WO2017180062A1 - Polymère poreux et ses procédés de production - Google Patents

Polymère poreux et ses procédés de production Download PDF

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WO2017180062A1
WO2017180062A1 PCT/SG2017/050207 SG2017050207W WO2017180062A1 WO 2017180062 A1 WO2017180062 A1 WO 2017180062A1 SG 2017050207 W SG2017050207 W SG 2017050207W WO 2017180062 A1 WO2017180062 A1 WO 2017180062A1
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atoms
compound
group
ring
attachment
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WO2017180062A8 (fr
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Kian Ping Loh
Wei Liu
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National University of Singapore
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National University of Singapore
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • 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
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3222—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more oxygen atoms as the only heteroatom, e.g. furan
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/514—Electron transport
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates broadly to a porous polymer, its precursor compound and related methods thereof.
  • Porous materials including porous solids such as porous zeolites, metal organic frameworks (MGFs), covalent organic frameworks (COFs), and porous polymers, for example, conjugated microporous polymers (CMPs), porous aromatic frameworks (PAFs) and porous organic polymers (POPs) have attracted great research interest in the past two decades due to their broad applications in science and technology, particu!aly in both the chemical and electronic fields.
  • CMPs conjugated microporous polymers
  • PAFs porous aromatic frameworks
  • POPs porous organic polymers
  • porous materials have also shown potential for use as proton conductors in light harvesting applications, energy transduction applications, energy storage applications, and in sensor applications such as molecular sensing.
  • porous solids are generally synthesized as insoluble fine powder, and the isolated form of porous solids is unsuitable for practical applications, in order for these porous solids to find greater use at an industrial scale, besides optimising material properties such as pore structure and surface area, it is also imperative for properties such as thermal stability, chemical stability, conductivity, and more importantly, the processability of the porous solids to be improved, so that advantages of porous solids can be better maximised in industrial applications.
  • porous materials that are organic porous polymers made from covalently bonded organic polygons
  • various cross linking methods have been studied to solvothermally synthesize organic porous polymers such as boronate, boroxine, hydrazone, and imine.
  • current soivothermal synthesis methods generally require the use of catalysts and rigorous reaction conditions, which is undesirable.
  • A is a 6-membered aromatic hydrocarbon ring, where up to three C atoms in the aromatic ring are optionally substituted with N atoms;
  • R is a monocyclic or polycyclic hydrocarbon ring system having 5 to 42 ring atoms, where up to two C atoms in each cyclic ring are optionally substituted with heteroatoms independently selected from the group consisting of Q, N, S and NH; — represents a single point of attachment;
  • n is at least 2.
  • the compound is a porous polymer comprising pore sizes of no more than about 0.8 nm.
  • the compound has a sheet-like structure with intrasheet conjugation.
  • the compound is represented by general formula (IA):
  • a 1 is a C or atom
  • R 1 is a H atom, or is connected to another adjacent R 1 to form a 6 ⁇ membered cyclic ring; wherein the cyclic ring has at least one C atom that is optionally substituted with heteroatoms independently selected from the group consisting of O, S, N and NH; Y is a heteroatom selected from the group consisting of O, S and NH;
  • n is at least 2
  • two adjacent R 1 atoms of the compound represented by general formula (IA) connect to form a cyclohexane or 1 ,4-dioxane.
  • the compound is represented by general fcrmul
  • R 2 ss a C or N atom
  • R 3 is a monocyclic or polycydic aromatic hydrocarbon ring system having 6 to 18 ring atoms, where up to two C atoms in each aromatic ring are optionally substituted with heteroaioms independently selected from the group consisting of O, S and NH; — represents a single point of attachment;
  • n is at least 2.
  • R 3 of the compound represented by general formula (HA) is selected from the group consisting of benzene, phenanthrene, benzod furan, benzodithiophene and benzodipyrrole.
  • the compound is represented by general formula
  • a 2 is a C or N atom
  • R 4 is optionally present as a 6-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 5 is optionally present as a 8-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 6 is a 8-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 7 is a 5 ⁇ membered or 8-membered aromatic ring, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH;
  • n is at least 2
  • R 4 ⁇ R 5 -R 6 of the compound represented by general formula (Hi A) is a fused aromatic hydrocarbon ring system selected from the group consisting of benzene, quinoxa!ine and phenazine.
  • R 7 of the compound represented by general formula ( ⁇ ) is selected from the group consisting of benzene, pyridine, furan, thiophene and pyrrole.
  • the compound s selected from the following:
  • lerein Y is a heteroatom selected from the group consisting of 0, S and NH; and n at least 2.
  • A is a 6 ⁇ membered aromatic hydrocarbon ring, where up to three C atoms in the aromatic ring are optionally substituted with N atoms;
  • R is a monocyclic or polycyclic hydrocarbon ring system having 5 to 42 ring atoms, where up to two C atoms in each cyclic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH; each X is a halogen independently selected from the group consisting of F, CI. Br and I;
  • the precursor compound is represented by genera formula (IVA):
  • a 1 is a C or N at
  • R is a H atom, or is connected to another adjacent R 1 to form a 8-membered cyclic ring; wherein the cyclic ring has at least one C atom that is optionally substituted with heteroatoms independently selected from the group consisting of O, S, N and NH; Y is a heteroatom selected from the group consisting of O, S and NH; and
  • each X is a halogen independently selected from the group consisting of F, CI, Br and I. !n one embodiment, two adjacent R 1 atoms of the precursor compound represented by general formula (IVA) connect to form a cyciohexane or dioxane.
  • the precursor compound is represented by genera! formula (VA):
  • R 2 is a C or N atom
  • R 3 is a monocyclic or polycyclic aromatic hydrocarbon ring system having 8 to 18 ring atoms, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independentiy selected from the group consisting of O, S and NH; each X is a halogen independently selected from the group consisting of F, CI, Br and I;
  • — represents one or more optional points of attachment.
  • R 3 of the precursor compound represented by general formula (VA) is selected from the group consisting of benzene, phenanthrene, benzodifuran, benzodithiophene and benzodipyrro!e.
  • the precursor compound is represented by genera formula (VIA):
  • a 2 is a C or N atom
  • R 4 is optionally present as a 6 ⁇ membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 5 is optionally present as a 8-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 6 is a 6 ⁇ membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 7 is a 5-membered or 6-membered aromatic ring, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH;
  • each X is a halogen independently selected from the group consisting of F, CI, Br and I;
  • fused R 4 ⁇ R 5 -R 6 rings of the precursor compound represented by general formula (VIA) are selected from the group consisting of benzene, qusnoxalsne and phenazine.
  • R 7 of the precursor compound represented by general formula (VIA) is selected from the group consisting of benzene, pyridine, furan, thiophene and pyrrole.
  • the precursor compound is selected from the following:
  • X is a halogen selected from the group consisting of F, Ci, Br and I: and Y is a heteroatom selected from the group consisting of O, S and NHL
  • a method of producing the compound disclosed herein comprising polymerizing the precursor compound disclosed herein to obtain the compound disclosed herein.
  • the polymerization comprises heating the precursor compound at a temperature above its dehalogenation temperature in the presence of a noble gas.
  • the step of polymerization is performed in the absence of at least a solvent or a catalyst.
  • an energy storage device having at least one electrode, the electrode comprising at least one compound disclosed herein.
  • aromatic refers broadly to hydrocarbons having a ring-shaped or cyclic structure with delocalised electrons between carbon atoms.
  • the term encompasses but is not limited to monovalent (“aryi”), divalent (“arylene”) monocyclic, polycyclic conjugated or fused aromatic groups having 5 to 42 atoms. Examples of such groups include but are not limited to benzene, naphthalene, indene, anthracene, phenanthrene, fluorene and the like.
  • heteroary as used herein when referring to hydrocarbons, refers broadly to aromatic hydrocarbons that have one or more carbon atoms replaced by a heteroatom.
  • aryi monovalent
  • arylene divailing
  • monocyclic polycyclic conjugated or fused aromatic groups having 5 to 42 atoms, where 1 to 8 atoms in each aromatic ring are heteroatoms selected from oxygen (O), nitrogen (N) or (NH) and sulfur (S).
  • Examples of such groups include but are not limited to furan, thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazote, benzofuran, benzothiophene, benzopyrrole, benzodifuran, benzodithiophene, benzodipyrrole, pyridine, diazine such as pyridazine (1 ,2-diazine), pyrimidine (1 ,3- diazine), pyrazine (1 ,4-diazine), triazine such as 1 ,2,3-triazine, 1 ,2,4-triazine and 1 ,3,5-tnazme, phenanfhroline, quinoxaline, phenazine, acridine and the like.
  • cyclic as used herein broadly refers to a structure where one or more series of atoms are connected to form a ring.
  • the term encompasses both “monocyclic” and “polycyclic” structures.
  • the term also encompasses both saturated and unsaturated fused rings.
  • the cyclic structure includes but is not limited to one, two, three, four, five, six or seven saturated or unsaturated fused rings having from 5 to 42 atoms, where 1 to 6 atoms in each ring are optionally heteroatoms selected from oxygen (O), nitrogen (N) or (NH) and sulfur (S).
  • groups having a cyclic structure include, but are not limited to cyc!opentane, ietrahydrofuran, 1 ,3-dioxolane, tefrahydrotbsophene, 1 ,2- oxathiolane, 1 ,3-oxathiolane, pyrrolidine, pyrazolidine, imidazolidine, furan, thiophene, 2H-pyrroie, 1 H-pyrroie, 3-pyrraline, 2-pyrroline, 2-pyrazoline, 2- imidazoline, pyrazole, imidazole, oxazole, thiazole, 1 ,2,4-triazole, 1 ,2,3-triazole, oxadiazote, fhiadiazole, tetrazole, cyclohexane, tetrahydropyran, 1 ,4 ⁇ dioxane, thiane, 1 ,
  • porous as used herein broadly refers to a material with a plurality of pores (holes or openings),
  • a “porous” material may be nanoporous, microporous, mesoporous or macroporous.
  • nano-pores may include pore sizes that are no more than about 1000 nm, no more than about 900 nm, no more than about 800 nm, no more than about 700 nm, no more than about 600 nm. no more than about 500 nm, no more than about 400 nm, no more than about 300 nm, no more than about 200 nm, no more than about 100 nm, no more than about 50 nm, no more than about 10 nm, no more than about 5 nm, or no more than about 1 nm.
  • the terms "monomer” or “precursor compound” as used herein refer to a chemical entity that may be covIERly linked to one or more of such entities to form a polymer.
  • polymer refers to a chemical compound comprising repeating structural units and is created through a process of polymerization. The units composing the polymer are typically derived from monomers, i.e. their precursor compounds.
  • dehalogenation refers to a process whereby halogen atom(s) is/are removed from a compound in a chemical reaction.
  • terms such as “about”, “approximately” and the like whenever used typically means a reasonable variation, for example a variation of +/ ⁇ 5% of the disclosed value, or a variance of 4% of the disclosed value, or a variance of 3% of the disctosed value, a variance of 2% of the disclosed value or a variance of 1 % of the disclosed value.
  • the disclosure may have disclosed a method and/or process as a particular sequence of steps. However, unless otherwise required, it will be appreciated the method or process should not be limited to the particular sequence of steps disclosed. Other sequences of steps may be possible. The particular order of the steps disclosed herein should not be construed as undue limitations. Unless otherwise required, a method and/or process disclosed herein should not be limited to the steps being carried out in the order written. The sequence of steps may be varied and still remain within the scope of the disclosure.
  • n is at least 2
  • A may be a benzene, pyridine or diazine selected from the group consisting of pyridazine (1 ,2-diazsne), pyrimsdine (1 ,3-diazine), pyrazine (1 ,4-diazine); or triazine selected from the group consisting of 1 ,2,3-triazine, 1 ,2,4-triazine and 1 ,3,5-friazine.
  • A is benzene, pyrazine or 1 ,3,5-triazine
  • R may be one ring, or two, three, four, five, six or seven fused rings system that is made up of 5-membered or 6 ⁇ membered saturated or unsaturated rings optionally containing one or two heteroatoms selected from O, N, S or NH.
  • R may be one ring, or two, three, four, five, six or seven rings selected from cyciopentane, tetrah drofuran, 1 ,3-dioxolane, tetrahydrothlophene, oxathio!ane pyrrolidine, pyrazolidine, imidazolidine, furan, thiophene, pyrrole, 3-pyrroiine, 2 ⁇ pyrroline, 2- pyrazo ine, 2-imidazolsne, pyrazo!e, imidazole, oxazole, thiazole, cyclohexane, tetrahydropyran, 1 ,4-dioxane, thiane, 1 ,3-dithiane, 1 ,4-dithiane, piperidine, piperazine, morpholine, thiomorpholine, benzene, 2H-pyran, 4H-pyran, 1 ,4-
  • R is a monocyclic or polycyclic hydrocarbon ring system having 5 to 30 ring atoms, where up to two C atoms in each cyclic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH. In some embodiments, R is a saturated or unsaturated monocyclic ring.
  • R is a saturated or unsaturated fused polycyclic, for example, bicydic, tricyclic, tetracyclic or pentacyclic hydrocarbon ring system.
  • R may be a 5-membered or 6-membered cycloalkane, heterocycloalkane, aromatic or heteroaromatic group optionally containing one or two heteroatoms selected from O, N, S or NH.
  • R may be a furan, thiophene or pyrrole.
  • R may be a two.
  • R may be a two, three, four or five tings selected from cyclohexane, 1 ,4-dioxane, benzene, furan, thiophene, pyrrole, pyridine and pyrazine, fused together in a polycyclsc hydrocarbon ring system.
  • R when R is bicyciic, R may be a benzopyrazine, furarvfused cyclohexane, thiophene-fused cyclohexane, pyrrole-fused cyclohexane, furan-fused 1 ,4-dioxane, thiophene-fused 1 ,4-dioxane, or pyrrole-fused 1 ,4-dioxane.
  • R when R is tricyclic, R may be phenanthrene, phenanthroline, benzodifuran, benzodithiophene or be zodi pyrrole.
  • R When R is tetracyclic, R may be pyrazine-fused rings such as pyrazine-fused phenanthrene, pyrazine-fused phenanthroline, pyrazine-fused benzodifuran, pyrazine-fused benzodithiophene or pyrazine-fused benzodipyrrole.
  • pyrazine-fused rings such as pyrazine-fused phenanthrene, pyrazine-fused phenanthroline, pyrazine-fused benzodifuran, pyrazine-fused benzodithiophene or pyrazine-fused benzodipyrrole.
  • R When R is pentacyclic, R may be benzopyrazine-fused rings such as benzopyrazine-fused phenanthrene, benzopyrazine-fused phenanthroline, benzopyrazine-fused benzodifuran, benzopyrazine-fused benzodithiophene or benzopyrazine-fused benzodipyrrole.
  • benzopyrazine-fused rings such as benzopyrazine-fused phenanthrene, benzopyrazine-fused phenanthroline, benzopyrazine-fused benzodifuran, benzopyrazine-fused benzodithiophene or benzopyrazine-fused benzodipyrrole.
  • each repeating unit in any one of general formulae (I), (II) or (III) contains a single point of attachment from ring R to another repeating unit of the same formula.
  • the compound having general formula (I) may have 3 points of attachment arising from each repeating unit of the compound.
  • the compound having generai formula (I!) may have 3 points of attachment arising from each repeating unit of the compound.
  • the compound having general formula (III) may have 2 points of attachment arising from each repeating unit of the compound, in some embodiments, each repeating unit in any one of general formulae (II) or (II! contains two points of attachment from ring R to another repeating unit of the same formula.
  • the compound having general formula (II) may have a total of 8 points of attachment arising from each repeating unit of the compound.
  • the compound having general formula (III) may have a total of 4 points of attachment arising from each repeating unit of the compound.
  • the compound having any one of the general formulae (I), (II) or (HI) as disclosed herein contains at least 2 repeating units.
  • n may have a vaiue of at least 2, at least 3, at least 4, at least 5, at least 6. at least 7, at least 8, at least 9 or at least 10.
  • the compound is a porous polymer.
  • the compound may comprise at least 3 monomers that are joined together via a cross-linking reaction to form a polymer.
  • the cross-linking reaction between the monomers may be in the form of a C ⁇ C coupling reaction.
  • the compound has at least 3 repeating units and at least one pore is formed within the compound.
  • the compound is a conjugated aromatic polymer.
  • the compound comprises an extended ⁇ cloud deiocalizatson in the ⁇ -conjugated organic skeleton of the polymers.
  • the compound is crystalline. In other embodiments, the compound is amorphous. I n some embodiments, the compound oomprises in-built porosity network of permanent nanoscale pores.
  • the compound has nano-pores comprising pore size of no more than about 0.8 nm.
  • the nano-pores may have pore size of no more than about 1 .5 nm, no more than about 1 .45 nm, no more than about 1 .40 nm, no more than about 1 .35 nm, no more than about 1 .30 nm, no more than about 1 .25 nm, no more than about 1 ,20 nm, no more than about 1 .15 nm, no more than about 1 .10 nm, no more than about 1 .05 nm, no more than about 1 .00 nm, no more than about 0.95 nm, no more than about 0.90 nm, no more than about 0.85 nm, no more than about 0.80 nm, no more than about 0,78 nm, no more than about 0.76 nm, no more than about 0.74 nm, no more than about 0.72 nm, no more than about 0,
  • the porous polymer has nano-pores having pore sizes of from about 0,51 nm to about 0.74 nm.
  • the compound has a sheet-like structure.
  • the compound may comprise a layered stacking structure such that the layers of sheets can be mechanically exfoliated into u Strath in sheets. Mechanical exfoliation may be performed by suspending the compound in an organic solvent.
  • the organic solvent may be selected from N-methy!-2-pyrro!idone, dimethyl sulfoxide, quinolone, and combinations thereof.
  • the compound comprises intrasheet conjugation.
  • the layers of sheets may be held together by stable intrasheet TMT interaction in the conjugated aromatic polymer network,
  • embodiments of the compound disclosed herein have strong and stable linkages, i.e. strong C ⁇ C bonds in the polymer, thus making the polymeric compounds chemically stable and highly desirable for many industrial applications.
  • the polymer comprises layers of sheets that are stacked in an orderly manner, which gives rise to a structure having highly-ordered porosity with substantially uniform pore size of no more than about 0,8 nm.
  • the compound represented by general formula (1) is further represented by general formula (IA):
  • a 1 is a C or N atom
  • R 1 is a H atom, or is connected to another adjacent R 1 to form a 6-membered cyclic ring; wherein the cyciic ring has at least one C atom that is optionally substituted with heteroatoms independently selected from the group consisting of O, S, N and NH;
  • Y is a heteroatom selected from the group consisting of O, S and NH;
  • n is at least 2.
  • the 8-membered ring containing three A 1 atoms may be benzene or 1 ,3,5- triazine.
  • R is a H atom
  • the two adjacent R 1 atoms connect to form a saturated 6-membered ring optionally containing one or two heteroatoms selected from O, S, N and NH.
  • the two adjacent R 1 atoms may connect to form a cyclohexane or a 1 ,4-dtoxane.
  • the compound having genera! formula (!A) contains 3 points of attachment arising from each repeating unit of the compound, in particular at the position ortho to the Y atoms,
  • the compound having general formula (lA) contains at least 2 repeating units, at least 3 repeating units, at least 4 repeating units, at least 5 repeating units, at least 6 repeating units, at least 7 repeating units, at least 8 repeating units, at least 9 repeating units or at least 10 repeating units.
  • the compound having general formula (IA) has at least 3 repeating units and at least one pore is formed within the compound.
  • the compound represented by genera! formula (II) is further represented by general formula (I I A):
  • R 2 is a C or N atom
  • R 3 is a monocyclic or polycyciic aromatic hydrocarbon ring system having 8 to 18 ring atoms, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independently selected from the group consisting of O s S and NH; — represents a single point of attachment;
  • n is at least 2.
  • R 2 is a N atom.
  • the 8-membered ring containing two R 2 atoms may be pyrazine.
  • R 3 is an unsaturated monocyclic ring.
  • R 3 is an unsaturated fused polycyciic, for example, tricyclic hydrocarbon ring system.
  • R 3 may be a 8 ⁇ membered aromatic or heteroaromatic group optionally containing one or two heteroatoms selected from O, N, S or NH,
  • R 3 may be benzene.
  • R 3 When R 3 is polycyclic, R 3 may be three fused rings that is made up of 5- membered or 6 ⁇ membered aromatic or heteroaromatic groups optionally containing one or two heteroatoms selected from G, N, S or NH,
  • R 3 may be phenanthrene, benzodifuran, benzodithiophene, benzodipyrrole or phenanthroiine.
  • R 3 is a monocyclic or polycyclic hydrocarbon ring system having 6 to 18 ring atoms, where up to one C atom in each cyclic ring is optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH.
  • R 3 is selected from the group consisting of benzene, phenanthrene, benzodifuran, benzodithiophene and benzodipyrrote.
  • each repeating unit of general formula (HA) contains a single point of attachment from ring R 3 to another repeating unit of the same formula.
  • the compound having general formula (HA) may have 3 points of attachment arising from each repeating unit of the compound.
  • each repeating unit of general formula (HA) contains two points of attachment from ring R 3 to another repeating unit of the same formula.
  • the compound having general formula (ISA) may have a total of 8 points of attachment arising from each repeating unit of the compound.
  • the compound having general formula (IIA) contains at least 2 repeating units.
  • n may have a value of at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9 or at least 10.
  • the compound having general formula (HA) has at least 3 repeating units and at least one pore is formed within the compound.
  • the compound represented by general formula ( ⁇ ) may be further represented by formula ( ⁇ -1 ):
  • R 2 is a C or N atom
  • n is at least 2.
  • R 2 is a N atom.
  • each repeating unit of general formula (IIA-1 ) contains a single point of attachment to another repeating unit of the same formula.
  • the compound having general formula (iiA ⁇ 1 ) may have 3 points of attachment arising from each repeating unit of the compound,
  • each repeating unit of general formula (!SA-1 ) contains two points of attachment to another repeating unit of the same formula.
  • the compound having general formula (NA-1 ) may have a total of 6 points of attachment arising from each repeating unit of the compound.
  • the compound represented by general formula (HA) may be further represented by formula (IiA-2):
  • R 2 is a C or N atom
  • R 8 is a 5-membered or 8 ⁇ membered aromatic hydrocarbon ring; where up to one C atom in each aromatic ring is optionally substituted with heteroatoms independently selected from the group consisting of O, S and NH;
  • n is at least 2
  • R 2 is a N atom.
  • R 8 is an unsaturated 5-membered or 6-membered aromatic or heteroaromatic ring optionally containing one heteroatom selected from O, S and NH.
  • R 8 may be benzene, furan, thiophene or pyrrole.
  • each repeating unit of general formula (!IA-2) contains two points of attachment to another repeating unit of the same formula.
  • the compound having general formula (IIA-2) may have a total of 8 points of attachment arising from each repeating unit of the compound.
  • a 2 is a C or N atom
  • R 4 is optionally as a 6-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 5 is optionally present as a 6-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 6 is a 6-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R ? is a 5-membered or 6-membered aromatic ring, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH;
  • ⁇ — represents a single point of attachment
  • n is at least 2
  • R 4 , R Li and R 6 are optionally substituted with N atoms at the 1 and 4 positions of the aromatic ring.
  • R 6 is benzene
  • both R 4 and R 5 are either absent or present together,
  • R 4 ⁇ R S -R 6 are present as three fused aromatic ring system that is made up of alternating sequence of benzene and pyrazine molecules. For example, if R 4 is benzene, R 5 s pyrazine and R 6 is benzene.
  • R 4 ⁇ R 5 ⁇ R 6 may be present as one, two or three fused aromatic hydrocarbon ring system selected from the group consisting of benzene, quinoxaline or phenazine.
  • R 7 is a 5-membered or 8-membered aromatic ring, where up to one C atom in each aromatic ring is optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH,
  • R ?" may be benzene, pyridine, furan, thiophene or pyrrole.
  • each repeating unit of general formula (SUA) contains four points of attachment to another repeating unit of the same formula.
  • the compound having general formula (IMA) may have a total of 4 points of attachment arising from each repeating unit of the compound.
  • the compound having general formula (H!A) contains at least 2 repeating units,
  • n may have a value of at least 2, at least 3, at least 4, at least 5 S at least 8, at least 7, at least 8. at least 9 or at least 10.
  • the compound having general formula (HIA) has at least 4 repeating units and at least one pore is formed within the compound.
  • the compound is selected from one of the follow
  • Y is a heteroatom selected from the group consisting of O, S and NH; and is at least 2.
  • A is a 8-membered aromatic hydrocarbon ring, where up to three C atoms in the aromatic ring are optionally substituted with N atoms;
  • R is a monocyclic or poiycyciic hydrocarbon ring system having 5 to 42 ring atoms, where up to two C atoms in each cyclic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, N, S and NH;
  • each X is a halogen independently selected from the group consisting of F, CI, Br and !;
  • — represents one or more optional points of attachment.
  • the precursor compound contains a single point of attachment from one ring R to X.
  • the compound having general formulae (IV) or (V) may be trihalogenated, i.e. attached to three X at three different points of attachment of the precursor compound.
  • the compound having general formula (VI) may be dihalogenated, i.e. attached to two X at two different points of attachment of the precursor compound.
  • the precursor compound contains two points of attachment from one ring R to X.
  • the compound having general formula (V) may be hexahalogenated, i.e. attached to six X at six different points of attachment of the precursor compound.
  • the compound having general formula (VI) may be tefrahalogenated, Le, attached to four X at four different points of attachment of the precursor compound.
  • the precursor compound represented by general formula (IV) is further represented by general formula (IVA): wherein
  • a 1 is a C or N atom
  • R 1 is a H atom, or is connected to another adjacent R 1 to form a 6-membered cyclic ring; wherein the cyclic ring has at teas! one C atom that is optionally substituted with heteroatoms independently selected from the group consisting of O, S, N and NH; Y is a heteroatom selected from the group consisting of O, S and NH; and
  • each X is a halogen independently selected from the group consisting of F, CI, Br and I.
  • a 1 and R 1 are similar to those described above.
  • the precursor compound having general formula (IVA) contains 3 points of attachment to X, in particular at the position ortho to the Y atoms.
  • the precursor compound represented by general formula (V) is further represented by general formula (VA):
  • R 2 is a C or N atom
  • R 3 is a monocyclic or polycy sc aromatic hydrocarbon ring system having 6 to 18 ring atoms, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independently selected from the group consisting of O, S and NH; each X is a halogen independently selected from the group consisting of F, CL Br and I;
  • — represents one or more optional points of attachment.
  • R 2 and R 3 are similar to those described above.
  • the precursor compound contains a single point of attachment from one ring R 3 to X.
  • the compound having general formula (VA) may be trihalogenated, i.e. attached to three X at three different points of attachment of the precursor compound
  • the precursor compound contains two points of attachment from one ring R 3 to X.
  • the compound having general formula (VA) may be hexahalogenated, i.e. attached to six X at six different points of attachment of the precursor compound.
  • the precursor compound represented by general formula (VA) may be further represented by formula (VA-1 ):
  • R 2 is a C or N atom
  • each X is a halogen independently selected from the group consisting of F, CI, Br represents a single point of attachment;
  • R 2 is a atom
  • the precursor compound contains a single point of attachment from each terminal benzene ring to X,
  • the compound having general formula (VA-1 ) may be trihafogenated, i.e. attached to three X at three different points of attachment of the precursor compound.
  • the precursor compound contains two points of attachment from each terminal benzene ring to X.
  • the compound having general formuia (VA-1 ) may he hexahalogenated, i.e. attached to six X at six different points of attachment of the precursor compound.
  • the compound represented by general formula (VA) may be further represented by formula (VA-2):
  • R 2 is a C or N atom
  • R 8 is a 5-membered or 8-rnembered aromatic hydrocarbon ring; where up to one C atom in each aromatic ring is optionally substituted with heteroatoms independently selected from the group consisting of O, S and NH;
  • each X is a halogen independently selected from the group consisting of F, CI, Br and I;
  • R 2 and R 8 are similar to those described above.
  • the precursor compound contains a single point of attachment from one ring R 8 to X.
  • the compound having general formula (VA-2) may be hexahalogenated, i.e. attached to six X at six different points of attachment of the precursor compound.
  • the precursor represented lenerai formula (VIA) may be further represented by formu
  • a 2 is a C or N atom
  • R 4 is optionally present as a 8-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 5 is optionally present as a 8-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 6 is a 8-membered aromatic hydrocarbon ring, where up to two C atoms in the aromatic ring are optionally substituted with N atoms;
  • R 7 is a 5-membered or 6-membered aromatic ring, where up to two C atoms in each aromatic ring are optionally substituted with heteroatoms independently selected from the group consisting of O f N, S and NH;
  • each X is a halogen independently selected from the group consisting of F, CI, Br and I;
  • R 4 when only R 4 is absent, R 5 is fused together with the central 6- membered aromatic ring containing A 2 ; when only R 5 is absent, R 4 and R 6 are fused together with the central 8-membered aromatic ring containing A 2 , and when both R 4 and R 5 are absent, R 6 is fused together with the central 6-membered aromatic ring containing A 2 .
  • a 2 , R 4 , R 5 , R 6 and R 7 are similar to those described above.
  • the precursor compound contains a single point of attachment from one ring R 7 to X.
  • the compound having general formula (VIA) may be tetrahafogenated, i.e. attached to four X at four different points of attachment of the precursor compound.
  • the precursor compound is selected from the following:
  • X is a halogen selected from the group consisting of F, CI, Br and I; and Y is a heteroatom selected from the group consisting of O, S and
  • the step of polymerization comprises heating the precursor compound at a temperature above its dehalogenatson temperature in the presence of noble gas.
  • the polymerization is a thermal-initiated dehalogenation polymerization and the compound obtained from the thermal-initiated dehalogenation polymerization is a thermosetting porous polymer.
  • the compounds obtained from the thermal-initiated dehalogenation polymerization are thermosetting porous plastics
  • the noble gas is argon or nitrogen
  • the step of polymerization is performed in the absence of solvent and/or a catalyst.
  • the method of producing the compound have shown to be an efficient and cost-effective process since quantitative yield is achieved without any solvent and/or catalyst.
  • the step of the polymerization is carried out at a temperature range of from about 30 C C to about 70Q°C, about 50°C to about 680°C, about 70°C to about 660°C, about 90°C to about 840°C, about 11 O to about 620°C, about 130°C to about 600°C, about 150 C C to about S8G°C, about 170°C to about 560°C, about 190 C C to about S4G°C, about 210°C to about 520°C, about 230°C to about SQQ°C, about 250°C to about 48Q°C, about 270°C to about 460°C, about 290°C to about 440°C, about 310 C C to about 420°C, about 330°C to about 400°C, or about 350°C to about 38G°C,
  • the step of the polymerization is carried out at 520° ⁇ .
  • the polymerization may be performed in liquid or solid state.
  • the ha!ogenated precursor molecules are heated at their melting state in order for dehalogenation polymerization to take place.
  • the step of the poiymerization is carried out over a time range of from about 0.1 hour to about 100 hours, from about 0.5 hour to about 90 hours, from about 1 hour to about 80 hours, from about 2 hour to about 70 hours, from about 3 hour to about 65 hours, from about 4 hour to about 80 hours, from about 5 hour to about 55 hours, from about 8 hour to about 50 hours, from about 7 hour to about 45 hours, from about 8 hour to about 40 hours, from about 9 hour to about 30 hours, from about 10 hour to about 20 hours.
  • the step of the polymerization is carried out in 3 hours, in various embodiments, the method further comprises, prior to the step of poiymerizing the precursor compound, the step of reacting a hatogenated aromatic dione with a heteroaromatic compound comprising at ieast 2 amine groups to form the precursor compound.
  • the step of reacting a ha!ogenated aromatic dione with a heteroaromatic compound comprising at !least 2 amine groups to form the precursor compound comprises adding an acid.
  • the acid may be a weak acid and/or an organic acid, in some embodiments, the acid is acetic acid, lactic acid, tartaric acid, citric acid, maleic acid or ascorbic acid.
  • the step of reacting a haiogenated aromatic dione with a heteroaromatic compound comprising at Ieast 2 amine groups to form the precursor compound further comprises adding a base.
  • the base may be a weak base and/or an organic base.
  • the base is an alkylamine.
  • the base may be triethylamine, N,N ⁇ diisopropylethylamine, trimethylamine, trkvpropylamine, triisopropylamine or the like.
  • the acid is acetic acid and the base is triethyiamine.
  • the haiogenated aromatic dione with the heteroaromatic compound comprising at least 2 amine groups react in a condensation reaction. Accordingly, in various embodiments, there is provided a method of producing the precursor compound, the method comprises reacting a haiogenated aromatic dione with a heteroaromatic compound comprising at least 2 amine groups.
  • the starting reactants used for the production of precursor molecule may be modified accordingly.
  • a method of making two-dimensional or three-dimensional polymers derived from haiogenated precursor molecules via solid-state thermal-initiated dehaiogenation polymerization without solvent or catalyst comprising: heating the haiogenated precursor molecules at temperature over their dehaiogenation temperature to form two-dimensional or three-dimensional polymers by cross-linking reaction, in some embodiments, the methods disclosed herein comprises isolating the exfoliated sheets of the two-dimensional polymers.
  • the exfoliated sheets of two- dimensional polymers may have a thickness of less than about 1 ⁇ , less than about 0.9 pm, less than about 0.8 pm, less than about 0.7 pm, less than about 0,8 m, or less than about 0,5 pm,
  • an energy storage device having at least one electrode, the electrode comprising at least one compound of general formulae (S), (II) or (HI) as disclosed herein.
  • the energy storage device is a supercapacitor.
  • the energy storage device is a battery,
  • the battery may be a rechargeable battery,
  • the battery may be a lithium or sodium battery.
  • the sodium battery is a room temperature sodium battery.
  • the electrode comprising at least one compound of general formulae (I), (II) or (III) as disclosed herein may be an anode.
  • the battery does not contain UC0O2, LiMnaC ⁇ , Si and Sn, which the constituent elements are derived from dwindling mineral resources.
  • the electrode materials of the batteries are made from recyclable organic materials.
  • FIG. 1 is a schematic flowchart for illustrating a method of producing a compound of general formulae (I), (I! and (III) in an example embodiment.
  • FIG, 2 is a schematic flowchart for illustrating a method of producing a precursor compound of general formulae (IV), (V) and (VI) in an example embodiment.
  • FIG. 3 is a schematic flowchart for illustrating a polymerization step of producing a compound of general formulae (I), (II) and (III) from a precursor compound of general formulae (IV), (V) and (VI) in an example embodiment.
  • FIGS. 4A-4C are solid state 13 C nuclear magnetic resonance spectroscopy (NMR) spectra of precursor compounds (2-TBTBP, 3-TBTBP and 2-TBQP) and compounds (11), (12) and (13) in accordance with various embodiments disclosed herein.
  • NMR nuclear magnetic resonance spectroscopy
  • FIGS. 5A and 5B are fourier transform infrared spectroscopy (FTSR) spectra of precursor compounds (2-TBQP and 3-TBQP) and compounds (13) and (14) in accordance with various embodiments disclosed herein.
  • FIG. 8 is the electronic absorption spectra of precursor compounds (2-TBQP and 3-TBQP) and compounds (13) and (14) in accordance with various embodiments disclosed herein.
  • FTSR Fourier transform infrared spectroscopy
  • FIGS. 7A-7H are nitrogen (l ) gas sorption isotherm profiles and crystalline structure analysis of compounds (11 ), (12), (13) and (14) in accordance with various embodiments disclosed herein,
  • RGS. 8A-8C are microscopic images of compounds (12), (13) and (14) in accordance with various embodiments disclosed herein.
  • FIGS, 9A and 9B are graphs showing the electrochemical characterization of compound (13) in room temperature sodiym(Na) ⁇ ion batteries and Iithium(Li) ⁇ ion batteries in accordance with various embodiments disclosed herein.
  • FIGS. 1 GA-1 GC are graphs showing the sodium storage performance of an electrode containing compound (13) in the potential range of +0.005 to +2.5 V vs. Na/Na ⁇ in accordance with various embodiments disclosed herein,
  • FIG. 1 1 is a graph showing the cycle performance of compound (13) in Li-ion battery up to 20,000 cycles at 5.0 A g ⁇ 1 in accordance with various embodiments disclosed herein.
  • FIG. 1 is a schematic flowchart 100 for illustrating a method of producing a compound of general formulae (I), (!l) and (HI) in an example embodiment
  • a precursor compound comprising any one of the general formulae (IV), (V) or (V!) is polymerized to obtain a compound comprising any one of the general formulae (I), (II) or (III).
  • the polymerization step comprises heating the precursor compound at a temperature above its dehalogenation temperature in the presence of noble gas.
  • a halogenated aromatic dione is reacted with a heteroaromatic compound comprising at least 2 amine groups to form the precursor compound,
  • FIG. 2 is a schematic flowchart 200 for illustrating a method of producing a precursor compound of genera! formulae (IV), (V) and (VI) in an example embodiment.
  • a halogenated aromatic dione is provided at step 202.
  • a heteroaromatic compound comprising at least 2 amine groups.
  • the halogenated aromatic dione is reacted with the heteroaromatic compound comprising at least 2 amine groups.
  • FIG. 3 is a schematic flowchart 300 for illustrating a polymerization step of producing a compound of genera! formulae (I), (II) and (!!!) from a precursor compound of general formulae (IV), (V) and (VI) in accordance with various embodiments disclosed herein.
  • compounds comprising general formulae (I), (II) and (III) are thermosetting porous polymers and the precursor compound comprising general formulae (IV), (V) and (VI) is halogenated precursor molecule.
  • FIG. 4A shows the solid state 3 C NMR spectra of precursor compound (2- TBTBP) vs. compound (11).
  • FIG. 4B shows the solid state 13 C NMR spectra of precursor compound (3-TBTBP) vs. compound (12)
  • FIG. 4C shows the solid state 13 C NMR spectra of precursor compound (2-TBQP) vs. compound (13).
  • the spectra obtained for the polymerized compounds (11), (12) and (13) are relatively similar to those of the precursor molecules, which is indicative of a similarity in their chemical structures.
  • FIG. 5A shows the FTIR spectra of precursor compound (2-TBQP) vs. compound (13).
  • FIG. 5B shows the FTIR spectra of precursor compound (3-TBQP) vs. compound (14).
  • the vibration bands of C— Br bond at 458 cm “1 for 2- TBQP and 512 cm “1 for 3-TBQP vanished after polymerization, while the characteristic bands of phenazine linkages (at 1338, 1443 and 1508 cnr 1 or 1312, 1338 and 1508 cnr 1 ) remained in the polymerized compounds (13) and (14).
  • FIG, 6 shows the electronic absorption spectra of precursor compounds (2- TBQP and 3-TBQP) and compounds (13) and (14) in accordance with various embodiments disclosed herein.
  • both precursor compounds (2-TBQP and 3-TBQP) display an absorbance in ultraviolet and visible (UV ⁇ vis) regions from 250 to 850 nm
  • compounds (13) and (14) have a much broader absorbance across the ultraviolet and visible (UV-vis) regions that further extends to near-infrared (IR) regions (1350 nm), which is indicative of an extended ⁇ cloud deloca!ization in the TF- conjugated organic skeleton of the polymers.
  • UV ⁇ vis ultraviolet and visible
  • IR near-infrared
  • FIG. 7A, 7C, 7E and 7G show the nitrogen (N2) gas sorption isotherm profiles of compounds (11 ) (12), (13) and (14) respectively in accordance with various embodiments disclosed herein.
  • FIG. 7B, 7D, 7F : 7H show the the crystalline structure analysis of compounds (11 ), (12), (13) and (14) respectively in accordance with various embodiments disclosed herein.
  • the nitrogen adsorption (filled) and desorption (open) isotherm profiles are obtained at 77K.
  • the crystalline structure analysis, i.e. pore size distribution is calculated by non-local density functional theory (NLDFT) modelling based on the N2 adsorption data.
  • NLDFT non-local density functional theory
  • the pore width of compound (11 ) is calculated to be 5.1 A
  • pore width of compound (12) is calculated to be 7.4 ⁇
  • pore width of compound (13) is calculated to be 6.0 ⁇
  • pore width of compound (14) is calculated to be 5.3A.
  • FIGS. 8A-8C are microscopic images of compounds (12), (13) and (14) in accordance with various embodiments disclosed herein.
  • FIG. 8A shows a SEM image of compound (12) taken at 250x magnification.
  • FIG, 8B shows a TEM image of exfoliated compound (13), with the scale bar representing 50 nm.
  • FIG. 8C shows a TEM image of exfoliated compound (14), with the scale bar representing 5 pm.
  • FIGS. 9A and 9B are graphs showing the electrochemical characterization of compound (13) in room temperature Na ⁇ ion batteries and Li-son batteries in accordance with various embodiments disclosed herein.
  • FIG. 9A shows a cyclic vo!tammogram of an electrode containing compound (13) cycling between +0.005 V and +2.5 V at a potential sweep rate of 0.1 mV/s as an anode in room temperature sodium (Na)-ion batteries.
  • FIG. 9B shows a cyclic voltammogram of an electrode containing compound (13) cycling between +0.005 V and +3.0 V at a potential sweep rate of 0.1 mV/s as an anode in room temperature lithium (Li)-ion batteries.
  • FIGS. 10A-10C are graphs showing the sodium storage performance of an electrode containing compound (13) in the potential range of +0.005 to +2.5 V vs. Na/ a 4 in accordance with various embodiments disclosed herein.
  • FIG. 10A shows the charge capacities of the electrode containing compound (13) at 0.1 , 0.5, 1.0, 3.0, 5.0, 10.0 A g "1 .
  • FIG. 10B shows the galvanostatic charge-discharge profiles of compound (13) at different current densities.
  • FIG. 10C shows the cycle performance of compound (13) in Na-ion battery up to 7,770 cycles at 5.0 A g "1 .
  • FIG. 1 1 is a graph showing the cycle performance of compound (13) in Li-son battery up to 20,000 cycles at 5.0 A g 1 in accordance with various embodiments disclosed herein.
  • porous polymers that are capable of addressing several problems of conventional methods used in the art, such as for example, the application of rigorous reaction conditions.
  • the examples describe a method of producing several example precursor compounds and a method of polymerizing the precursor compounds to obtain porous polymers in an effective and cost-efficient process.
  • these porous polymers possess nanopores with pore sizes of as low as 0.5 nm, which increases the processability of the polymers for industrial applications.
  • the polymer is believed to possess highly uniform pore size of -0.5 nm, which is a result of the aligned open channels created by the polymerization process.
  • 2,7,11 ,16-ietrabromotetrabenzophenazine (2-TBTBP) and 3,6,12,15- tetrabromo-tetrabenzophenazine (3-TBTBP) were synthesized according to the method shown in Scheme 1.
  • 3,6 ⁇ Dibromophenanthrene-9,10 ⁇ dione (3,8-DBPD, 0.73 g, 2.0 mmol) and 3,6- Dibromophenanthrene-9,1 Diamine chloride (3,6-DBPDA, 0.88 g, 2,0 mmol) were transferred into a round bottom flask with a magnetic spin bar, and suspended in 6 mL of ethanol and 20 mL of acetic acid to make a suspension in Ar atmosphere, which was heated to 100°C. After the addition of 1.0 ml of triethyiamine, the mixture 3 b was further refluxed at 130°C for 6 hours. Once cooled to room temperature, the mixture was diluted with acetic acid and poured into 200 mL of water.
  • the precipitate was coiiected and exhaustively washed by soxhiet extraction with water, ethanol, chloroform, tetrahydrofuran (THF), V,A/-dimetbylformarnide and ethanol again, and dried at 120°C overnight in vacuum oven to yield 3-TBTBP as yellow powder in quantitative yield.
  • the structure was confirmed with single crystal XRD data analysis. All reagents were obtained from Aldrich.
  • 2,7-Dibromophenanthrene-9,10-dione (2,7-DBPD, 0.76 g, 2.1 mmol) and benzene-1 ,2,4,5 ⁇ tetraamine tetrahydrochioride (0.28 g, 1.0 mmol) were transferred into a round bottom flask with a magnetic spin bar, and suspended in 6 mL of ethanol and 20 mL of acetic acid to make a brown suspension in Ar atmosphere, and 30 heated to 100°C. After the addition of 1.0 mL of triethylamine, the mixture immediately changed to red color, and was further refluxed at 130°C for 6 hours.
  • Porous polymers of the embodiments of the present disclosure are synthesized in quantitative yield by heating the corresponding precursor molecules at 520°C for 3 hours in argon according to the reaction shown in the following schemes. The reaction may also be conducted at 500°C for 10 hours.
  • Characterization studies of embodiments of the porous polymers and their precursor compounds were performed with various methods including elemental analysis, solid state carbon nuclear magnetic resonance ( 13 C-NMR) spectroscopy, fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM), The following characterization methods demonstrate the effectiveness of the polymerization process.
  • elemental analysis, 13 C N R spectroscopy, FTIR and UV ⁇ vis spectroscopy analysis were performed on the precursor compounds and the results are illustrated alongside with the results obtained from the polymerized compounds in FIGS, 4 to 8.
  • Elemental analysis results show that the calculated values (wt%: C, 50.91 ; H, 2,28; N, 6.98; Br, 39,84) match well with the found values (wt%: C, 51.44; H, 2.01 ; N, 7,19; Br, 39.38) for precursor compound, 2-TBQP.
  • Calculated values (wt%: C, 85.34; H, 2,95; N, 1 1.71 ; Br, 0) also match the found values (wt%: C, 81 .07; H, 2,78; N, 1 1.14; Br, 5.01 ) for compound (13), although there is still about 5% of the bromine remaining in the polymer compound.
  • Elemental analysis results for compounds (11 ) and (12) show that the bromine remaining in the polymer compounds are less than 0.5%.
  • Solid state 13 C NMR spectra obtained for precursor compounds (2-TBTBP, 3- TBTBP and 2-TBQP) and compounds (11 ), (12) and (13) are provided in FIG. 4A- 4C. Similar 13 C chemical shifts were observed for both the precursor compounds and the polymer compounds, which indicates the similarity in their chemical structures and confirms that the polymeric structure formed via cross coupling of the monomers.
  • FTIR spectra obtained for precursor compounds (2-TBQP and 3-TBQP) and compounds (13) and (14) are provided in FIG. 5A and 5B.
  • the FTIR spectra obtained before polymerization show characteristic bands of phenazine linkages at 1338, 1443 and 1508 cm -1 (1312, 1338, 1508 cm “1 ) as well as vibration bands of Ar- Br unit at 458 cm 1 for precursor compound (2-TBQP) and 512 cm "1 for precursor compound (3-TBQP) respectively.
  • FTIR spectra obtained for compounds (11) and (12) also found that the peaks corresponding to the C-Br bond in precursor compounds (2-TBTBP and 3- TBTBP) vanished after polymerization, which is strong evidence of a denomination process during the thermosetting polymerization.
  • FIG, 8 shows the UV-vis spectra obtained for precursor compounds (2-TBQP and 3-TBQP) and compounds (13) and (14).
  • 2-TBQP and 3 ⁇ TBQP display an absorbance in ultraviolet and visible regions from 250 to 650 nm.
  • compounds (13) and (14) have a much broader absorbance across the ultraviolet and visible regions that further extends to near-IR regions (1350 nm), which is indicative of an extended ⁇ cloud delocalization in the ⁇ conjugated organic skeleton of the polymers.
  • UV-vis spectra obtained for compounds (11 ) and (12) also show a broad absorbance across the ultraviolet and visible regions that further extends to near-IR regions, which indicates extended ⁇ cloud delocalization in the skeleton of the polymers.
  • FIG. 7A, 7C, 7E and 7G show the nitrogen (N2) adsorption (filled) and desorptlon (open) isotherm profiles of compounds (11 ), (12), (13) and (14) respectively.
  • FIG. 7B, 7D, 7F, 7H show the crystalline structure analysis (i.e. pore size distribution calculated by non-local density functional theory (NLDFT) modelling based on the i adsorption data) of compounds (11 ), (12), (13) and (14). As calculated from the N2 adsorption and desorptlon data in FIG.
  • NLDFT non-local density functional theory
  • compound (11 ) has shown to possess permanent pores smaller than 0.8 nm
  • compound (12) has a pore size around 0.7 nm
  • compounds (13) and (14) have shown to possess permanent nano-pores as small as 0.6 and 0.5 nm respectively.
  • this pore size of 0.5 nm is the smallest pore ever achieved in porous polymers.
  • the compounds possess highly ordered porosity (i.e. the pore width is relatively homogeneous) as indicated by the narrow peak in the differential pore volume plots.
  • the TEM image of exfoliated compound (13) shows a rectangular shape and the layers in the purple circle indicate a two-dimensional structure (see FIG. 8B).
  • the TEM image of exfoliated compound (14) shows a triangular sheet with sides -15 ⁇ and neat edges of compound (14) under a TEM.
  • a uniform slurry was prepared by mixing compound (13) (75 wt%), Super P carbon black (10 wt%) and sodium alginate binder (Sigma Aldrich, 15 wt%) in wafer and stirring overnight.
  • the slurry was coated on copper foil and dried at 80°C in vacuum oven for 24 h.
  • the coated copper foil was cut into discs 12 mm in diameter.
  • the CR2018 coin cells were assembled in an Ar-filled glove box by using sodium metal as the reference electrode and counter electrode, with a glass microfiber filter (Whatman) as the separator.
  • NaCI04 (1.0 ) in anhydrous propylene carbonate was used as the electrolyte. Cyclic voltammetry curves are collected with Iviumn station.
  • the cells were galvanostatically discharged/charged at various current densities n the voltage range of 0.005-2.5 V (versus Na/Na + ) on a Bitrode battery tester system (Model SCN-12-4-5/18) with a data collection time interval of 0.3 s. The capacity was calculated based on the mass of active materials, which is 75% of the electrode. All regents were bought from Sigma Aldrich.
  • FIG. 9A shows the cyclic voltammogram (CV) of an electrode containing compound (13) between +0.005 V and +2.5 V at a potential sweep rate of 0.1 mV/s as an anode in room temperature sodium (Na)-ion batteries.
  • FIG. 9B shows the cyclic voltammogram (CV) of an electrode containing compound (13) between +0.005 V and +3,0 V at a potential sweep rate of 0.1 mV/s as an anode in room temperature lithium (Li) ⁇ ion batteries,
  • the synthesized polymer namely compound (13) is electrochemical active in the tested potential range.
  • FIG. 10A shows the charge capacities of electrode containing compound (13) at 0.1 , 0.5, 1.0, 3.0, 5.0, 10.0 A g -1 while FIG. 10B shows the galvanostatic charge- discharge profiles of compound (13) at different current densities.
  • compound (13) was used as an anode in sodium battery, it was shown that compound (13) achieved excellent cycle performance at ultrafast charge/discharge rates. The material allows a fast charge and discharge of sodium ions.
  • FIG. 10C compound (13) achieved an excellent cycle performance, cycling over 7,700 cycles while retaining 70% of its initial capacity of 114 mAh g- and at a high current density of 5.0 A g "1 in ambient temperature sodium cell.
  • compound (13) based electrodes is also analyzed in Li-ion battery as illustrated in FIG. 11.
  • the inventors have found that compound (13) is also a promising anode material for lithium battery. After 20, 000 cycles at a charging/discharging current of as high as 10.0 A g _1 , compound (13) maintained 60% of its initial capacity.
  • the polymerization method of the embodiments of the present disclosure have shown to be more efficient and cost-effective because the preparation of porous polymers using the embodiments of method disclosed herein can achieve quantitative yield without any sumble or catalyst
  • These compounds show superior cycle performance at ultrafast discharge rate when employed as organic anode materials in lithium and sodium battery.
  • the compounds when used as organic anode materials are able to cycle over 7,700 cycles while retaining 70% of its initial capacity 1 14 mAh g ⁇ 1 , at a high current density of 5.0 A g "1 in an ambient temperature sodium cell. As can be seen from the comparison table below, this is the best performance for sodium battery ever reported at such a high rate.
  • Various embodiments of the present disclosure provide porous polymer compounds which possess uniform nano-sized pores having pore size of as low as about 0,5 nm.
  • Embodiments of the compounds disclosed herein can be scalable and processed into any shape, size or dimensions that are desirable for industrial applications.
  • the compound may be mechanically exfoliated into sheets with a thickness of less than 1 prn. The mechanical exfoliation may be performed by suspending the polymer in an organic solvent. These exfoliated sheets of the polymer may be transferred onto substrates for further appiications.
  • the compounds disclosed herein can be used in various applications such as in energy storage and production, gas separation and storage, fuel separation and catalysis.
  • the compounds disclosed herein can be conductive or semi-conductive, thus making them attractive for use as electrode materials in micro energy storage devices such as micro-batteries.
  • the polymerization process does not involve the use of any solvent or catalyst, thereby making the production process efficient and cost-effective on a large scale.
  • embodiments of the compounds disclosed herein have shown that they can be used as organic electrode materials in energy storage devices.
  • compounds having general formula (III), i.e. compound (13) employed as organic anode materials in sodium and lithium battery have achieved high capacity and an excellent cycle performance at ultrafast charge and discharge rate, better than any state of the art materials.
  • Various embodiments of the present disclosure provide compounds which may be used as a porous polymer to create i new and improved etectrode materials with a wide range of applications, The present disclosure has demonstrated the principles involved, and opens the way for further scale-up in many applications.

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L'invention concerne un composé comprenant l'une quelconque des formules générales (I), (II) ou (III), son composé précurseur et leurs procédés associés.
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CN113318609A (zh) * 2021-05-25 2021-08-31 林健峯 具有高渗透性及选择性的刚性网络微孔氢气分离膜制造方法
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CN118878792A (zh) * 2024-07-12 2024-11-01 广西民族师范学院 菲并[9,10]吡嗪类共轭微孔聚合物、基于该聚合物的光电传感器、其制备方法及应用

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WO2022097626A1 (fr) * 2020-11-04 2022-05-12 株式会社Kyulux Composé, matériau électroluminescent, matériau à fluorescence retardée, et élément électroluminescent organique
JP2022074226A (ja) * 2020-11-04 2022-05-18 株式会社Kyulux 化合物、発光材料、遅延蛍光材料および有機発光素子
CN113422053A (zh) * 2021-05-12 2021-09-21 暨南大学 基于三环喹唑啉及其衍生物的电池负极材料及其在碱金属离子电池中的应用
CN113318609A (zh) * 2021-05-25 2021-08-31 林健峯 具有高渗透性及选择性的刚性网络微孔氢气分离膜制造方法
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WO2023065820A1 (fr) * 2021-10-20 2023-04-27 浙江时间新材料有限公司 Polymère microporeux conjugué à base de pyridine-et-thiazole-bifonctionnalisé, son procédé de préparation et son utilisation
CN114759196A (zh) * 2022-05-07 2022-07-15 青岛大学 一种负载金属纳米颗粒的共轭微孔高分子电催化剂及其制备方法和应用
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