WO2016143876A1 - Composé de type ligand, et polymère de coordination à un seul ou plusieurs trous - Google Patents

Composé de type ligand, et polymère de coordination à un seul ou plusieurs trous Download PDF

Info

Publication number
WO2016143876A1
WO2016143876A1 PCT/JP2016/057669 JP2016057669W WO2016143876A1 WO 2016143876 A1 WO2016143876 A1 WO 2016143876A1 JP 2016057669 W JP2016057669 W JP 2016057669W WO 2016143876 A1 WO2016143876 A1 WO 2016143876A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
optionally substituted
monoporous
ring
ion
Prior art date
Application number
PCT/JP2016/057669
Other languages
English (en)
Japanese (ja)
Inventor
進 北川
亮太郎 松田
暢彦 細野
Original Assignee
国立大学法人京都大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人京都大学 filed Critical 国立大学法人京都大学
Priority to JP2017505410A priority Critical patent/JPWO2016143876A1/ja
Publication of WO2016143876A1 publication Critical patent/WO2016143876A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/36—Esters of dithiocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Definitions

  • the present invention relates to a ligand compound and a monoporous or porous coordination polymer.
  • Organometallic polyhedra which are complexed with organic ligands and metal ions and built in a self-organized manner, are cage-like compounds with voids of several to several nanometers inside.
  • MOP Metal-Organic Polyhedra
  • Non-Patent Document 1 MOP can incorporate various small molecules inside the cage structure, and not only as a supramolecular host, but also in recent years as an adsorption and / or separation material for substances such as gases using its pores. Widely studied (for example, Non-Patent Document 2).
  • a simple MOP is usually obtained as a crystal or powdered solid, is hardly soluble in various solvents, and does not melt even when heated. Therefore, it has poor molding processability such as solution coating and thermoforming, which are indispensable for widespread use as a general-purpose material.
  • Non-Patent Document 3 As described above, although MOP has poor molding processability, various methods for forming a film have been attempted in order to utilize its unique structure (for example, Non-Patent Document 3). However, any of these methods is a method for forming a film by dispersing MOP in a polymer matrix, and there is no method for forming a film of MOP without using a polymer matrix.
  • MOP has its unique structure, application to various uses is attempted, but it can be treated only as a powdery microcrystalline solid for the purpose of adsorption and / or separation of substances, Further, it is poor in solvent solubility and molding processability, so that it can be formed into a film only by a method of dispersing in a polymer matrix.
  • a material that can be processed by a general-purpose process such as thermoforming and coating is preferable.
  • the present invention designs a compound in which MOP and a polymer are chemically bonded, MOP that can be formed into a film without using a polymer matrix, imparted solvent solubility and thermoforming processability, and It aims at providing the ligand compound which can manufacture the said MOP.
  • the present invention also provides a material separation membrane (especially a gas separation membrane) using MOP that has been provided with solvent solubility and thermoforming processability by chemically bonding MOP and polymer in this way. Also aimed.
  • the present inventors have conducted reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) of a desired polymer compound from the outer surface of the MOP, while maintaining the characteristics of the MOP, It has been found that high solvent solubility derived from a polymer compound, molding processability, and the like can be imparted.
  • the MOP to which such solvent solubility and moldability are imparted is formed by a specific metal ion and a specific organic ligand being alternately coordinated. Based on such knowledge, the present inventors have further studied and completed the present invention. That is, the present invention includes the following configurations.
  • m represents an integer of 1 to 3.
  • X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group.
  • X 2 represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different.
  • R 2 is
  • Item 2 The ligand compound according to Item 1, which is a group represented by:
  • X 2 represents the general formula (2):
  • R 3 represents a hydrogen atom or an optionally substituted alkyl group.
  • R 4 represents a hydrogen atom, an optionally substituted alkyl group or a cyano group.
  • X 3 represents a single bond, an optionally substituted alkylene group, or a group represented by —R 5 —COO— (R 5 represents an optionally substituted alkylene group).
  • Item 3 The ligand compound according to Item 1 or 2, which is a group represented by:
  • Y in the general formula (3) is a single ring composed of a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or thiophene ring, or a condensed ring in which one or two or more benzene rings are condensed to the single ring.
  • R 8 is the same or different and represents a carbon atom or a nitrogen atom.
  • R 9 represents a divalent aromatic hydrocarbon group which may be substituted.
  • k represents an integer of 0-2.
  • Item 4 The ligand compound according to any one of Items 1 to 3, which may contain a group represented by:
  • m represents an integer of 1 to 3.
  • X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group.
  • X 2 represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different.
  • R 2 is
  • Y represents an aromatic hydrocarbon ring or a heteroaromatic ring.
  • Z is the same or different and represents an optionally substituted ethylene chain.
  • n represents an integer of 5 to 20000.
  • a monoporous or porous coordination polymer comprising an organic ligand represented by the formula (1) and wherein the metal ion and the organic ligand are alternately coordinated.
  • a monoporous or porous coordination polymer according to Item 5 which is a group represented by:
  • X 2 represents the general formula (2):
  • R 3 represents a hydrogen atom or an optionally substituted alkyl group.
  • R 4 represents a hydrogen atom, an optionally substituted alkyl group or a cyano group.
  • X 3 represents a single bond, an optionally substituted alkylene group, or a group represented by —R 5 —COO— (R 5 represents an optionally substituted alkylene group).
  • Item 7 The monoporous or porous coordination polymer according to Item 5 or 6, which is a group represented by:
  • R 6 represents a hydrogen atom or an optionally substituted alkyl group.
  • R 7 is a hydroxyl group, an optionally substituted carboxy group, an optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl Indicates a group.
  • Item 8 The monoporous or porous coordination polymer according to any one of Items 5 to 7, which is a chain represented by:
  • Item 9 A monoporous or porous coordination polymer according to any one of Items 5 to 8, comprising the metal ion and the organic ligand.
  • Item 10 The monoporous or porous coordination polymer according to any one of Items 5 to 9, which contains 4 or more metal ions and 4 or more organic ligands.
  • Item 11 The monoporous or porous coordination polymer according to any one of Items 5 to 10, wherein the metal ion is a divalent metal ion.
  • Item 12. The monoporous or porous coordination polymer according to any one of Items 5 to 11, wherein the metal ion is a transition metal ion.
  • the metal ion is at least one selected from the group consisting of copper ion, zinc ion, cobalt ion, cadmium ion, rhodium ion, calcium ion, magnesium ion, manganese ion, nickel ion, palladium ion, lanthanum ion, and zirconium ion.
  • Item 15 The monoporous or porous coordination polymer according to any one of Items 5 to 12, wherein
  • Y in the general formula (3) is a single ring composed of a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, or thiophene ring, or a condensed ring in which one or two or more benzene rings are condensed to the single ring.
  • R 8 is the same or different and represents a carbon atom or a nitrogen atom.
  • R 9 represents a divalent aromatic hydrocarbon group which may be substituted.
  • k represents an integer of 0-2.
  • Item 14 The monoporous or porous coordination polymer according to any one of Items 5 to 13, which may contain a group represented by:
  • Item 15 The monoporous or porous coordination polymer according to any one of Items 5 to 14, which is an organometallic polyhedron.
  • Item 16 The monoporous or porous coordination polymer according to Item 15, having an average diameter of 2 nm to 100 nm.
  • Item 17. The monoporous or porous coordination polymer according to Item 15 or 16, which has one pore having an average diameter of 2 nm or less inside.
  • Item 18 A method for producing an organometallic polyhedron having polymer chains introduced therein, Using an organometallic polyhedron and a monomer compound, and a step of performing reversible addition-fragmentation chain transfer polymerization, The organometallic polyhedron has a divalent or higher valent metal ion and a general formula (5):
  • m represents an integer of 1 to 3.
  • X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group.
  • X 2 represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different.
  • R 2 is
  • Y represents an aromatic hydrocarbon ring or a heteroaromatic ring.
  • a metal ion and the organic ligand are alternately coordinate-bonded to each other.
  • Item 19 A material for adsorbing and / or separating a substance comprising a monoporous or porous coordination polymer according to any one of Items 5 to 17.
  • Item 20 The material for adsorbing and / or separating a substance according to Item 19, which is at least one member selected from the group consisting of a gas and / or ion adsorbing material and a gas and / or ion separating material.
  • Item 21 A substance separation membrane comprising the monoporous or porous coordination polymer according to any one of Items 5 to 17, or the substance adsorption and / or separation material according to Item 19 or 20.
  • Item 22 The substance separation membrane according to Item 21, which is a gas and / or ion separation membrane.
  • a polymer chain can be easily introduced into a monoporous or porous coordination polymer.
  • This ligand compound is a novel compound not described in any literature.
  • the monoporous or porous coordination polymer of the present invention thus produced has high solvent solubility and molding processing derived from the polymer while maintaining the properties of the original monoporous or porous coordination compound. Therefore, it is possible to expand the applicability to existing mass production molding processes.
  • 6 is a photograph showing the appearance of a substance separation membrane obtained in Example 6.
  • 4 is a graph showing the results of GPC measurement of the compounds obtained in Synthesis Examples 1 to 3.
  • 3 is a graph showing the results of GPC measurement of the compounds obtained in Examples 1 to 5 and Synthesis Examples 4 to 8.
  • 6 is a graph showing the results of GPC measurement and reaction rate of the compounds obtained in Synthesis Examples 4 to 8. It is an electron micrograph which shows the surface structure of the substance separation membrane obtained in Example 7 and 8 (Example 7: Transmission electron microscope (TEM), Example 8: Atomic force microscope (AFM)).
  • 6 is a graph showing the results of nitrogen and carbon dioxide adsorption / desorption tests of MOP1 obtained in Synthesis Example 2.
  • Example 6 is a graph showing the results of GPC measurement of the compounds obtained in Examples 9 to 10 and Synthesis Examples 8 to 9.
  • 4 is a graph showing the measurement results of the diameters of the compounds obtained in Synthesis Example 2, Example 1 and Example 8.
  • 3 is a graph showing the results of GPC measurement of the compounds obtained in Examples 11 to 15 and Synthesis Examples 18 to 23.
  • (A) is a plot of polymerization reaction time and monomer conversion
  • (b) is a plot of monomer conversion and MOP number average molecular weight ( ⁇ : number average molecular weight, ⁇ : molecular weight dispersion (Mw / Mn))
  • (c) is 2 is a graph showing a plot of monomer conversion and number average molecular weight of decomposed organic ligand ( ⁇ : number average molecular weight, ⁇ : molecular weight dispersion (Mw / Mn)).
  • Ligand Compound The ligand compound of the present invention has the general formula (1):
  • m represents an integer of 1 to 3.
  • X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group.
  • X 2 represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different.
  • R 2 is
  • Y represents an aromatic hydrocarbon ring or a heteroaromatic ring.
  • the ligand compound (1) is obtained from the viewpoint of obtaining a monoporous or porous coordination polymer having a three-dimensional framework structure by connecting metal ions and clusters thereof by the production method described later. It has a plurality (two) of carboxy groups capable of coordinating with metal ions. When there is only one carboxy group, a three-dimensional framework structure cannot be constructed, and a monoporous or porous coordination polymer cannot be obtained.
  • the ligand compound (1) has a dithioester structure that can be the starting point of reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) employed in the production method described later.
  • RAFT polymerization reversible addition-fragmentation chain transfer polymerization
  • MOP monoporous or porous coordination compound
  • examples of the aromatic hydrocarbon group represented by X 1 include a benzene ring, a pentalene ring, an indene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, a perylene ring, and triphenylene.
  • aromatic hydrocarbon rings such as a ring, an azulene ring, a heptalene ring, a biphenylene ring, an indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring and a phenanthrene ring.
  • groups derived from aromatic hydrocarbon rings include, for example, 0 to 4 substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (methyl groups, ethyl groups, propyl groups, etc.). It can also have about 1 (particularly 1 to 3).
  • examples of the heteroaromatic group represented by X 1 include a furan ring, a thiophene ring, a pyrrole ring, a silole ring, a borol ring, a phosphole ring, an oxazole ring, a thiazole ring, a pyridine ring, and a pyridazine ring.
  • Groups derived from heteroaromatic rings such as pyrimidine ring, pyrazine ring, thienothiophene ring and quinoline ring.
  • heteroaromatic ring-derived groups for example, 0 to 4 substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (methyl groups, ethyl groups, propyl groups, etc.) ( In particular, it may have about 1 to 3).
  • substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups (methyl groups, ethyl groups, propyl groups, etc.) ( In particular, it may have about 1 to 3).
  • X 1 in the general formula (1) is various in the monoporous or porous coordination polymer of the present invention in order to give easy synthesis and good living radical polymerization reactivity to various monomers in the production method described later. From the viewpoint of giving such characteristics, a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group, and the like are preferable, and a sulfur atom is more preferable.
  • examples of the divalent linking group represented by X 2 include the general formula (2):
  • R 3 represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group.
  • R 4 represents a hydrogen atom, an optionally substituted alkyl group, a cyano group, or an optionally substituted aryl group.
  • X 3 represents a single bond, an optionally substituted alkylene group, or a group represented by —R 5 —COO— (R 5 represents an optionally substituted alkylene group).
  • the group etc. which are represented by these are mentioned.
  • examples of the alkyl group represented by R 3 include acyclic alkyl groups having 1 to 6 carbon atoms such as a methyl group. These alkyl groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.).
  • examples of the aryl group represented by R 3 include a phenyl group and a naphthyl group. These aryl groups may have about 0 to 5 (especially 1 to 3) substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.) and the above alkyl groups.
  • R 3 in the general formula (2) is preferably an alkyl group which may be substituted, from the viewpoint of easy synthesis and good living radical polymerization reactivity for various monomers in the production method described later.
  • the methyl group which may be sufficient is more preferable, and a methyl group (unsubstituted) is further more preferable.
  • examples of the alkyl group represented by R 4 include acyclic alkyl groups having 1 to 6 carbon atoms such as a methyl group. These alkyl groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.).
  • R 4 in the general formula (2) is preferably a cyano group or an optionally substituted aryl group from the viewpoint of ease of synthesis and good living radical polymerization reactivity for various monomers in the production method described below.
  • a cyano group is more preferable.
  • examples of the alkylene group represented by X 3 include methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, propylidene group, tetramethylene group, 1-methyltrimethylene group, 2- Acyclic alkylene group such as methyltrimethylene group, 3-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group (preferably having 1 to 6 carbon atoms, particularly having 1 to 4 carbon atoms) Acyclic alkylene group); cyclic alkylene group such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, etc.
  • a linear acyclic alkylene group can also be employ
  • These alkylene groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.).
  • X 3 in the general formula (2) is an ester group in which these alkylene groups are linked (the group represented by the above -R 5 -COO- (R 5 represents an optionally substituted alkylene group)).
  • R 5 represents an optionally substituted alkylene group
  • X 3 in the general formula (2) is an ester group in which an alkylene group is linked from the viewpoint of ease of synthesis (the above -R 5 -COO- (wherein R 5 represents an optionally substituted alkylene group)). Are preferred.
  • the alkyl group represented by R 1 is not particularly limited, and any of a straight chain alkyl group and a branched chain alkyl group may be employed. From the viewpoint of further improving the solvent solubility mainly in a nonpolar solvent, a linear alkyl group is preferable for the compound.
  • the number of carbon atoms of such an alkyl group is preferably 1 to 100 from the viewpoint of further improving the solubility of the monoporous or porous coordination compound such as MOP mainly in a nonpolar solvent. 20 is more preferable, and 8 to 16 is more preferable.
  • alkyl group examples include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group.
  • These alkyl groups can also have about 0 to 10 (especially 1 to 5) substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.).
  • substituents such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.).
  • R 1 when m which is the number of R 1 is 2 or more, R 1 may be the same or different.
  • R 1 in the general formula (1) is preferably an alkyl group which may be substituted from the viewpoint of ease of synthesis and good living radical polymerization reactivity with respect to various monomers in the production method described later. Groups are more preferred.
  • m which is the number of R 1 , is a number determined by the type of X 1 , valence, etc., and is an integer of 1 to 3, preferably 1 or 2.
  • R 2 represents a dithioester structure
  • the ligand compound (1) and a metal ion described later are coordinated alternately.
  • the angle formed by two Y—COO — bonds is preferably less than 180 °.
  • the angle between the two Y—COO — bonds is less than 180 °, the angle between the two Y—COO — bonds can be used, Spherical monoporous or porous coordination polymers can be produced.
  • an organometallic polyhedron (monoporous coordination polymer) having micropores inside can be produced.
  • an aromatic hydrocarbon ring which may have a hetero atom is preferred, and a benzene ring, naphthalene ring, pyridine ring, pyrrole ring, thiophene ring, etc., or one in these rings or two or more benzene rings include condensed rings, etc. these rings and COO - in the binding of the group, the general formula (6):
  • R 8 is the same or different and represents a carbon atom or a nitrogen atom.
  • R 9 represents a divalent aromatic hydrocarbon group which may be substituted.
  • k represents an integer of 0-2.
  • the group represented by may be included.
  • k is preferably an integer of 0 to 2, more preferably 0 or 1.
  • Y is preferably a benzene ring, a naphthalene ring, a pyridine ring, a pyrrole ring, a thiophene ring, or the like, or a ring in which one or two or more benzene rings are condensed to these rings, a benzene ring, a naphthalene ring, A pyridine ring, a pyrrole ring, a thiophene ring and the like are more preferable, and a benzene ring is more preferable.
  • Such Y is, for example,
  • Such a ligand compound (1) can be obtained by adjusting the synthesis conditions (temperature, concentration, mixing ratio, etc.) for coordination with metal ions by the production method described later. Can give. In particular, it is possible to produce a porous coordination polymer having a jungle gym-like three-dimensional framework structure, and it is also possible to confine a large number of compounds inside.
  • ligand compounds (1) that satisfy these conditions include:
  • the monoporous or porous coordination polymer of the present invention comprises a divalent or higher valent metal ion and a general formula (3):
  • m represents an integer of 1 to 3.
  • X 1 represents a sulfur atom, an oxygen atom, a nitrogen atom, a carbon atom, an optionally substituted aromatic hydrocarbon group or an optionally substituted heteroaromatic group.
  • X 2 represents a single bond or a divalent linking group.
  • R 1 represents a hydrogen atom or an optionally substituted alkyl group. When m is 2 or more, R 1 may be the same or different.
  • R 2 is
  • Y represents an aromatic hydrocarbon ring or a heteroaromatic ring.
  • Z is the same or different and represents an optionally substituted ethylene chain.
  • n represents an integer of 5 to 20000.
  • organic ligand (3) the metal ion and the organic ligand are alternately coordinated and bonded to each other (hereinafter also referred to as “organic ligand (3)”). ing.
  • a transition metal ion can be preferably used, but it must be coordinated with the organic ligand (3).
  • a divalent metal ion (particularly a divalent transition metal ion) is preferable. Specifically, copper ion, zinc ion, cobalt ion, cadmium ion, rhodium ion, calcium ion, magnesium ion, manganese ion, nickel ion, palladium ion, lanthanum ion, zirconium ion, etc.
  • the metal ion is preferably used alone from the viewpoint of easy formation of a monoporous or porous coordination polymer by coordination bond with the organic ligand (3), but it should be used in combination of two or more. You can also.
  • the monoporous or porous coordination polymer of the present invention contains an organic ligand (3).
  • the organic ligand (3) is coordinated with the metal ion from the viewpoint of obtaining a monoporous or porous coordination polymer having a three-dimensional framework structure by linking the metal ion and its cluster. It has a plurality (two) of carboxy groups. When there is only one carboxy group, a three-dimensional framework structure cannot be constructed, and thus the monoporous or porous coordination polymer of the present invention cannot be obtained.
  • the organic ligand (3) has a dithioester structure that can be the starting point of reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) employed in the production method described later.
  • RAFT polymerization reversible addition-fragmentation chain transfer polymerization
  • MOP monoporous or porous coordination compound
  • the aromatic hydrocarbon group and heteroaromatic group represented by X 1 those described above can be adopted.
  • the kind and number of substituents are the same.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3).
  • X 1 in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.
  • the divalent linking group represented by X 2 those described above can be adopted.
  • the kind and number of substituents are the same.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3).
  • X 2 in all organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.
  • the alkyl group represented by R 1 those described above can be adopted.
  • the kind and number of substituents are the same.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3).
  • R 1 in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, R 2 in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3). Specifically, m in all organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.
  • the aromatic hydrocarbon group and heteroaromatic group represented by Y those described above can be adopted.
  • the kind and number of substituents are the same.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to arrange each organic ligand (3).
  • Y in all organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention can be the same.
  • Z is an ethylene chain which may be substituted, and means a monomer unit of a polymerized polymer. More specifically, this optionally substituted ethylene chain (monomer unit of the polymerized polymer) is introduced into a monoporous or porous coordination compound such as MOP by RAFT polymerization in the production method described later. It is a structural unit derived from the monomer compound used in the process. That is, depending on the type of Z, various characteristics can be imparted to a monoporous or porous coordination compound such as MOP. As such Z, general formula (4):
  • R 6 represents a hydrogen atom or an optionally substituted alkyl group.
  • R 7 is a hydroxyl group, an optionally substituted carboxy group, an optionally substituted acyloxy group, an optionally substituted carbamoyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl Indicates a group.
  • the chain represented by is preferred.
  • examples of the alkyl group represented by R 6 include acyclic alkyl groups having 1 to 6 carbon atoms such as a methyl group. These alkyl groups can also have about 0 to 5 (particularly 1 to 3) substituents such as halogen atoms (fluorine atom, chlorine atom, bromine atom, etc.).
  • R 6 maintains the characteristics of a monoporous or porous coordination compound such as MOP (having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.)
  • MOP having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.
  • an optionally substituted alkyl group is preferred, an unsubstituted alkyl group is more preferred, and a methyl group is more preferred.
  • the carboxy group represented by R 7 is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an n-hexyl group; an isobornyl group; a polyethylene glycol ( It can also have about 0 to 5 (especially 1 to 3) substituents such as (PEG) residues.
  • examples of the acyloxy group represented by R 7 include an acetoxy group, an ethanoyloxy group, a propionyloxy group, and the like, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • an alkyl group such as an n-hexyl group; an isobornyl group; and a substituent such as a polyethylene glycol (PEG) residue may have about 0 to 5 (particularly 1 to 3) substituents.
  • the carbamoyl group represented by R 7 is an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an n-hexyl group; an isobornyl group; a polyethylene glycol ( It can also have about 0 to 5 (especially 1 to 3) substituents such as (PEG) residues.
  • examples of the heteroaryl group represented by R 7 include a pyridyl group, a pyrrolyl group, a thienyl group, and the like.
  • An alkyl group such as an n-hexyl group; an isobornyl group; and 0 to 5 (particularly 1 to 3) substituents such as a polyethylene glycol (PEG) residue may be included.
  • R 7 maintains the characteristics of a monoporous or porous coordination compound such as MOP (having micropores inside, selectively absorbing carbon dioxide in the case of MOP).
  • MOP monoporous or porous coordination compound
  • an optionally substituted carboxy group or an optionally substituted aryl group is preferred, and the carboxy substituted with an alkyl group is preferred.
  • a group or an unsubstituted aryl group is more preferable, and a carbonylmethoxy group or a phenyl group is more preferable.
  • Examples of Z satisfying such conditions include methacrylic acid or a derivative residue thereof (methyl methacrylate residue, n-butyl methacrylate residue, tert-butyl methacrylate residue, hexyl methacrylate residue, methacrylic acid residue).
  • examples of the solvent that can improve the solvent solubility include toluene, chloroform, tetrahydrofuran, N, N′-dimethylformamide, dichloromethane, benzene, 1,4-dioxane, carbon tetrachloride, acetone, dichlorobenzene and the like. Is mentioned. In particular, it is useful in that it can be dissolved in a solvent having a low polarity such as toluene, chloroform, or benzene.
  • polymethacrylic acid polysodium methacrylate, polyacrylic acid, polyacrylic, such as methacrylic acid residue, acrylic acid residue, vinyl alcohol residue, methoxy acrylate acrylate residue, 4-vinylpyridine residue, etc.
  • groups derived from water-soluble polymer compounds such as sodium acrylate, polyvinyl alcohol, methoxy PEG polyacrylate, and poly (4-vinylpyridine)
  • MOP internal In the case of MOP, the water solubility can be improved while maintaining the selective absorption of carbon dioxide.
  • Z is a methyl methacrylate residue. Or as a styrene residue,
  • a single group may be employed, or two or more groups may be employed.
  • an organic ligand (3) having two or more kinds of Z is employed, the properties possessed by two or more different polymer compounds may be imparted to a monoporous or porous coordination compound such as MOP. Is possible.
  • n which is the number of repeating Z, is not particularly limited, and is a characteristic of a monoporous or porous coordination compound such as MOP (in the case of MOP, carbon dioxide in the case of MOP having micropores inside) From the viewpoint of further improving the molding processability (especially thermoforming processability) and imparting ion exchange ability, further improving the solvent solubility, and the like.
  • An integer is preferable, and an integer of 10 to 500 is more preferable.
  • the monoporous or porous coordination polymer of the present invention has a large number of organic ligands (3), but it is also possible to align the length of each organic ligand (3). . Specifically, it is possible to narrow the dispersion of n in all the organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention.
  • such an organic ligand (3) can give a porous coordination polymer by adjusting the synthesis conditions (temperature, concentration, mixing ratio, etc.) when coordinated with a metal ion.
  • a porous coordination polymer having a jungle gym-like three-dimensional framework structure can be used, and a large number of compounds can be confined inside.
  • Such an organic ligand (3) is not particularly limited, and specifically includes a general formula:
  • Etc. are more preferable.
  • the number of metal ions possessed by the monoporous or porous coordination polymer of the present invention is the type of metal ion, the angle between two Y-COO - bonds, the monoporous or porous coordination of the present invention. Depending on the average diameter of the polymer, etc., it is preferably 4 to 128, more preferably 12 to 48, and particularly preferably 24.
  • the number of organic ligands (3) possessed by the monoporous or porous coordination polymer of the present invention depends on the type of metal ion, the angle formed by two Y—COO — bonds, Depending on the average diameter of the porous or porous coordination polymer, etc., it is preferably 4 to 128, more preferably 12 to 48, and particularly preferably 24.
  • copper ions (Cu 2+ ) are used as metal ions and organic ligands (Y) are organic ligands where Y is a benzene ring, copper ions (Cu 2+ ) and organic Organometallic polyhedra (monoporous coordination polymers) each having 24 ligands are easily generated.
  • Y aromatic hydrocarbon ring or heteroaromatic ring
  • the monoporous or porous coordination polymer of the present invention has a configuration in which the divalent or higher-valent metal ion and the organic ligand (3) are alternately coordinated.
  • the monoporous or porous coordination polymer of the present invention may contain ions or ligands other than the divalent or higher metal ion and the organic ligand (3), From the viewpoint of ease of synthesis and analysis, and from the viewpoint of stably presenting a monoporous or porous coordination compound such as MOP, the monoporous or porous coordination polymer of the present invention comprises the above-described divalent or higher-valent metal ions and It is preferable to consist only of the organic ligand (3).
  • the monoporous or porous coordination polymer of the present invention can be a spherical compound.
  • This spherical compound can be an organometallic polyhedron (monoporous coordination polymer) having micropores inside.
  • the average diameter is not particularly limited, but it may be a monoporous or porous coordination such as MOP.
  • MOP monoporous or porous coordination
  • the average diameter of the pores present in the interior is not particularly limited, but a single unit such as MOP can be used. From the viewpoint of maintaining the characteristics of the porous or porous coordination compound (having micropores inside, in the case of MOP, selectively absorbing carbon dioxide, etc.), it is preferably 2 nm or less, preferably 0.1 to 1.5 nm. More preferred.
  • the average molecular weight is not particularly limited, but it may be a monoporous or porous coordination such as MOP. From the viewpoint of imparting ion exchange capacity and further improving solvent solubility, while maintaining the properties of the coordination compound (having micropores inside, selectively absorbing carbon dioxide in the case of MOP, etc.)
  • the number average molecular weight is preferably 5000-2000000, and more preferably 7000-200000.
  • a porous coordination polymer in the organic ligand (3), can be provided by adjusting the synthesis conditions (temperature, concentration, mixing ratio, etc.) for coordination with metal ions.
  • a porous coordination polymer having a jungle gym-like three-dimensional framework structure can be used, and a large number of compounds can be confined inside.
  • the production method of the monoporous or porous coordination polymer of the present invention is not particularly limited, and can be synthesized by various methods.
  • reaction formula 1 when synthesizing an organometallic polyhedron (monoporous coordination polymer) as the monoporous or porous coordination polymer of the present invention, for example, reaction formula 1:
  • Ligand compound (1) The ligand compound (1) in the above reaction formula 1 is the above-described ligand compound of the present invention.
  • X 2 is a group represented by the above general formula (2) as a divalent linking group, and X 3 is —R 5 —COO— (where R 5 is substituted).
  • X 3 is —R 5 —COO— (where R 5 is substituted).
  • the carboxy group is protected with a protecting group such as a silyl group (such as t-butyldimethylsilyl group), and the compound (8 ), And then esterification, preferably under neutral conditions, by known methods (eg, adding oxalyl chloride and a catalytic amount of N, N′-dimethylformamide to produce acid chloride in the reaction system). Preferably it is done.
  • the amount of the compound (7) used is not particularly limited, but from the viewpoint of yield and the like, it is preferable to use 0.2 to 1 mol (particularly 0.5 to 0.9 mol) with respect to 1 mol of the compound (8).
  • a base such as pyridine and amines (trimethylamine, N, N′-diisopropylethylamine, etc.) may be added to accelerate the reaction.
  • organic solvent that can be used in this step
  • known ones may be employed.
  • cyclic ethers such as tetrahydrofuran and dioxane
  • halogen solvents such as dichloromethane and chloroform
  • These solvents are preferably strictly dehydrated.
  • the reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, -20 to 100 ° C., particularly 0 to 50 ° C., 1 to 48 hours, particularly 2 to 24 hours. After completion of the reaction, usual isolation and purification steps can be performed as necessary.
  • the ligand compound (1) has, for example, R 2
  • the cation represented by M is preferably an alkali metal cation, and examples thereof include a sodium cation and a potassium cation.
  • examples of the halogen atom represented by X 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the carboxy group is protected with a protecting group such as a silyl group (t-butyldimethylsilyl group, etc.) or a tert-butyl group.
  • a protecting group such as a silyl group (t-butyldimethylsilyl group, etc.) or a tert-butyl group.
  • the reaction is preferably carried out under neutral conditions by a known method (for example, a method of adding trifluoroacetic acid to form an ester in the reaction system).
  • the amount of compound (9) used is not particularly limited, but from the viewpoint of yield and the like, it is preferable to use 0.2 to 2 mol (particularly 0.5 to 1.5 mol) with respect to 1 mol of compound (10).
  • the organic solvent that can be used in this step may be a known one.
  • cyclic ethers such as tetrahydrofuran and dioxane
  • halogen solvents such as dichloromethane and chloroform
  • ketones such as acetone and methyl ethyl ketone; preferable.
  • the reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, -20 to 100 ° C., particularly 0 to 50 ° C., 1 to 48 hours, particularly 2 to 24 hours.
  • usual isolation and purification steps can be performed as necessary.
  • the ligand compound which is a group represented by the formula (1), can also be produced according to the above method (by changing the raw materials or the like to a desired one).
  • the ligand compound (1) has, for example, X 1 -R 2
  • the carboxy group is protected with a protecting group such as a silyl group (t-butyldimethylsilyl group, etc.) or a tert-butyl group.
  • a protecting group such as a silyl group (t-butyldimethylsilyl group, etc.) or a tert-butyl group.
  • the amount of the compound (11) and CS 2 used is not particularly limited, but from the viewpoint of further improving the yield and further suppressing the production of by-products, 1 mol of the compound (10), Compound (11) is preferably used in an amount of 0.2 to 2 mol (particularly 0.5 to 1.5 mol), and CS 2 is preferably used in an amount of 0.2 to 2 mol (particularly 0.5 to 1.5 mol).
  • the organic solvent that can be used in this step may be a known one.
  • cyclic ethers such as tetrahydrofuran and dioxane
  • halogen solvents such as dichloromethane and chloroform
  • ketones such as acetone and methyl ethyl ketone; preferable.
  • the reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, -20 to 100 ° C., particularly 0 to 50 ° C., 1 to 48 hours, particularly 2 to 24 hours.
  • usual isolation and purification steps can be performed as necessary.
  • an organometallic polyhedron (MOP) can be obtained by reacting the ligand compound (1) in the above reaction formula 1 with a metal compound in an organic solvent. it can.
  • the metal compound is not particularly limited, but a divalent metal salt is preferable from the viewpoint of easily configuring MOP.
  • the metal species constituting such a divalent metal salt is not particularly limited, from the viewpoint of easily forming a monoporous or porous coordination polymer by coordination bond with the organic ligand (3), Transition metals such as copper, zinc, cobalt, cadmium, rhodium, calcium, magnesium, manganese, nickel, palladium, lanthanum, and zirconium are preferable, and copper or zinc is more preferable.
  • organic acid salts such as acetates and formates; inorganic acid salts such as sulfates, nitrates, carbonates, hydrochlorides, and hydrobromides can be used.
  • metal compounds include copper (II) acetate, copper (II) nitrate, copper (II) chloride, zinc nitrate, cobalt (II) nitrate, cadmium acetate, and nickel (II) chloride. It can be preferably used.
  • the metal compound may be a hydrate or a solvate.
  • the metal compound is preferably used alone from the viewpoint of easy synthesis and structural analysis and from the viewpoint of easy formation of a stable MOP, but may be used in combination of two or more.
  • the amount of the metal compound used is preferably 0.5 to 2.0 moles per mole of the ligand compound (1).
  • the organic solvent that can be used in this step a known solvent may be employed.
  • amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, N-methylpyrrolidone are preferable.
  • the reaction conditions are not limited as long as the reaction proceeds sufficiently, and can be, for example, ⁇ 50 to 100 ° C., particularly 10 to 40 ° C., 10 minutes to 24 hours, particularly 30 minutes to 12 hours. After completion of the reaction, it may be purified by precipitation in an alcohol solvent such as methanol, if necessary.
  • X 1 , X 2 , R 1 , R 2 , Y and m are the same as defined above.
  • the metal ion and the organic ligand are alternately coordinated. That is, it is MOP in which a polymer chain is not introduced, and the description of the above “monoporous or porous coordination polymer” can be used for other characteristics.
  • RAFT polymerization a polymer chain can be introduced into MOP by causing RAFT polymerization using a desired monomer compound according to the required characteristics for MOP. Maintaining pores, selectively absorbing carbon dioxide, etc., while providing ion exchange capability, further improving solvent solubility, and further improving molding processability (especially thermoforming processability) Can do.
  • the compound of the present invention can be obtained by RAFT polymerization of MOP and a monomer compound in an organic solvent using a radical polymerization initiator.
  • R 6 and R 7 are the same as defined above.
  • methacrylic acid or a derivative thereof methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, isobornyl methacrylate, methacrylic acid, methoxy methacrylate is preferable.
  • methyl methacrylate is particularly preferred from the viewpoint of ease of synthesis and imparting solvent solubility and thermoforming processability to MOP.
  • These monomer compounds can be used alone or in combination of two or more. In particular, if a plurality of monomer compounds are used, it is possible to introduce a copolymer polymer chain and impart characteristics derived from a plurality of different polymers.
  • the radical polymerization initiator is not particularly limited, and tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyoctanoate, tert-butyl peroxyneodecanoate, peroxy Hydrogen peroxides such as tert-butyl isobutyrate, lauroyl peroxide, tert-amyl peroxypivalate, tert-butyl peroxypivalate, dicumyl peroxide, benzoyl peroxide, potassium persulfate, ammonium persulfate; 2,2'- Azobis (isobutyronitrile), 2,2'-azobis (2-butenonitrile), 4,4'-azobis (4-pentanoic acid), 1,1'-azobis (cyclohexanecarbonitrile), 2- (tert- Butylazo) -2
  • the amount of the monomer compound and radical polymerization initiator used is not particularly limited. From the viewpoints of yield and molecular weight dispersion of the polymer obtained by RAFT polymerization, the ligand compound (1) residue 1 in MOP It is preferable to use 20 to 10000 mol (particularly 50 to 2000 mol) of the monomer compound and 0.01 to 2 mol (particularly 0.5 to 1 mol) of the radical polymerization initiator with respect to mol.
  • the organic solvent that can be used in this step may be a known one.
  • an aromatic solvent such as benzene, toluene, xylene, mesitylene, and anisole
  • a cyclic ether such as 1,4-dioxane
  • the reaction conditions may be such that the reaction proceeds sufficiently, and can be, for example, 10 to 150 ° C., particularly 50 to 100 ° C., 10 minutes to 24 hours, particularly 30 minutes to 12 hours. After completion of the reaction, normal isolation and purification steps may be performed as necessary.
  • the completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by gas chromatography, high performance liquid chromatography or the like, but is not limited thereto.
  • the obtained mixed solution is put into a poor polymer solvent (especially an alcohol-based organic solvent such as methanol), subjected to suction filtration to collect a precipitate, washed with the poor solvent, and if necessary.
  • the organometallic polyhedron (monoporous coordination polymer) of the present invention is vacuum-dried at a temperature at which the organometallic polyhedron (monoporous coordination polymer) does not decompose (for example, 25 to 250 ° C.) for several hours. ) Can be obtained. Cleaning with an organic solvent and vacuum drying can be replaced by cleaning with supercritical carbon dioxide, which is more effective.
  • This method can be applied to random copolymerization and block copolymerization of different monomers, and a monoporous or porous coordination polymer into which a copolymerized polymer chain is introduced can be obtained in the same manner.
  • a monoporous or porous coordination polymer into which a copolymerized polymer chain is introduced can be obtained in the same manner.
  • ATRP atom transfer radical polymerization
  • NMP nitroxide-mediated radical polymerization
  • anionic polymerization method etc.
  • the above-described monoporous or porous coordination polymer of the present invention is used as a substance adsorption and / or separation material by taking advantage of its unique substance absorption characteristics. be able to.
  • the monoporous or porous coordination polymer of the present invention can adsorb and / or separate a substance in a gas state and can capture and / or separate a substance in an ionic state. Therefore, the monoporous or porous coordination polymer of the present invention can be preferably used as a gas and / or ion adsorbing material or a gas and / or ion separating material.
  • the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron
  • a carbon dioxide adsorbing material or a carbon dioxide is utilized by utilizing the property of selectively adsorbing carbon dioxide. It can be suitably used as a separation material.
  • other gas species and ionic species can be similarly adsorbed and / or separated.
  • a vacuum is used in order to remove moisture and solvent adsorbed on the monoporous or porous coordination polymer. Pre-drying is preferably performed.
  • a film can be easily produced using the monoporous or porous coordination polymer of the present invention.
  • a film can be used as a material separation membrane.
  • the monoporous or porous coordination polymer of the present invention can adsorb and / or separate a substance in a gas state and can capture and / or separate a substance in an ionic state.
  • the substance separation membrane of the present invention can be a gas and / or ion separation membrane.
  • the monoporous or porous coordination polymer of the present invention is an organometallic polyhedron, it is suitably used as a carbon dioxide separation membrane by utilizing the property of selectively adsorbing carbon dioxide. can do.
  • a suitable design is applied to the monoporous or porous coordination polymer of the present invention, other gas species and ionic species can be similarly adsorbed and / or separated.
  • Such a material separation membrane can be produced using, for example, a coating composition containing the monoporous or porous coordination polymer (material adsorption and / or separation material) of the present invention.
  • a coating composition for example, a solution obtained by dissolving the monoporous or porous coordination polymer of the present invention in an organic solvent can be used.
  • the monoporous or porous coordination polymer (substance adsorption and / or separation material) of the present invention can be used alone or in combination of two or more.
  • organic solvents examples include toluene, chloroform, tetrahydrofuran, benzene, N, N′-dimethylformamide, and the like.
  • the concentration of the monoporous or porous coordination polymer (substance adsorption and / or separation material) of the present invention is 1 to 100 mg / mL from the viewpoint of forming a more homogeneous and self-supporting film. 5 to 50 mg / mL is more preferable.
  • a binder resin may be used.
  • the monoporous or porous coordination polymer of the present invention (substance adsorption and / or separation) can be used without using a binder resin.
  • the binder resin should not be used. preferable.
  • a leveling agent, a coupling agent, a thickener, an ultraviolet absorber, a light stabilizer, an antifreezing agent, and the like may be added to the coating composition as long as the effects of the present invention are not adversely affected. However, it is preferably not used for the same reason as described above.
  • the substance separation membrane of the present invention can be coated on a substrate by, for example, coating or spraying.
  • the coating method is not particularly limited. For example, drop casting method, spin coating method, dip coating method, flow coating method, spray coating method, roll coating method, screen printing method, bar coater method, brush coating, sponge coating, etc. Conventionally known coating methods can be used.
  • an intermediate layer may be coated before coating the coating composition (material adsorption and / or separation material) on the substrate.
  • the film thickness of the coating film (substance separation film) formed by coating is not particularly limited, and is preferably from 100 to 10 ⁇ m, more preferably from 200 to 1.5 ⁇ m, from the viewpoint of material separation characteristics.
  • the substrate that can be coated is not particularly limited, and the material thereof is metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, paper, combinations thereof, laminates thereof, and coatings thereof. Examples include the body.
  • the thus obtained material separation membrane of the present invention is a membrane made of a monoporous or porous coordination polymer having an average diameter of about 8 to 100 nm (particularly about 10 to 50 nm).
  • Such a material separation membrane of the present invention can be applied to molecular sensing, drug delivery, etc. in addition to substance (particularly gas) adsorption, substance (particularly gas) separation, substance (particularly gas) occlusion, and the like.
  • Synthesis Example 1 Synthesis of ligand compound 1 (organic ligand 1)
  • TBDMS-Cl represents tert-butyldimethylsilyl chloride.
  • DMF represents dimethylformamide.
  • CDPA 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid
  • TDMS-Cl tert-butyldimethylsilyl chloride
  • imidazole 0.17 g, 2.5 mmol
  • DMF dimethylformamide
  • the extracted organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous sodium chloride solution, and dehydrated by adding anhydrous magnesium sulfate.
  • the solution was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using chloroform as a mobile phase to obtain a CDPA-protected TBDMS (CDPA-TBDMS) (0.58 g, 92%).
  • DMF dimethylformamide
  • THF tetrahydrofuran
  • CDPA-TBDMS (0.2 g, 0.39 mmol) was dissolved in dichloromethane (1 mL), the solution was cooled to 0 ° C. with an ice-water bath, and 1 or 2 drops of DMF were added (catalyst). To this, a solution of oxalyl chloride ((COCl) 2 ; 40.6 ⁇ L, 0.47 mmol) dissolved in 0.1 mL of dichloromethane was added dropwise little by little (at this time, carbon monoxide gas was generated as a by-product) ). The solution was allowed to react for 3 hours while gradually returning to room temperature, and then the solvent was completely distilled off.
  • Target 1 50 mg, 23%).
  • 1 H NMR 400 MHz, CDCl 3 , using JEOL ECX-400, solvent peak as internal standard: TM (ppm) 8.67 (s, 1H), 8.03 (s, 2H), 3.39 (tr, 2H) , 2.97 (tr, 2H), 2.79-2.64 (m, 1H), 2.58-2.48 (m, 1H), 1.97 (s, 3H), 1.80-1.68 (m, 2H), 1.48-1.20 (m, 21H) , 0.89 (tr, 3H).
  • Cu (OAc) 2 .H 2 O represents copper acetate monohydrate.
  • DMF represents dimethylformamide.
  • AIBN represents azobisisobutyronitrile
  • MOP1 (5 mg) obtained in Synthesis Example 2 and methyl methacrylate monomer (0.16 kg) were dissolved in toluene (1 ml). MOP1 is insoluble in toluene, but can be dissolved in a small amount when mixed with methyl methacrylate. To this was added a 0.1 M toluene solution (80 ⁇ L) of azobisisobutyronitrile (AIBN). The solution was freeze degassed (3 times) to remove dissolved oxygen, and then the solution was heated to 70 ° C. in an oil bath to initiate the reaction. The solution was polymerized for 4 hours with stirring.
  • AIBN azobisisobutyronitrile
  • Example 2 A part of the reaction solution of Example 1 was taken out after 65 minutes from the start of the reaction to obtain a polymer graft MOP.
  • Example 3 A part of the reaction solution of Example 1 was taken out after 130 minutes from the start of the reaction to obtain a polymer graft MOP.
  • Example 4 A part of the reaction solution of Example 1 was taken out after 205 minutes from the start of the reaction to obtain a polymer graft MOP.
  • Example 5 A part of the reaction solution of Example 1 was taken out after 265 minutes from the start of the reaction to obtain a polymer graft MOP.
  • Synthesis Examples 4 to 7 Decomposition of polymer chain-introduced organometallic polyhedron Synthesis Example 3 except that the polymer graft MOP obtained in Examples 2 to 5 was used in place of the polymer graft MOP obtained in Example 1 It was confirmed that an organic ligand having a structure in which methyl methacrylate was polymerized on the ligand compound 1 was obtained.
  • Example 6 Production of a material separation membrane (production of a self-supporting film)
  • the polymer graft MOP obtained in Example 5 was dissolved in chloroform to a concentration of 10 mg / mL, and the resulting solution was drop-cast on a glass substrate as a coating composition and dried at room temperature.
  • the material separation membrane was obtained by peeling the glass substrate. The appearance is shown in FIG.
  • Example 7 Production of a material separation membrane (production of a film for TEM observation)
  • the polymer graft MOP obtained in Example 5 was dissolved in chloroform so that the concentration was 5 mg / mL, and the obtained solution was drop-cast on a copper grid as a coating composition, and dried at room temperature. A material separation membrane was obtained.
  • Example 8 Production of a material separation membrane (production of a film for AFM observation)
  • the polymer graft MOP obtained in Example 5 was dissolved in chloroform so as to have a concentration of 5 mg / mL, and the obtained solution was dropped on a glass substrate as a coating composition, and dried at room temperature. A material separation membrane was obtained.
  • Example 9 Synthesis of Polymer Chain-Introduced Organometallic Polyhedron MOP1 (5 mg) and n-butyl methacrylate monomer (0.23 g) obtained in Synthesis Example 2 were dissolved in toluene (1 mL). A 0.1 M toluene solution (80 ⁇ L) of azobisisobutyronitrile (AIBN) was added thereto. The solution was freeze degassed (3 times) to remove dissolved oxygen, and then the solution was heated to 70 ° C. in an oil bath to initiate the reaction. The solution was polymerized for 2 hours with stirring. Thereafter, the solution was quenched with liquid nitrogen to stop the reaction, and the solution was poured into methanol (20 mL) to precipitate a polymer.
  • AIBN azobisisobutyronitrile
  • Example 10 Synthesis of copolymer polymer chain-introduced organometallic polyhedron MOP1-graft-PBMA (10 mg) and styrene monomer (0.2 g) obtained in Example 9 were dissolved in toluene (1 mL). A 0.1 M toluene solution (80 ⁇ L) of azobisisobutyronitrile (AIBN) was added thereto. The solution was freeze degassed (3 times) to remove dissolved oxygen, and then the solution was heated to 70 ° C. in an oil bath to initiate the reaction. The solution was allowed to polymerize for 2 hours 30 minutes with stirring.
  • AIBN azobisisobutyronitrile
  • Test example 1 Gel permeation chromatography (GPC) measurement
  • GPC Gel permeation chromatography
  • Test Example 2 Electron Microscope Observation The surface structure of the material separation membrane obtained in Examples 7 and 8 was observed with an electron microscope (Example 7: Transmission electron microscope (TEM), Example 8: Atomic force microscope (AFM) )). The results are shown in FIG. As a result, it can be understood that the surface is composed of particles (polymer graft MOP) of about 10 to 20 nm.
  • TEM Transmission electron microscope
  • AFM Atomic force microscope
  • Test Example 3 Gas Adsorption / Desorption Test With respect to MOP1 obtained in Synthesis Example 2, the nitrogen adsorption amount and nitrogen desorption amount at a temperature of 77 K, and the carbon dioxide adsorption amount and the carbon dioxide desorption amount at a temperature of 195 K were measured.
  • a Belsorp Max volumetric adsorption device manufactured by Nippon Bell Co., Ltd. was used for the measurement. The measurement was performed at a temperature of 77 K using a Belsorp Max cryosystem. The obtained result is shown in FIG. In FIG. 6, ads is an adsorption amount and des is a desorption amount.
  • MOP1 selectively adsorbs and desorbs carbon dioxide as compared with nitrogen. Since the characteristic of selectively adsorbing and desorbing carbon dioxide is derived from the unique structure of MOP, the compound of the present invention into which a polymer chain is introduced also selectively absorbs and desorbs carbon dioxide. Can do.
  • Test example 4 Gel permeation chromatography (GPC) measurement (2) As a measuring instrument, Measuring equipment: HPLC Prominence manufactured by Shimadzu Corporation (Liquid feeding pump: LC-20AD, Autosampler: SIL-20A, Column oven: CTO-20AC Detector: RI (differential refraction) detector (RID-10A) Column used: Shodex KF-804L 2 Column temperature: 40 ° C Mobile phase and flow rate: Tetrahydrofuran 1mL / min It was used.
  • GPC Gel permeation chromatography
  • Example 10 GPC measurement of the compounds obtained in Examples 9 to 10 and Synthesis Examples 8 to 9 was performed, and the molecular weight (number average molecular weight) of each compound was measured. The results are shown in FIG. In the same manner as in Example 1, in Example 9, n-butyl methacrylate monomer and MOP1 were reacted and GPC measurement was performed. As a result, it can be understood that the molecular weight is increased (number average molecular weight 132300) by introducing a polymer chain into MOP1. In Example 10, the compound (MOP1-graft-PBMA) obtained in Example 9 and the styrene monomer were reacted successively to perform GPC measurement.
  • MOP1-graft-PBMA number average molecular weight
  • the styrene monomer is continuously introduced into MOP1-graft-PBMA, thereby further increasing the molecular weight (number average molecular weight 269300). That is, through Examples 9 and 10, it was found that a block copolymer of butyl methacrylate and styrene could be introduced into MOP1 by performing two-step RAFT polymerization from MOP1. In addition, as described above, when PMDETA is allowed to act on the organometallic polyhedron, each organic ligand can be decomposed one by one.
  • the compound obtained in Synthesis Example 9 (number average molecular weight 14500) is the compound obtained in Synthesis Example 8 ( The molecular weight is certainly larger than the number average molecular weight 13400), which means that the living block copolymerization is proceeding on MOP1.
  • Test Example 5 MOP1 obtained in Diameter Synthesis Example 2, the polymer chain-introduced organometallic polyhedron obtained in Example 1, and the copolymer polymer chain-introduced organometallic polyhedron obtained in Example 8 were analyzed by Zetasizer Nano ZSP manufactured by Malvern. The diameter was measured. The results are shown in FIG. As a result, in the THF solution, MOP1 is distributed in the range of about 3 to 7 nm, the polymer chain-introduced organometallic polyhedra are in the range of about 10 to 30 nm, and the copolymer polymer chain-introduced organometallic polyhedra are in the range of about 12 to 50 nm.
  • the average diameter was about 5 nm for MOP1, about 18 nm for the polymer chain-introduced organometallic polyhedron, and about 20 nm for the copolymer polymer chain-introduced organometallic polyhedron.
  • Synthesis Example 12 Synthesis of ligand compound 2 (organic ligand 2)
  • t-Bu represents a tert-butyl group.
  • t-Bu represents a tert-butyl group.
  • TFA indicates trifluoroacetic acid.
  • Synthesis Example 13 Synthesis of ligand compound 3 (organic ligand 3)
  • t-Bu represents a tert-butyl group.
  • t-Bu represents a tert-butyl group.
  • TFA indicates trifluoroacetic acid.
  • Synthesis Example 14 Synthesis of ligand compound 4 (organic ligand 4)
  • t-Bu represents a tert-butyl group.
  • t-Bu represents a tert-butyl group.
  • TFA indicates trifluoroacetic acid.
  • Synthesis Example 15 Synthesis of ligand compound 5 (organic ligand 5)
  • t-Bu represents a tert-butyl group.
  • t-Bu represents a tert-butyl group.
  • TFA indicates trifluoroacetic acid.
  • Synthesis Example 16 Synthesis of ligand compound 6 (organic ligand 6)
  • t-Bu represents a tert-butyl group.
  • t-Bu represents a tert-butyl group.
  • TFA indicates trifluoroacetic acid.
  • Synthesis Example 17 Synthesis of ligand compound 7 (organic ligand 7)
  • t-Bu represents a tert-butyl group.
  • t-Bu represents a tert-butyl group.
  • TFA indicates trifluoroacetic acid.
  • Cu (OAc) 2 .H 2 O represents copper acetate monohydrate.
  • NMP represents N-methylpyrrolidone.
  • An organometallic polyhedral MOP2 was obtained in the same manner as in Synthesis Example 2, except that the ligand compound 3 (organic ligand 3) obtained in Synthesis Example 13 was used as a raw material and N-methylpyrrolidone was used as a solvent. It was.
  • Polymer grafting was carried out in the same manner as in Example 1, except that MOP2 obtained in Synthesis Example 18 was used as the raw material, tert-butyl acrylate was used as the monomer compound, tetrahydrofuran was used as the solvent, and the reaction time was 15 minutes. MOP (MOP2-graft-PtBA39) was obtained. In addition, since this polymer graft MOP is also highly soluble in a solvent, a film can be produced by coating and drying.
  • Example 12 A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was 45 minutes.
  • Example 13 A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was 75 minutes.
  • Example 14 A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was changed to 105 minutes.
  • Example 15 A polymer graft MOP was obtained in the same manner except that the reaction time in Example 11 was 135 minutes.
  • Synthesis Examples 19 to 23 Decomposition of polymer chain-introduced organometallic polyhedra Synthesis Example 3 except that the polymer graft MOP obtained in Examples 11 to 15 was used instead of the polymer graft MOP obtained in Example 1 It was confirmed that an organic ligand having a structure in which tert-butyl acrylate was polymerized to the ligand compound 2 was obtained.
  • Test Example 6 Gel permeation chromatography (GPC) measurement (Part 3) As a measuring instrument, Measuring equipment: HPLC Prominence manufactured by Shimadzu Corporation (Liquid feeding pump: LC-20AD, Autosampler: SIL-20A, Column oven: CTO-20AC Detector: RI (differential refraction) detector (RID-10A) Column used: Shodex KF-804L 2 Column temperature: 40 ° C Mobile phase and flow rate: Tetrahydrofuran 1mL / min It was used.
  • GPC Gel permeation chromatography
  • Example 11 GPC measurement of the compounds obtained in Examples 11 to 15 and Synthesis Examples 18 to 23 was performed, and the molecular weight (number average molecular weight) of each compound was measured. The results are shown in FIG. In the same manner as in Example 1, in Examples 11 to 15, tert-butyl acrylate monomer and MOP2 were reacted and GPC measurement was performed. As a result, in comparison with MOP2 obtained in Synthesis Example 18 (number average molecular weight 5090 g / mol), Example 11 (number average molecular weight 6500 g / mol) was carried out by introducing a polymer chain.
  • Example 12 (number average molecular weight 18000 g / mol), Example 13 (number average molecular weight 30700 g / mol), Example 14 (number average molecular weight 46800 g / mol), Example 15 (number average molecular weight 59200 g / mol) It can be understood that both increase in molecular weight.
  • the organic ligands can be decomposed one by one.
  • the compounds obtained in Synthesis Examples 19 to 23 are the organic ligands of the polymer graft MOP.
  • FIG. 10 (a) a plot of the polymerization reaction time and the monomer conversion rate is shown in FIG. 10 (b) ( ⁇ : number average molecular weight, ⁇ : molecular weight.
  • FIG. 10 (b) a plot of the monomer conversion rate and the MOP number average molecular weight is shown in FIG. 10 (b) ( ⁇ : number average molecular weight, ⁇ : molecular weight.
  • the monomer conversion rate and the number average molecular weight of the decomposed organic ligand are plotted in FIG. 10 (c) ( ⁇ : number average molecular weight, ⁇ : molecular weight dispersion (Mw / Mn)).
  • Mw / Mn molecular weight dispersion
  • Example 16 Ligand compound 2 (organic ligand 2) obtained in Synthesis Example 12 instead of ligand compounds 1 and 3 (organic ligands 1 and 3) as the ligand compound (organic ligand)
  • a polymer graft MOP was obtained in the same manner as in Example 1 except that was used. It was also confirmed that polymer graft MOP was obtained by this method. In addition, since this polymer graft MOP is also highly soluble in a solvent, a film can be produced by coating and drying.
  • ligand compound (organic ligand)
  • ligand compound 4 (organic ligand) obtained in Synthesis Example 14 4
  • ligand compound 5 obtained in Synthesis Example 15
  • ligand compound 6 obtained in Synthesis Example 16
  • ligand obtained in Synthesis Example 17 Similar results are expected to be obtained when compound 7 (organic ligand 7) or the like is used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une membrane de séparation de substances (en particulier, une membrane de séparation de gaz) obtenue à l'aide d'un composé de type ligand apte à la production de MPO. L'invention concerne également un polymère de coordination à un seul ou plusieurs trous qui comprend des ions métalliques ayant une valence de 2 ou plus et un ligand organique représenté par la formule générale (3), les ions métalliques et le ligand organique ayant été liés en alternance par des liaisons de coordination. Le polymère de coordination peut être converti en film sans avoir à recourir à une matrice polymère et peut être doué de solubilité dans les solvants et d'aptitude au moulage. [Dans la formule, m est un nombre entier de 1-3; X1 représente un atome de soufre, un atome d'oxygène, un atome d'azote, un atome de carbone, un groupe hydrocarbure aromatique éventuellement substitué, ou un groupe hétéroaromatique éventuellement substitué; X2 représente une simple liaison ou un groupe de liaison divalent; R1représente un atome d'hydrogène ou un groupe alkyle éventuellement substitué et quand m est 2 ou plus, alors les fragments R1 peuvent être identiques ou différents; R2 est un groupe représenté par la formule BB; Y représente un cycle hydrocarbure aromatique ou un cycle hétéroaromatique; les fragments Z peuvent être identiques ou différents et représentent chacun une chaîne éthylène éventuellement substituée; et n est un nombre entier de 5-20 000].
PCT/JP2016/057669 2015-03-10 2016-03-10 Composé de type ligand, et polymère de coordination à un seul ou plusieurs trous WO2016143876A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017505410A JPWO2016143876A1 (ja) 2015-03-10 2016-03-10 配位子化合物、並びにそれを用いた単孔性若しくは多孔性配位高分子

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015047768 2015-03-10
JP2015-047768 2015-03-10

Publications (1)

Publication Number Publication Date
WO2016143876A1 true WO2016143876A1 (fr) 2016-09-15

Family

ID=56879815

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/057669 WO2016143876A1 (fr) 2015-03-10 2016-03-10 Composé de type ligand, et polymère de coordination à un seul ou plusieurs trous

Country Status (2)

Country Link
JP (1) JPWO2016143876A1 (fr)
WO (1) WO2016143876A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017104724A1 (fr) * 2015-12-14 2017-06-22 国立大学法人京都大学 Polymère en étoile
CN110975940A (zh) * 2019-12-12 2020-04-10 万华化学集团股份有限公司 一种复合金属光催化体系及其制备方法和应用
CN111939771A (zh) * 2020-07-01 2020-11-17 华南理工大学 一种具有取向结构的聚苯乙烯-金属有机多面体及其制法和用途
CN114213575A (zh) * 2021-12-15 2022-03-22 华南理工大学 一种金属-有机配位聚合物及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH063869A (ja) * 1992-06-23 1994-01-14 Fuji Photo Film Co Ltd 静電写真用液体現像剤
WO2007054581A2 (fr) * 2005-11-14 2007-05-18 Basf Se Materiau structurel organometallique poreux contenant un autre polymere
WO2007102501A1 (fr) * 2006-03-09 2007-09-13 The University Of Tokyo Complexes de metaux de transition spheriques polymerisables, complexes de metaux de transition spheriques et procedes de production des deux types de complexes
WO2008082087A1 (fr) * 2007-01-03 2008-07-10 Insilicotech Co., Ltd Cristal polymère de coordination comportant des structures métalliques-organiques poreuses et procédé de préparation de celui-ci
JP2011529789A (ja) * 2008-08-05 2011-12-15 ポリマーズ シーアールシー リミテッド 官能化薄膜ポリアミド膜
WO2015012373A1 (fr) * 2013-07-26 2015-01-29 国立大学法人京都大学 Complexe pcp
JP2015136697A (ja) * 2014-01-20 2015-07-30 中原大學 不純物イオンを液晶材料から除去する方法
WO2015170506A1 (fr) * 2014-05-08 2015-11-12 国立大学法人北海道大学 Cadre métallo-organique/composite de polymère répondeur à un stimulus capable de contrôler la libération d'invité

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH063869A (ja) * 1992-06-23 1994-01-14 Fuji Photo Film Co Ltd 静電写真用液体現像剤
WO2007054581A2 (fr) * 2005-11-14 2007-05-18 Basf Se Materiau structurel organometallique poreux contenant un autre polymere
WO2007102501A1 (fr) * 2006-03-09 2007-09-13 The University Of Tokyo Complexes de metaux de transition spheriques polymerisables, complexes de metaux de transition spheriques et procedes de production des deux types de complexes
WO2008082087A1 (fr) * 2007-01-03 2008-07-10 Insilicotech Co., Ltd Cristal polymère de coordination comportant des structures métalliques-organiques poreuses et procédé de préparation de celui-ci
JP2011529789A (ja) * 2008-08-05 2011-12-15 ポリマーズ シーアールシー リミテッド 官能化薄膜ポリアミド膜
WO2015012373A1 (fr) * 2013-07-26 2015-01-29 国立大学法人京都大学 Complexe pcp
JP2015136697A (ja) * 2014-01-20 2015-07-30 中原大學 不純物イオンを液晶材料から除去する方法
WO2015170506A1 (fr) * 2014-05-08 2015-11-12 国立大学法人北海道大学 Cadre métallo-organique/composite de polymère répondeur à un stimulus capable de contrôler la libération d'invité

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HOSONO NOBUHIKO ET AL.: "Polymer Grafted Metal- Organic Polyhedra", DAI 95 ANNUAL MEETING OF THE CHEMICAL SOCIETY OF JAPAN IN SPRING KOEN YOKOSHU III, pages 777, ISSN: 0285-7626 *
SHU XIAOWEN ET AL.: "Determination of trace uranyl ion by thermoresponsive porphyrin- terminated polymeric sensor", TALANTA, vol. 131, pages 198 - 204, XP029050236, ISSN: 0039-9140, [retrieved on 20150000] *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017104724A1 (fr) * 2015-12-14 2017-06-22 国立大学法人京都大学 Polymère en étoile
CN110975940A (zh) * 2019-12-12 2020-04-10 万华化学集团股份有限公司 一种复合金属光催化体系及其制备方法和应用
CN110975940B (zh) * 2019-12-12 2022-09-20 万华化学集团股份有限公司 一种复合金属光催化体系及其制备方法和应用
CN111939771A (zh) * 2020-07-01 2020-11-17 华南理工大学 一种具有取向结构的聚苯乙烯-金属有机多面体及其制法和用途
CN111939771B (zh) * 2020-07-01 2022-03-25 华南理工大学 一种具有取向结构的聚苯乙烯-金属有机多面体及其制法和用途
CN114213575A (zh) * 2021-12-15 2022-03-22 华南理工大学 一种金属-有机配位聚合物及其制备方法和应用
CN114213575B (zh) * 2021-12-15 2022-12-16 华南理工大学 一种金属-有机配位聚合物及其制备方法和应用

Also Published As

Publication number Publication date
JPWO2016143876A1 (ja) 2017-12-28

Similar Documents

Publication Publication Date Title
Lee et al. Toward ultimate control of radical polymerization: functionalized metal–organic frameworks as a robust environment for metal-catalyzed polymerizations
WO2016143876A1 (fr) Composé de type ligand, et polymère de coordination à un seul ou plusieurs trous
Hosono et al. Metal–organic polyhedral core as a versatile scaffold for divergent and convergent star polymer synthesis
WO2018159791A1 (fr) Monomère polymérisable contenant un groupe hôte, matière polymère, son procédé de production, et composé de clathrate et son procédé de production
Robinson et al. Synthesis of controlled-structure sulfate-based copolymers via atom transfer radical polymerisation and their use as crystal habit modifiers for BaSO 4
US8247498B2 (en) Star polymer and method for producing the same
Feng et al. Preparation and properties of optically active poly (N-methacryloyl L-leucine methyl ester)
JP2017515931A (ja) 光によるアクリレートの制御ラジカル重合の調節
Jiang et al. The first amphiphilic graft copolymer bearing a hydrophilic poly (2-hydroxylethyl acrylate) backbone synthesized by successive RAFT and ATRP
EP3271155A1 (fr) Procédé de fabrication additive par polymérisation radicalaire photorégulée
Zhao et al. Synthesis of Poly (methyl acrylate) Grafted onto Silica Particles by Z‐supported RAFT Polymerization
Jin et al. Dynamic polymer brushes on the surface of silica particles
JP5798396B2 (ja) ブロック共重合体、その製造方法、粘着組成物及び粘着シート
Qian et al. A new ferrocene/disulfide-containing methacrylate monomer: synthesis, ATRP and nanocomposite
JP7113509B2 (ja) 高分子金属錯体の製造方法
Ruehl et al. Nitroxide-mediated polymerization to form symmetrical ABA triblock copolymers from a bidirectional alkoxyamine initiator
JP2011522087A (ja) マトリックス材料中におけるナノ粒子の分散のための高効率な分散剤
JP5101816B2 (ja) 多分岐高分子
He et al. Double‐Hydrophilic Polymer Brushes: Synthesis and Application for Crystallization Modification of Calcium Carbonate
CN100418992C (zh) 一种主、侧链长度均可控的亲水-疏水性接枝聚合物的制备方法
Fleet et al. Synthesis of novel glycopolymer brushes via a combination of RAFT-mediated polymerisation and ATRP
WO2009113148A1 (fr) Procédé de fabrication de polymères avec un catalyseur à base d'un complexe de fer
Yang et al. Preparation of core–shell attapulgite particles by redox-initiated surface reversible addition–fragmentation chain transfer polymerization via a “graft from” approach
Saikia et al. Mn2+ anchored CdS polymer nanocomposites: An efficient alternative for Mn2+ doped CdS nanoparticles
WO2017104724A1 (fr) Polymère en étoile

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16761842

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017505410

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16761842

Country of ref document: EP

Kind code of ref document: A1