly limited, but the average number per molecule is preferably 5 to 1000, preferably 8 to 800. More preferably.
• the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption.
• the proportion of the repeating unit represented by the general formula (1) in the polyether compound of the present invention is not particularly limited, but is 90 mol% or more and 100 mol% with respect to all the repeating units of the polyether compound of the present invention. It is preferably 95 mol% or more, more preferably 100 mol% or less, and most preferably substantially 100 mol%.
• the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption.
• the proportion of the repeating unit represented by the general formula (2) in the polyether compound of the present invention is not particularly limited, but is 50 mol% or more 100 with respect to the entire repeating unit represented by the general formula (1). It is preferably mol% or less, more preferably 70 mol% or more and 100 mol% or less, further preferably 90 mol% or more and 100 mol% or less, and particularly preferably substantially 100 mol%. preferable.
• the proportion of the repeating unit represented by the general formula (2) in the above range the polyether compound of the present invention can be made more excellent in carbon dioxide adsorption.
• the proportion of the oxylan monomer unit having a crosslinkable group in the polyether compound of the present invention is not particularly limited, but is based on the entire oxylan monomer unit constituting the polyether compound having a cationic group. It is preferably 50 mol% or less, and more preferably 20 mol% or less.
• the lower limit of the proportion of the oxylan monomer unit having a crosslinkable group is not particularly limited, but a crosslinked product obtained by using the polyether compound of the present invention as a crosslinkable composition and crosslinking the composition. May be 1 mol% or more from the viewpoint of making the shape retention more excellent.
• the method for synthesizing the polyether compound of the present invention is not particularly limited, and any synthesis method can be adopted as long as the desired polyether compound can be obtained.
• a base polymer (a polyether compound having no repeating unit represented by the general formula (2)) is obtained by the following method (A) or (B).
• a monomer containing an oxylan monomer containing at least epihalohydrin such as epichlorohydrin, epibromohydrin, and epiiodohydrin is disclosed in JP-A-2010-53217 as a catalyst.
• epihalohydrin such as epichlorohydrin, epibromohydrin, and epiiodohydrin
• JP-A-2010-53217 A monomer containing an oxylan monomer containing at least epihalohydrin such as epichlorohydrin, epibromohydrin, and epiiodohydrin is disclosed in JP-A-2010-53217 as a catalyst.
• an onium salt of a compound containing atoms of Group 15 or Group 16 of the periodic table and a catalyst containing trialkylaluminum in which all the contained alkyl groups are linear alkyl groups.
• a monomer containing an oxylan monomer containing at least epihalohydrin such as epichlorohydrin, epibromohydrin, and epiiodohydrin is disclosed in Japanese Patent Publication No. 46-27534.
• the halogen group constituting the epihalohydrin monomer unit of the base polymer is imidazole. It is converted to a rhium halide group to obtain an imidazolium halide structural unit-containing polyether compound.
• the imidazolium halide structural unit-containing polyether compound obtained, nitrogen, carbon, anion containing any one or more of oxygen (X -) and reacting the salt with the metal cation, the anion exchange reaction
• the halide ion constituting the imidazolium halide group into an anion (X ⁇ ) containing any one or more of nitrogen, carbon and oxygen
• the polyether compound of the present invention can be obtained. be able to.
• the imidazole compound used when reacting the base polymer with the imidazole compound is an imidazole compound corresponding to the imidazolium structure contained in the repeating unit represented by the general formula (2).
• the imidazole compound is not particularly limited, and examples thereof include 1-butyl imidazole, 1-pentyl imidazole, and 1-hexyl imidazole.
• the method for reacting the base polymer with the imidazole compound is not particularly limited, but a method of mixing the base polymer and the imidazole compound is preferable.
• the method for mixing the base polymer and the imidazole compound is not particularly limited, and for example, a method of adding and mixing the imidazole compound to a solution containing the base polymer, a method of adding and mixing the base polymer to the solution containing the imidazole compound, and an imidazole compound.
• a method of preparing each of the compound and the base polymer as separate solutions and mixing the two solutions can be mentioned.
• an inert solvent is preferably used, and it may be non-polar or polar.
• the non-polar solvent include aromatic hydrocarbons such as benzene and toluene; chain saturated hydrocarbons such as n-pentane and n-hexane; and alicyclic saturated hydrocarbons such as cyclopentane and cyclohexane. Be done.
• Polar solvents include ethers such as tetrahydrofuran, anisole and diethyl ether; esters such as ethyl acetate and ethyl benzoate; ketones such as acetone, 2-butanone and acetophenone; aprotic polar solvents such as acetonitrile, dimethylformamide and dimethylsulfoxide. ; Protic and aprotic solvents such as ethanol, methanol and water; and the like. As the solvent, a mixed solvent of these is also preferably used.
• the amount of the solvent used is not particularly limited, but it is preferably used so that the concentration of the base polymer is 1 to 50% by mass, and more preferably 3 to 40% by mass.
• the amount of the imidazole compound used in reacting the base polymer with the imidazole compound is not particularly limited, and depends on the content ratio of the repeating unit represented by the general formula (2) of the target polyether compound and the like. You just have to decide. Specifically, the amount of the imidazole compound used is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, more preferably 0.03, based on 1 mol of the epichlorohydrin unit of the base polymer used. It is in the range of ⁇ 10 mol, more preferably 0.05 ⁇ 2 mol.
• the pressure at which the base polymer is reacted with the imidazole compound is not particularly limited, but is usually 1 to 500 atm, preferably 1 to 100 atm, and particularly preferably 1 to 50 atm.
• the temperature during the reaction is also not particularly limited, and is usually 0 to 200 ° C, preferably 20 to 170 ° C, and more preferably 40 to 150 ° C.
• the reaction time is usually 1 minute to 1,000 hours, preferably 3 minutes to 800 hours, more preferably 5 minutes to 500 hours, and even more preferably 30 minutes to 200 hours.
• imidazolium halide structural unit-containing polyether compound, nitrogen, carbon, anion containing any one or more of oxygen (X -) a method of performing a by reacting a salt of a metal cation, an anion exchange reaction,
• an imidazolium halide structural unit-containing polyether compound, an anion (X ⁇ ) containing at least one of nitrogen, carbon, and oxygen and a salt of a metal cation are mixed and reacted. The method is preferred.
• the conditions under which the anion exchange reaction is carried out are not particularly limited, and are a salt of an imidazolium halide structural unit-containing polyether compound, an anion (X ⁇ ) containing at least one of nitrogen, carbon, and oxygen, and a metal cation. Only may be mixed, or may be carried out under conditions in the presence of other compounds such as organic solvents.
• the amount of the salt used is not particularly limited, but is usually 0.01 to 100 mol, preferably 0.02 to 50 mol, based on 1 mol of the imidazolium halide structural unit of the imidazolium halide structural unit-containing polyether compound used. , More preferably in the range of 0.03 to 10 mol.
• the salt of the anion (X ⁇ ) containing at least one of nitrogen, carbon, and oxygen and the metal cation used in the anion exchange reaction is not particularly limited, but is, for example, lithium (bisfluorosulfone) imide.
• Li (FSO 2 ) 2 N Lithium (bistrifluoromethylsulfone) imide (Li (CF 3 SO 2 ) 2 N), Lithium (bispentafluoroethyl sulfone) imide (Li (CF 3 CF 2 SO 2 ) 2) N), sodium acetate (CH 3 COONa), lithium butyrate (C 3 H 7 COOLi), lithium trifluoroacetate (CF 3 COOLi), lithium benzoate (PhCOOLi), potassium tetracyanoborate (KB (CN) 4 ) , lithium thiocyanate (LiSCN), lithium (Bisushiano) imide (Li (NC) 2 N), lithium methylsulfonate (LiCH 3 SO 3
• the pressure at which the anion exchange reaction is carried out is usually 1 to 500 atm, preferably 1 to 100 atm, and particularly preferably 1 to 50 atm.
• the temperature during the reaction is usually ⁇ 30 to 200 ° C., preferably ⁇ 15 to 180 ° C., and more preferably 0 to 150 ° C.
• the reaction time is usually 1 minute to 1000 hours, preferably 3 minutes to 100 hours, more preferably 5 minutes to 10 hours, and even more preferably 5 minutes to 3 hours.
• metal cations, halide ions, salts thereof, etc. are removed by washing with water or the like and membrane separation by a membrane such as a semipermeable membrane, and a mixture containing a polyether compound is recovered.
• a membrane such as a semipermeable membrane
• the mixture containing the polyether compound can be recovered by extracting the polyether compound with a solvent such as methanol.
• the target polyether compound can be recovered according to a conventional method such as drying under reduced pressure.
• the polyether compound of the present invention includes ionic liquids, metal salts such as LiPF 6 , LiTFSI, and KI, low molecular weight compounds such as water, methanol, ethylene carbonate, ethylene glycol, and tetraethylene glycol, fillers such as carbon materials and inorganic materials, and the like. Can be blended and used as a composition.
• metal salts such as LiPF 6 , LiTFSI, and KI
• low molecular weight compounds such as water, methanol, ethylene carbonate, ethylene glycol, and tetraethylene glycol
• fillers such as carbon materials and inorganic materials, and the like.
• the ionic composition of the present invention contains the above-mentioned polyether compound and an ionic liquid.
• the ionic liquid may be an organic salt compound having a melting point of 150 ° C. or lower, preferably an organic salt compound having a melting point of 100 ° C. or lower, more preferably an organic salt compound having a melting point of 80 ° C. or lower, and having a melting point of room temperature. Organic salt compounds having a temperature of (25 ° C.) or lower are more preferable.
• the ionic liquid is preferably an organic salt compound composed of a cation and an anion, and as a cation, an organic molecule having only one positive charge and a counter anion having only one negative charge are used. It is more preferable that the organic salt compound has.
• the ionic liquid may also be referred to as an ionic liquid or a room temperature molten salt.
• the ionic liquid used in the present invention preferably has a viscosity at 25 ° C. in the range of 10 to 1000 mPa ⁇ s, and more preferably in the range of 10 to 500 mPa ⁇ s.
• a liquid having a molecular weight (molecular weight of a cation and an anion combined) in the range of 100 to 700 is preferable, and a liquid having a molecular weight in the range of 120 to 500 is more preferable.
• cations forming an ionic liquid include ammonium ions; mono-substituted products containing cationic nitrogen atoms such as methylammonium ions, butylammonium ions, cyclohexylammonium ions, anilinium ions, benzylammonium ions, and ethanolammonium ions.
• an ion containing a cationic nitrogen atom is preferable, a heterocyclic ion containing a cationic nitrogen atom is more preferable, and an ion containing a pyrrolidinium ring, an ion containing an imidazolium ring, and a pyridinium ring are contained. Ions are particularly preferred.
• the anion forming the ionic liquid include the above-mentioned specific examples of the anion represented by X ⁇ in the general formula (2). Among them, (CF 3 SO 2 ) 2 N ⁇ and CH 3 COO ⁇ or B (CN) 4 is preferred, and (CF 3 SO 2 ) 2 N ⁇ is more preferred. Further, the anion forming the ionic liquid is preferably the same as the anion represented by X ⁇ contained in the polyether compound.
• the ionic liquid used in the present invention all of the cations and anions may be composed of the same ionic species, or two or more ionic species are mixed as either one or both of the cations and anions. It may be a thing. That is, the ionic liquid may be a single liquid or a mixture of two or more types.
• the ionic liquid used in the present invention examples include 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, and 1-ethyl-. 3-Methylimidazolium hexafluorophosphate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, N-butylpyridinium bis (trifluoromethanesulfonyl) imide, tributyldodecaphosphonium bis (trifluoromethanesulfonyl) imide, etc. Can be mentioned. Of these, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide is preferable.
• the content ratio of the ionic liquid in the ionic composition of the present invention is not particularly limited, but is preferably 10 parts by mass or more and 4000 parts by mass or less, preferably 30 parts by mass or more, with respect to 100 parts by mass of the polyether compound. It is preferably 3000 parts by mass or less, and more preferably 50 parts by mass or more and 2000 parts by mass or less.
• the ionic composition of the present invention can be made excellent in carbon dioxide absorption and low temperature characteristics.
• the molded product of the present invention contains the above-mentioned polyether compound or the above-mentioned ionic composition.
• the molded product of the present invention is not particularly limited, but may be, for example, a product obtained by casting a polyether compound or an ionic composition onto a base material such as a sheet, and the polyether compound or the ionic composition may be used. It may be impregnated with a non-woven fabric or a porous body.
• the molding method is not particularly limited, but A method for obtaining a film-like molded product by casting a polyether compound or an ionic composition onto a substrate as it is or in a state of being dissolved or dispersed in a solvent to form a liquid composition. A method of obtaining a molded product by impregnating a non-woven fabric or a porous body with a polyether compound or an ionic composition as it is or in a state of being dissolved or dispersed in a solvent to form a liquid composition. And so on.
• a reinforcing agent In a polyether compound or ionic composition, a reinforcing agent; an antiaging agent; an ultraviolet absorber; a light-resistant stabilizer; a tackifier; a surfactant; a conductivity-imparting agent; an electrolyte substance; a coloring agent (dye / pigment); After blending additives such as a fuel agent; an antistatic agent; the molded product may be molded.
• a crosslinking agent is blended to obtain a crosslinkable composition, which is then molded and crosslinked to obtain a molded product. Can be done.
• the polyether compound, the ionic composition and the molded product of the present invention are excellent in carbon dioxide absorption, they can be suitably used as a carbon dioxide absorbent.
• the polyether compound, the ionic composition and the molded product of the present invention are excellent in carbon dioxide absorption, they are suitably used as a member for carbon dioxide separation, a member for carbon dioxide storage, and a member for carbon dioxide transport. Can be done.
• the polyether compound, the ionic composition and the molded product of the present invention are excellent in carbon dioxide absorption under both normal pressure and high pressure (for example, 5000 hPa to 10000 hPa). Therefore, the polyether compound, the ionic composition and the molded product of the present invention are suitable as, for example, as a member of equipment for separating carbon dioxide under normal pressure and as a member of equipment for separating carbon dioxide under high pressure. Can be used.
• the polyether compounds, ionic compositions and moldings of the present invention include, for example, absorption of carbon dioxide from natural gas, absorption of carbon dioxide from biogas, absorption of carbon dioxide from CO 2 / CH 3 containing gas, It can be suitably used for applications such as absorption of carbon dioxide from CO 2 / N 2 containing gas.
• the gas to be absorbed by carbon dioxide may contain hydrogen sulfide, mercaptan (thiol), disulfide, carbon disulfide and the like.
• the number average molecular weight (Mn) of the polyether compound was determined as follows. That is, first, the average molecular weight of the repeating unit of polyepichlorohydrin A, the average molecular weight of the imidazolium structure-containing oxylan monomer unit, and the content of the imidazolium structure-containing oxylan monomer unit determined in (3) below. From the rate, the average molecular weight of all the repeating units constituting the polyether compound was determined. Then, the value obtained by multiplying the number of repeating units of polyepichlorohydrin A by the average molecular weights of all the repeating units constituting the polyether compound is taken as the number average molecular weight (Mn) of the polyether compound. bottom.
• the structure of the polyether compound and the content of the imidazolium structure-containing oxylan monomer unit in the polyether compound were measured as follows using a nuclear magnetic resonance apparatus (NMR). That is, first, 30 mg of the sample polyether compound was added to 1.0 mL of deuterated chloroform or deuterated dimethyl sulfoxide, and the mixture was uniformly dissolved by shaking for 1 hour. Then, the obtained solution was subjected to NMR measurement to obtain a 1 H-NMR spectrum, and the structure of the polyether compound was assigned according to a conventional method. The content of the imidazolium structure-containing oxylan monomer unit in the polyether compound was calculated by the following method.
• the number of moles B1 of the total oxylan monomer unit was calculated from the integrated value of the protons derived from the oxylan monomer unit of the main chain.
• the number of moles B2 of the imidazolium structure-containing oxylan monomer unit was calculated from the integrated value of the protons derived from the imidazolium structure.
• the ratio (percentage) of B2 to B1 was determined as the content of the imidazolium structure-containing oxylan monomer unit in the polyether compound.
• a polyether compound or ionic composition saturated with carbon dioxide is transferred together with a glass substrate to a closed container, and a temperature-temperature desorption gas analyzer (Temperature Projection-Mass Spectrometry: TPD-MS; Rigaku) filled with helium is used. It was introduced into the reaction tube of the heated desorption gas analyzer TPD type V). After the introduction of the polyether compound or ionic composition into a heating furnace, the amount of carbon dioxide detected by the detector is quantified while raising the temperature to per gram of the polyether compound or ionic composition. The amount of carbon dioxide absorbed was determined.
• the obtained oily substance has an oligomer (average 11-mer) composed of epichlorohydrin units having a bromomethyl group at the polymerization initiation terminal and a hydroxyl group at the polymerization termination terminal (hereinafter, polyepichlorohydrin). It can be said that it is Rin A).
• reaction product was washed with an equal mass mixed solution of toluene / methanol / water, the organic phase containing 1-normal butyl imidazole and toluene was removed, and the aqueous phase was dried under reduced pressure at 50 ° C. for 12 hours. , 11.7 g of a pale red solid was obtained.
• 1 H-NMR measurement and elemental analysis were performed on this solid, all the chloro groups in the repeating unit of the starting material polyepichlorohydrin A were converted to 1-normalbutylimidazolium chloride groups, and bromomethyl at the polymerization initiation terminal.
• Example 1 (Anion exchange of polyether compound B with lithium (bistrifluoromethanesulfonyl) imide) 5.0 g of the polyether compound B obtained in Production Example 2, 7.9 g of lithium (bistrifluoromethanesulfonyl) imide, and 20 mL of ion-exchanged water were added to a glass reactor with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50 ° C. for 12 hours, and the obtained solid-liquid mixture was washed with water to remove inorganic salts, and then the liquid phase was extracted with acetone. The obtained toluene solution was dried under reduced pressure at 50 ° C.
• Example 2 (Anion exchange of polyether compound B with sodium acetate) 5.0 g of the polyether compound B obtained in Production Example 2, 1.9 g of sodium acetate, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, dialysis was performed for 24 hours using a semipermeable membrane to remove inorganic salts. When the aqueous solution was dried under reduced pressure at 50 ° C. for 12 hours, 5.6 g of a light red solid was obtained.
• Example 3 (Anion exchange of polyether compound B with potassium tetracyanoborate) 5.0 g of the polyether compound B obtained in Production Example 2, 3.6 g of potassium tetracyanoborate, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50 ° C. for 12 hours, and the soluble part was extracted with methanol to remove inorganic salts. The obtained methanol solution was dried under reduced pressure at 50 ° C. for 12 hours to obtain 6.8 g of a viscous solid substance.
• the obtained reaction product was washed with an equal mass mixed solution of toluene / methanol / water, the organic phase containing 1-normal hexylimidazole and toluene was removed, and the aqueous phase was dried under reduced pressure at 50 ° C. for 12 hours. , 13.1 g of a light red solid was obtained. 1 H-NMR measurement and elemental analysis were carried out on this solid. As a result, all the chloro groups in the repeating unit of the starting material, polyepichlorohydrin A, were converted to 1-normalhexylmidazolium chloride groups, and the polymerization initiation terminal was bromomethyl.
• Example 4 (Anion exchange of polyether compound F with lithium bis (trifluoromethanesulfonyl) imide) 5.0 g of the polyether compound F obtained in Production Example 3, 6.5 g of lithium (bistrifluoromethanesulfonyl) imide, and 20 mL of ion-exchanged water were added to a glass reactor with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50 ° C. for 12 hours, and the obtained solid-liquid mixture was washed with water to remove inorganic salts, and then the liquid phase was extracted with acetone. The obtained acetone solution was dried under reduced pressure at 50 ° C.
• Example 5 (Anion exchange of polyether compound F with sodium acetate) 5.0 g of the polyether compound F obtained in Production Example 3, 1.7 g of sodium acetate, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, dialysis was performed for 24 hours using a semipermeable membrane to remove inorganic salts. When the aqueous solution was dried under reduced pressure at 50 ° C. for 12 hours, 5.5 g of a light red solid was obtained.
• Example 6 (Anion exchange of polyether compound F with potassium tetracyanoborate) 5.0 g of the polyether compound F obtained in Production Example 3, 3.2 g of potassium tetracyanoborate, and 20 mL of ion-exchanged water were added to a glass reactor equipped with a stirrer. After reacting at room temperature for 30 minutes, the mixture was dried under reduced pressure at 50 ° C. for 12 hours, and the soluble part was extracted with methanol to remove inorganic salts. The obtained methanol solution was dried under reduced pressure at 50 ° C. for 12 hours to obtain 6.6 g of a viscous solid substance.
• Example 7 50 parts of the polyether compound C obtained in Example 1 and 50 parts of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (viscosity at 25 ° C.: 51 mPa ⁇ s, molecular weight: 419.36). And were mixed in acetone. Then, the solvent was distilled off to obtain a transparent ionic composition. Using the obtained ionic composition, the amount of carbon dioxide absorbed was measured according to the above method. The results are shown in Table 1.
• Example 8 5 parts of the polyether compound C obtained in Example 1 and 95 parts of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide were mixed in acetone. Then, the solvent was distilled off to obtain a transparent ionic composition. Using the obtained ionic composition, the amount of carbon dioxide absorbed was measured according to the above method. The results are shown in Table 1.
• reaction product was washed with an equal mass mixed solution of toluene / methanol / water, the organic phase containing 1-ethylimidazole and toluene was removed, and the aqueous phase was dried under reduced pressure at 50 ° C. for 12 hours. 10.0 g of a light red solid was obtained.
• all the chloro groups in the repeating unit of the starting material polyepichlorohydrin A were 1-ethylimidazolium chloride groups and the bromomethyl groups at the initiation terminal of polymerization.
• the polyether compounds represented by the general formula (2) and containing a specific repeating unit were excellent in carbon dioxide absorption (Examples 1 to 8).
• the polyether compound when the polyether compound has an anion containing no nitrogen, carbon or oxygen as a counter anion, the polyether compound is inferior in carbon dioxide absorption (Comparative Examples 1, 2 and 3, 6). Further, when the polyether compound having an imidazolium structure does not have an alkyl group having 3 or more carbon atoms at a specific position of the imidazolium structure, the polyether compound is inferior in carbon dioxide absorption. There were (Comparative Examples 2, 3, 4, 6). Furthermore, the ionic composition consisting only of 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide was inferior in carbon dioxide absorption (Comparative Example 5).

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