WO2012133737A1 - Composé amine réticulable, membrane polymère utilisant un composé amine réticulable, et procédé de production de membrane polymère - Google Patents

Composé amine réticulable, membrane polymère utilisant un composé amine réticulable, et procédé de production de membrane polymère Download PDF

Info

Publication number
WO2012133737A1
WO2012133737A1 PCT/JP2012/058521 JP2012058521W WO2012133737A1 WO 2012133737 A1 WO2012133737 A1 WO 2012133737A1 JP 2012058521 W JP2012058521 W JP 2012058521W WO 2012133737 A1 WO2012133737 A1 WO 2012133737A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
represented
amine compound
integer
Prior art date
Application number
PCT/JP2012/058521
Other languages
English (en)
Japanese (ja)
Inventor
育雄 谷口
照彦 甲斐
淑紅 段
伸吾 風間
Original Assignee
公益財団法人地球環境産業技術研究機構
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 公益財団法人地球環境産業技術研究機構 filed Critical 公益財団法人地球環境産業技術研究機構
Publication of WO2012133737A1 publication Critical patent/WO2012133737A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C237/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a novel crosslinkable amine compound, a polymer membrane for separating carbon dioxide from a mixed gas containing carbon dioxide using the compound, a method for producing the polymer membrane, and a gas using the polymer membrane It relates to a separation method.
  • a gas component can be separated by a film composed of the polymer material (see, for example, Non-Patent Document 1).
  • a gas component separation technique using a membrane has advantages such as low energy consumption, miniaturization of the apparatus, and easy maintenance of the apparatus, and is used in various fields.
  • a technique for selectively separating carbon dioxide among techniques for separating a gas component by a membrane has been energetically studied. This technology can be used to separate and recover carbon dioxide from off-gas in oil fields, waste incineration, exhaust gas from thermal power generation, natural gas, and the like.
  • Patent Document 1 discloses a film thickness of about 500 ⁇ m or more.
  • phase separation occurs and the polyamidoamine dendrimer is easily detached from the polymer membrane.
  • the polymer film of Document 1 may be damaged under pressure, further improvement has been demanded for practical use.
  • the present invention is a novel cross-linking for producing a polymer membrane capable of separating carbon dioxide from other gases with high selectivity at a pressure difference for practical use and causing no phase separation even when the film thickness is reduced. It is an object to provide a functional amine compound, a polymer membrane using the compound, a method for producing the polymer membrane, and a gas separation method using the polymer membrane.
  • a group represented by the following formula (4) (In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.) Obtained by reacting an amine compound (A) having one or more groups selected from the group consisting of groups represented
  • the crosslinkable amine compound is represented by the following formula (5): A compound represented by the following formula (6): A compound represented by the following formula (7): A compound which is a polyamidoamine represented by the following formula (8): A compound that is not a polyamidoamine represented by formula (9): A compound which is not a polyamidoamine represented by the following formula (10): A compound which is not a polyamidoamine represented by formula (11): The crosslinkable amine compound according to the above [1], which is at least one compound selected from the group consisting of compounds other than the polyamidoamine represented by formula (1).
  • the polyamidoamine-based dendrimer has the following formula [10] The polymer film as described in [10] above, which is at least one kind of 0th generation dendrimer selected from the group consisting of 1st to 5th generation dendrimers corresponding thereto.
  • the polyfunctional polymerizable monomer is one or more selected from the group consisting of polyfunctional (meth) acrylamide, polyfunctional (meth) acrylate, polyfunctional vinyl ether and divinylbenzene.
  • the polymer membrane according to any one of [11].
  • Di (meth) acrylate is (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) )
  • Monofunctional polymerizable monomer is monofunctional (meth) acrylamide, monofunctional (meth) acrylate, monofunctional vinyl ether, monofunctional N-vinyl compound, monofunctional vinyl compound and monofunctional ⁇ , ⁇ -unsaturated
  • Monofunctional (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, Selected from the group consisting of methoxypolyethylene glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, (poly) ethylene glycol (meth) acrylate and (poly) propylene glycol (meth) acrylate.
  • the polymer film as described in [16] above, wherein the polymer film is at least one kind.
  • a method for producing a polymer film comprising a step of immobilizing the compound (B).
  • the following formula (1) (In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.)
  • a group represented by the following formula (4) (In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
  • the polyamidoamine dendrimer is represented by the following formula: The method for producing a polymer film as described in [22] above, which is at least one kind of 0th generation dendrimer selected from the group consisting of 1st to 5th generation dendrimers corresponding thereto. [24] including a step of bringing a mixed gas containing carbon dioxide into contact with the polymer membrane according to any one of [8] to [19] to selectively permeate carbon dioxide in the mixed gas.
  • a polymer membrane capable of separating carbon dioxide from other gases with high selectivity at a pressure difference for practical use and a method for producing the polymer membrane are provided.
  • the present invention also provides a method for efficiently separating carbon dioxide from other gases using the polymer membrane.
  • the amine compound having carbon dioxide separation ability is not supported on the surface of the polymer membrane, but is immobilized in the polymer membrane, Even if the film is thinned, it does not cause phase separation and has a feature of excellent stability. By making the film thinner, the gas permeation rate can be increased and gas separation can be performed efficiently. Further, the polymer membrane obtained in the present invention does not cause phase separation even when pressure is applied, the amine compound (B) does not leak, and the membrane does not break down, and is stable for a long time. It can be used and is useful as a practical gas separation membrane.
  • GC gas chromatography
  • a circle indicates an amine compound.
  • a circle indicates an amine compound.
  • 6 is a scanning electron microscope image of Test Example 4. The left shows the comparative product 1 and the right shows the product 15 of the present invention. 10 is a fluorescence image of Test Example 5. The left shows the comparative product 8 and the right shows the product 16 of the present invention. 10 is a graph showing measurement results of X-ray small angle scattering in Test Example 6.
  • the crosslinkable amine compound of the present invention is characterized by having 3 or more acrylic groups and / or methacrylic groups in the molecule at the branch ends.
  • the crosslinkable amine compound is not particularly limited as long as the effect of the present invention is not hindered.
  • a 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.
  • a group represented by formula (2) (In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.)
  • a group represented by the following formula (4) In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.
  • the crosslinkable amine compound is preferred.
  • (i) a compound obtained by reacting an acrylic ester and / or methacrylic ester with a haloformate (hereinafter also referred to as compound (i));
  • (ii) Acrylic acid ester having at least one group selected from the group consisting of hydroxyl group, carboxyl group, glycidyl group, isocyanate group, isocyanurate group, carbodiimide group, aldehyde group, amino group and alkoxysilyl group, and / or Methacrylic acid ester (hereinafter also referred to as compound (ii)).
  • crosslinkable amine compound examples include: Following formula (5) A compound represented by formula (6): A compound represented by formula (7): A compound represented by formula (8): A compound represented by formula (9): A compound represented by formula (10): And a compound represented by the following formula (11) Preferred examples include compounds represented by:
  • the crosslinkable amine compound of the present invention is a compound having 3 or more acrylic groups and / or methacryl groups in the molecule at the branch end. From the viewpoint of improving the crosslink density and preventing phase separation, an acrylic group is present at the branch end. A compound having 4 or more methacrylic groups in the molecule is more preferred. Further, the crosslinkable amine compound of the present invention may contain a metal atom, but it is preferable to exclude one containing a metal atom (particularly a trivalent or higher-valent metal atom).
  • the amine compound (B) is immobilized in the polymer without causing phase separation. Therefore, when a polymer membrane of 100 ⁇ m or less is produced, the phase separation is performed. The cloudiness which shows is not produced. Moreover, since the crosslink density can be increased by using the crosslinkable amine compound, there is no possibility of breakage under high pressure, and a practical polymer membrane for gas separation can be obtained.
  • the ester used for the reaction with the haloformate is more preferably a methacrylic acid ester from the viewpoint that a stronger crosslinked structure can be obtained for the produced polymer film.
  • the acrylic ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, -Ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl Acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, 2- (p-hydroxyphenyl) ethyla
  • Examples include relate, furfuryl acrylate, tetrahydrofurfuryl acrylate
  • 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate and 2- (p- Acrylic acid esters having one or more hydroxy groups selected from hydroxyphenyl) ethyl acrylate are preferred.
  • the acrylic ester may be used alone or in combination of two or more.
  • the methacrylic acid ester is not particularly limited.
  • the haloformate is not particularly limited, and examples thereof include a haloformate having an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, and the like. Preferred are haloformates having an aromatic ring group.
  • the haloformate group in the haloformate has the following formula: —OC ( ⁇ O) X (In the formula, X means Cl, Br or I.) It is group shown by these. Although it does not specifically limit as a haloformate which has the aromatic ring group which may have the said substituent, The aromatic chloroformate which may have a substituent is preferable.
  • the aromatic chloroformate which may have a substituent is not particularly limited, but a chloroformate having a phenyl group which may have a substituent is preferable, and 2,4,5-trichlorophenylchloro Formate (chloroformate 2,4,5-trichlorophenyl) or p-nitrophenyl chloroformate is particularly preferred.
  • the substituent in the above-described compound is not particularly limited as long as the effect of the present invention is not hindered.
  • the amount of the haloformate used is usually about 1.0 to 5.0 moles, preferably about 1.2 to 2.0 moles per mole of acrylic acid ester and / or methacrylic acid ester.
  • the temperature of the reaction is not particularly limited, but is usually about 20 ° C to 60 ° C.
  • the reaction time is not particularly limited, but is usually about 3 hours to 1 day.
  • the reaction of the acrylic ester and / or methacrylic ester with haloformate is preferably carried out in the presence of a catalyst, and the catalyst used in the reaction is not particularly limited, but N, N-dimethyl-4-aminopyridine is used. (DMAP) or 4-pyrrolidinepyridine.
  • the amount of the catalyst used is not particularly limited, but is preferably 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 3 equivalents per 1 mol of the acrylic ester and / or methacrylic ester of the raw material, and 1 ⁇ 10 ⁇ 7 to 5 ⁇ 10.
  • the solvent used in the reaction is not particularly limited, and examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned. Any of these may be used alone or in combination of two or more at any ratio.
  • the compound (ii) has one or more groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an isocyanurate group, a carbodiimide group, an aldehyde group, an amino group, and an alkoxysilyl group.
  • a hydroxyl group a carboxylic acid group, a glycidyl group, an isocyanate group, an isocyanurate group, a carbodiimide group, an aldehyde group, an amino group, and an alkoxysilyl group.
  • Acrylic acid ester and / or methacrylic acid ester having a glycidyl group is preferable from the viewpoint of increasing affinity with a certain polyethylene glycol compound and the like.
  • crosslinking compound (ii) examples include dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, alkyl methacrylamide (for example, methacrylamide, dimethylmethacrylamide, N-isopropylmethacrylamide, n-butylmethacrylamide, tert-butyl methacrylamide and tert-octyl methacrylamide), 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, 3-butenoic acid, allyl isothiocyanate, isothiocyanate 3- Examples include buten-1-yl, allyl glycidyl ether, and glycidyl methacrylate, and glycidyl methacrylate is particularly preferable.
  • alkyl methacrylamide for example, methacrylamide, dimethylmethacrylamide, N-isopropylmethacrylamide, n
  • the reaction between the amine compound (A) and one or more compounds selected from the group consisting of the compounds (i) and (ii) will be described.
  • the amount of the compounds (i) and (ii) to be used is not particularly limited, but is usually about 1.0 to 10 mol, preferably 1.2 to 2. mol per mol of the amine compound (A). About 0 mole.
  • the temperature of the reaction is not particularly limited, but is usually about 20 ° C to 60 ° C.
  • the reaction time is not particularly limited, but is usually about 3 hours to 1 day.
  • the solvent used in the reaction is not particularly limited.
  • Examples include formamide, chloroform, dichloromethane, methylene chloride, ethyl acetate, dimethyl sulfoxide, dioxane, benzene, toluene, tetrahydrofuran, water, methanol, ethanol, isopropanol, etc., and these may be used alone or in combination of two or more. Good. Moreover, the said reaction may be performed in absence of a catalyst and may be performed in presence of a catalyst.
  • the catalyst is not particularly limited.
  • the cross-linking agent of the present invention can be obtained.
  • the amine compound (A) is an amine compound having one or more groups selected from the group consisting of the groups represented by the formulas (1) to (4).
  • Examples of the divalent organic residue having 1 to 3 carbon atoms represented by A 1 , A 2 , A 3 , A 4 , A 5 and A 6 include, for example, linear or branched C 1 to 3 carbon atoms.
  • An alkylene group is mentioned. Specific examples of such alkylene groups, -CH 2 -, - CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) - , and the like, Of these, —CH 2 — is particularly preferable.
  • the number of the groups is not particularly limited as long as at least one group represented by the formulas (1) to (4) is contained, but preferably 2 to 4096 groups, More preferably, those having 3 to 128 groups are exemplified.
  • the polymer film of the present invention has the following formula (1) in a polymer obtained by polymerizing a polyfunctional polymerizable monomer that is crosslinked using the crosslinkable amine compound as a crosslinking agent.
  • a 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.
  • a 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.
  • a group represented by the following formula (4) In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.
  • the amount of the crosslinkable amine compound used in the production of the polymer is not particularly limited as long as the effect of the present invention is not hindered, but is usually 5 to 95 wt% with respect to the polyfunctional polymerizable monomer. From the viewpoint of improving the durability of the resulting polymer film and the stability of the amine compound (B), it is preferably 10 to 80 wt%, more preferably 15 to 50 wt%.
  • the weight fraction occupied by one or more groups selected from the group consisting of the groups represented by the formulas (1) to (4) is not particularly limited, but carbon dioxide and hydrogen From the viewpoint of improving the separation ability of the amine compound, it is preferable that the weight fraction of one or more groups selected from the group consisting of groups represented by formulas (1) to (4) in the amine compound is 5% or more. More preferred is 10 to 94%, and further preferred is 15 to 53%.
  • examples of the skeleton to which one or more groups selected from the group consisting of groups represented by formulas (1) to (4) are bonded include the following. [Wherein n represents an integer of 0 to 10. ]
  • a bond which is bonded directly or via an alkylene group and is not bonded with one or more groups selected from the group consisting of the groups represented by formulas (1) to (4) includes a hydrogen atom, an alkyl group, amino A compound in which an alkyl group, a hydroxyalkyl group or the like is bonded.
  • Examples of the amine compound (B) include 0th generation polyamidoamine dendrimers represented by the following formula, and 1st generation or more corresponding to these 0 th generation polyamidoamine dendrimers.
  • polyamidoamine dendrimers examples of particularly suitable compounds include the following polyamidoamine dendrimers.
  • the polyamidoamine-based dendrimers used in the present invention include those having all equal branch lengths and those having at least one of them substituted with a hydroxyalkyl group or an alkyl group and having different branch lengths.
  • various polyamidoamine dendrimers having different numbers of surface groups [namely, groups represented by the formula (1), (2), (3) or (4)] can be used. .
  • the relationship between the number of surface groups and the generation of the polyamidoamine-based dendrimer is as follows. If the number of the 0th generation surface groups is a (a represents an integer of 3 or more), the b generation (b represents an integer).
  • the number c of surface groups is as follows.
  • 0th to 10th generation PAMAM dendrimers manufactured by Aldrich can be used, and in particular, 0th to 5th generation polyamidoamine dendrimers can be preferably used.
  • Table 1 below shows the number of surface groups for each generation when the number of surface groups of the 0th generation is four.
  • the polyamidoamine dendrimer the first generation or higher is preferable from the viewpoint of increasing the crosslink density of the obtained polymer film.
  • the second generation or higher is particularly preferable. preferable.
  • the amine compound having a group represented by the formula (1) can be produced according to a known organic synthesis method.
  • a method of reacting a mother nucleus compound having a methyl ester group with an amine compound represented by the following formula (1a) is exemplified.
  • the methyl ester group of a compound having a methyl ester group is converted to a group represented by the formula (1a), and an amine compound having a group represented by the formula (1) can be produced.
  • the following formula is a formula in which a methyl ester group is converted into a group represented by formula (1) in the synthesis method. (In the formula, A 1 and p have the same meaning as described above.)
  • the reaction between the compound having a methyl ester group and the amine compound represented by the formula (1a) is usually carried out by adding 3 to 20 mol of the amine compound represented by the formula (1a) with respect to 1 mol of the compound having a methyl ester group. , Preferably 5 to 10 moles.
  • the reaction between the compound having a methyl ester group and the amine compound represented by the formula (1a) is usually carried out in a suitable solvent.
  • a suitable solvent known solvents can be widely used as long as they do not inhibit the reaction. Examples of such a solvent include methanol, ethanol, 2-propanol, tetrahydrofuran, 1,4-dioxane and the like. These solvents do not prevent water from being contained.
  • the reaction between the compound having a methyl ester group and the amine compound represented by (1a) is usually continued at 0 to 40 ° C., preferably 20 to 30 ° C., for 90 to 180 hours, preferably 160 to 170 hours. Is done.
  • compounds of known compounds can be used as the compound having a methyl ester group used as a raw material and the amine compound represented by the formula (1a).
  • the reaction mixture obtained by the above reaction is cooled, for example, and then subjected to an isolation operation such as filtration, concentration, extraction, etc. to separate the crude reaction product, and if necessary, column chromatography, recrystallization, etc.
  • the amine compound having a group represented by the formula (1) can be isolated and purified by performing a normal purification operation.
  • the amine compound having a group represented by the formula (2) is obtained by reacting, for example, a mother nucleus compound having an amino group and an amine compound having a methyl ester group at the terminal represented by the following formula (2a) in the same manner as described above. Can be manufactured. (In the formula, A 2 and q have the same meaning as described above.)
  • the amine compound having a group represented by the formula (3) is, for example, a mother nucleus compound having an alkenyl group at the terminal represented by the following formula (3a) and a diamine compound represented by the following formula (3b) in the same manner as described above. It can be produced by reacting. (In the formula, A 3 , A 4 , r and s have the same meaning as described above.)
  • the amine compound having a group represented by the formula (4) for example, reacts a mother nucleus compound having a carbonyl group represented by the following formula (4a) and a diamine compound represented by the following formula (4b) in the same manner as described above. Can be manufactured.
  • a 5 , A 6 and t have the same meaning as described above, and A 7 represents an organic residue.
  • Preferable examples of the organic residue having 1 to 3 carbon atoms represented by A 7 include a linear or branched alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group). .
  • the polyfunctional polymerizable monomer used in the present invention is not particularly limited as long as it is a polymerizable compound having two or more carbon-carbon unsaturated bonds.
  • examples thereof include polyfunctional acrylic monomers such as polyfunctional (meth) acrylamide and polyfunctional (meth) acrylate, and polyfunctional vinyl monomers such as polyfunctional vinyl ether or divinylbenzene. These polyfunctional polymerizable monomers can be used alone or in combination of two or more.
  • polyfunctional (meth) acrylamides examples include N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethidium bromide-N, N′-bisacrylamide, and ethidium. Examples include bromide-N, N′-bismethacrylamide, N, N′-ethylenebisacrylamide, N, N′-methylenebisacrylamide, and the like. Examples of the polyfunctional (meth) acrylates include di (meth) acrylates, tri (meth) acrylates, and tetra (meth) acrylates.
  • di (meth) acrylates examples include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) And alkylene glycol di (meth) acrylates such as acrylate and pentaerythritol di (meth) acrylate.
  • tri (meth) acrylates examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, and the like. .
  • Examples of the tetra (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate.
  • Examples of the polyfunctional vinyl ethers include trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, and the like.
  • the polymerization reaction may be carried out by using the polyfunctional polymerizable monomer and the monofunctional polymerizable monomer in combination. By using in combination, the size of the network in the polymer can be adjusted.
  • Monofunctional polymerizable monomers include monofunctional acrylic monomers such as monofunctional (meth) acrylamides and monofunctional (meth) acrylates, monofunctional vinyl ethers, monofunctional N-vinyl compounds or monofunctional vinyl compounds. And monofunctional vinyl monomers and monofunctional ⁇ , ⁇ -unsaturated compounds.
  • Examples of the monofunctional (meth) acrylamide include 2-acetamidoacrylic acid, (meth) acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, N- (butoxymethyl) acrylamide, N-tert-butylacrylamide, and diacetone acrylamide.
  • Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxy
  • Examples include polyethylene glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, (poly) ethylene glycol methacrylate, and polypropylene glycol (meth) acrylate.
  • Examples of the monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, and methoxypolyethylene glycol vinyl ether.
  • Examples of the monofunctional N-vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and the like.
  • Examples of the monofunctional vinyl compounds include styrene, ⁇ -methylstyrene, vinyl acetate and the like.
  • Examples of the monofunctional ⁇ , ⁇ -unsaturated compounds include maleic anhydride, maleic acid, dimethyl maleate, diethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, monomethyl fumarate, monoethyl fumarate, and itaconic anhydride.
  • Examples thereof include acid, itaconic acid, dimethyl itaconate, methylene malonic acid, dimethyl methylene malonate, cinnamic acid, methyl cinnamate, crotonic acid, and methyl crotonic acid.
  • the amount of the amine compound (B) having one or more groups selected from the group consisting of the groups represented by the formulas (1) to (4) immobilized in the polymer is determined by the polymer 100
  • the amount is usually about 2 to 400 parts by weight, preferably about 25 to 250 parts by weight, more preferably about 40 to 100 parts by weight from the viewpoint of obtaining sufficient gas separation performance.
  • the thickness of the polymer membrane of the present invention is not particularly limited as long as the effects of the present invention are not hindered, but is usually about 1000 ⁇ m or less from the viewpoints of high gas permeation rate and preferable performance of gas separation. About 600 ⁇ m or less, more preferably about 250 ⁇ m or less, and even more preferably about 100 ⁇ m or less.
  • the lower limit of the film thickness is not particularly limited as long as gas separation can be effectively performed, but is preferably about 5 ⁇ m or more, and more preferably about 10 ⁇ m or more from the viewpoint of durability.
  • the film thickness when used as a self-supporting film having no support is not particularly limited as long as the effects of the present invention are not hindered.
  • the film thickness when used as a composite film having a support is not particularly limited as long as the effects of the present invention are not hindered, but is preferably about 5 ⁇ m or more and 150 ⁇ m or less from the viewpoint of the strength of the film and the gas permeation rate, More preferably, it is about 10 ⁇ m or more and 100 ⁇ m or less.
  • the gas permeation rate when using the polymer membrane of the present invention is not particularly limited as long as the effect of the present invention is not hindered, but is about 1 ⁇ 10 ⁇ 13 m 3 from the viewpoint of gas separation efficiency.
  • (STP) / (m 2 Spa) or more is preferable, and about 1 ⁇ 10 ⁇ 12 m 3 (STP) / (m 2 Spa) or more is more preferable.
  • the pressure applied to the membrane when using the polymer membrane of the present invention is preferably about 0.1 MPa or more, more preferably about 1 to 4 MPa.
  • a support is not essential, but a support may be provided as necessary.
  • a porous support membrane is preferably used from the viewpoint of gas separation.
  • the thickness of the porous support membrane is not particularly limited as long as the effect of the present invention is not hindered, but is preferably about 50 ⁇ m to 1000 ⁇ m, more preferably about 100 ⁇ m to 500 ⁇ m from the viewpoint of strength and gas permeation rate.
  • the porous support membrane and the polymer membrane integrally formed can be used as a gas separation composite membrane.
  • the composite membrane refers to one in which a polymer membrane having gas separation ability and a porous support membrane are integrally formed.
  • the porous support membrane used in the present invention can be produced using, for example, a polymer described later, and ceramics, polyethylene phthalate (PET) film, and the like can also be used. Specifically, when producing using a polymer, the polymer is dissolved in a solvent to obtain a raw material solution, and then the raw material solution is brought into contact with a coagulation liquid (a mixed solution of a solvent and a non-solvent).
  • a porous support membrane can be produced by a method of inducing phase separation by increasing the solvent concentration (non-solvent induced phase separation method; NIPS method, see Japanese Patent Publication No. 1-2003).
  • the ceramic include alumina, zirconia, titania, and silica.
  • Examples of the polymer used for the production of the porous support membrane include polyethersulfone (PES), polysulfone (PSF), polyphenylenesulfone, triacetylcellulose, cellulose acetate, carbon, polyacrylonitrile, polyvinylidene fluoride, aromatic nylon, and polyethylene.
  • Examples thereof include phthalate (PET), polyethylene naphthalate, polyarylate, polyimide, polyether, cellophane, aromatic polyamide, polyethylene, and polypropylene.
  • Examples of the solvent include N-methylpyrrolidone (NMP), acetone, dimethylformamide and the like. There is no particular limitation as long as the solvent dissolves in the coagulation liquid during coagulation.
  • non-solvent examples include water, monohydric alcohol, polyhydric alcohol, ethylene glycol, and tetraethylene glycol.
  • a swelling agent for example, one or a mixture of two or more selected from polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, sodium chloride, lithium chloride, and magnesium bromide can be used.
  • polyethylene glycol is preferable, and polyethylene glycol having a weight average molecular weight of 400 to 800 is particularly preferable.
  • the concentration of the raw material solution and the coagulation liquid is not particularly limited as long as the concentration is such that the raw material solution and the coagulation liquid are brought into contact with each other and a porous support membrane can be obtained by a non-solvent induced phase separation method.
  • the raw material solution is preferably a 20 to 35 wt% PES solution in view of film forming properties.
  • the method for contacting the raw material solution with the coagulating liquid is not particularly limited, and examples thereof include a method of immersing the raw material solution in the coagulating liquid.
  • the concentration of the solvent in the coagulation liquid is not particularly limited, but by changing the solvent concentration in the coagulation liquid in the coagulation of the raw material solution, the structure of the support film can be changed and the pressure resistance can be increased.
  • the pore diameter of the pores of the porous support membrane is preferably 100 nm or less, more preferably 10 nm or less.
  • the thickness of the porous support membrane is not particularly limited as long as the gas permeability of the polymer membrane does not become larger than the gas permeability of the porous support membrane.
  • a crosslinkable amine compound having 3 or more branched ends having an acrylic group and / or methacrylic group as a polymerizable functional group and the following formula (1)
  • a 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.
  • a 3 and A 4 represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.
  • a group represented by the following formula (4) In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.
  • Examples include a method including a step of immobilizing the compound (B) to form a polymer film (step [I]). Moreover, the process (process [II]) which laminates
  • This step is a polyfunctional polymerizable compound in the presence of the crosslinkable amine compound having three or more branched ends with the acrylic group and / or methacrylic group as the polymerizable functional group in the molecule, and the amine compound (B).
  • This is a step of forming a polymer film by immobilizing the amine compound in the polymer polymer produced by polymerizing the monomer.
  • the polymerization reaction is not particularly limited as long as the effects of the present invention are not hindered.
  • the polymerization reaction may be thermal polymerization or photopolymerization. In this case, a polymerization initiator is usually used (heat or light).
  • thermal polymerization initiator known ones can be used. Specifically, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide Organic peroxides such as octoate, t-butylperoxybenzoate, and lauroyl peroxide; azo compounds such as azobisisobutyronitrile are suitable.
  • a curing accelerator may be used by mixing at the time of thermal polymerization, and as the curing accelerator, cobalt naphthenate, cobalt octylate, etc., or tertiary amine is suitable.
  • the addition amount of the thermal polymerization initiator is preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable monomer. More preferably, it is about 0.1 to 1 part by weight.
  • Benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1 -T-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal
  • Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone Thioxanthones such as -9-one mesochloride; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldi
  • Benzyldimethyl ketal (eg, 2,2-dimethoxy-1,2-diphenylethane-1-one), ⁇ -hydroxyalkylphenone (eg, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one), ⁇ -aminoalkylphenone (eg, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinofe Nyl) -butanone-1,2- (dimethylamino) -2-[(4-[2-
  • the addition amount of the photopolymerization initiator is preferably about 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable monomer. More preferably, it is about 2 to 3 parts by weight.
  • a basic compound can be used as a sensitizer together with a photopolymerization initiator.
  • an amine compound is preferably used, and the amine compound is not particularly limited. Specifically, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropyl are used. Examples include amine, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, and polyethyleneimine. Of these, tertiary amine compounds are particularly preferred.
  • tertiary amine compound examples include triethanolamine, triisopropanolamine, tributanolamine, methyldiethanolamine, methyldiisopropanolamine, methyldibutanolamine, ethyldiethanolamine, ethyldiisopropanolamine, ethyldibutanolamine, propyldiethanolamine, propyl Diisopropanolamine, propyldibutanolamine, dimethylethanolamine, dimethylisopropanolamine, dimethylbutanolamine, diethylethanolamine, diethylisopropanolamine, diethylbutanolamine, dipropylethanolamine, dipropylisopropanolamine, dipropylbutanolamine, dibutylethanol Amine, dibutylisopropano Triethanolamine, dibutyl butanolamine, methyl ethyl ethanolamine, methyl
  • hydroxyl group-containing tertiary amine compounds are added with ethylene oxide to introduce a polyethylene glycol chain, and the hydroxyl group-containing tertiary amine compound is added with a monomer containing a functional group reactive with a hydroxyl group to obtain a polymerizable group. What introduced the heavy bond, what introduce
  • These amine compounds can be used alone or in combination of two or more.
  • the amount of the sensitizer used is preferably about 1 to 10 parts by weight with respect to 100 parts by weight of the photopolymerization initiator. More preferably, it is about 5 to 8 parts by weight.
  • the polymerization reaction is preferably carried out in a suitable solvent by heating in the case of thermal polymerization and by irradiation with ultraviolet rays in the case of photopolymerization.
  • the solvent is not particularly limited as long as it dissolves the amine compound and the polyfunctional polymerizable monomer, but usually an alcohol (for example, methanol, ethanol, etc.) can be preferably used.
  • Heating in the thermal polymerization is usually performed at about 40 to 90 ° C., preferably about 60 to 70 ° C., usually about 2 to 24 hours, preferably about 5 to 10 hours.
  • the ultraviolet irradiation of the photopolymerization is usually performed for about 30 seconds to 10 minutes, preferably about 1 to 3 minutes, using a wavelength of about 200 to 400 nm, preferably about 250 to 360 nm.
  • thermal polymerization and photopolymerization can be performed in combination.
  • photopolymerization can be performed after thermal polymerization, thermal polymerization can be performed after photopolymerization, or photopolymerization and thermal polymerization can be performed simultaneously. .
  • a polymer film is obtained in which the amine compound (B) is physically or chemically immobilized in the polymer at the same time as the polymer is produced.
  • Suitable examples of the obtained polymer film include those in which the amine compound (B) is sealed and fixed in the network structure of the polymer having the three-dimensional network structure.
  • the high molecular polymer has a cross-linked structure of the cross-linkable amine compound, a high polymer film having excellent strength and gas separation property can be obtained.
  • the crosslinkable amine compound the amine compound (B) having carbon dioxide gas separation performance does not phase-separate even if the film thickness is reduced, the membrane is subjected to high pressure, etc. A gas separation membrane that is preferable in this respect is obtained.
  • phase separation can be confirmed, for example, by X-ray small angle scattering using CuK ⁇ rays (wavelength 0.1542 nm). When no peak is observed at a scattering vector of 0.6 nm ⁇ 1 or more, it can be seen that a particularly excellent gas separation performance can be maintained because there is no structure due to a phase separation structure of 200 nm or less.
  • the polymer membrane of the present invention may be provided with a support as necessary.
  • This step is a step of obtaining a composite membrane obtained by laminating the polymer membrane obtained in the step (1) and a porous support membrane.
  • a method of laminating the polymer membrane and the porous support membrane a method known per se can be employed, and examples thereof include a laminating method. Examples of the laminating method include known dry laminating and hot melt laminating. Is mentioned.
  • the polymer membrane and the porous support membrane are usually cut to have a diameter (diameter) of 20 to 60 mm, preferably about 25 to 50 mm, and bonded together using an adhesive or an adhesive film.
  • the adhesive used for laminating is not particularly limited, but an aqueous adhesive (eg, ⁇ -olefin adhesive, aqueous polymer-isocyanate adhesive, etc.), an aqueous dispersion adhesive (eg, acrylic resin emulsion adhesive) , Epoxy resin emulsion adhesives, vinyl acetate resin emulsion adhesives, etc.), solvent adhesives (eg, nitrocellulose adhesives, vinyl chloride resin solvent adhesives, chloroprene rubber adhesives, etc.), reactive adhesives (eg, , Cyanoacrylate adhesives, acrylic resin adhesives, silicone adhesives, etc.), hot melt adhesives (eg, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, polyamide resin hot melt adhesives) , Polyolefin resin hot melt adhesive, etc.).
  • an aqueous adhesive eg, ⁇ -olefin adhesive, aqueous polymer-isocyanate adhesive, etc.
  • the adhesive film examples include films made of a thermoplastic transparent resin such as polyvinyl butyral, polyurethane, and ethylene-vinyl acetate copolymer resin.
  • the thickness of the adhesive or adhesive film layer is not particularly limited as long as it does not interfere with the gas permeability of the polymer membrane of the present invention and the gas permeability of the porous support membrane.
  • the gas separation method of the present invention includes a step of bringing the mixed gas containing carbon dioxide into contact with the polymer membrane or the composite membrane obtained above to selectively permeate carbon dioxide in the mixed gas.
  • the gas separation method it is preferable to provide a pressure difference between the gas supply side and the gas permeation side of the separation membrane. This pressure difference is usually provided by reducing the pressure on the gas permeation side.
  • the mixed gas applicable to the separation method of the present invention is not particularly limited as long as it is a mixed gas containing carbon dioxide.
  • the relative humidity of the mixed gas is set to 30. % Or more, preferably 60 to 100%.
  • the gas separation method can be applied to, for example, separating carbon dioxide (CO 2 ) from combustion exhaust gas generated in a thermal power plant, a steel plant, or the like.
  • Example 1 Following formula 2 generation polyamidoamine (PAMAM) dendrimer (surface group: —CONHCH 2 CH 2 NH 2 ; number of amino groups: 4; manufactured by Sigma-Aldrich), polyethylene glycol dimethacrylate (PEGDMA, molecular weight 750) , Sigma-Aldrich) 1.7 g (2.27 mmol) and 4 GMAP (Synthesis Example 1) 300 mg (0.28 mmol) as a crosslinking agent are dissolved in 4 g of water, and IRGACURE 2959 (trade name, BASF) is used as a polymerization initiator.
  • PAMAM polyamidoamine
  • PEGDMA polyethylene glycol dimethacrylate
  • 4 GMAP Synthesis Example 1
  • 300 mg (0.28 mmol) as a crosslinking agent are dissolved in 4 g of water, and IRGACURE 2959 (trade name, BASF) is used as a polymerization initiator.
  • Example 2 A polymer film was obtained in the same manner as in Example 1 except that the film thickness was changed to the value shown in Table 3 (Invention products 2 to 4).
  • Example 3 A polymer film was obtained in the same manner as in Example 1 except that the film thickness was changed to the value described in Table 4.
  • the polymer membrane and a porous support membrane (polyethersulfone ultrafiltration membrane, fractional molecular weight 300,000, manufactured by Millipore) were laminated to obtain composite membranes (Invention products 5 to 10).
  • Example 4 A composite film was obtained in the same manner as in Example 3 except that 300 mg (0.35 mol) of GM4TA obtained in Synthesis Example 5 was used instead of 4GMAP, and the film thickness was changed to 60 ⁇ m (Product 11 of the present invention).
  • Example 5 A composite film was obtained in the same manner as in Example 3 except that 300 mg (0.52 mol) of GM3TA obtained in Synthesis Example 6 was used instead of 4GMAP, and the film thickness was changed to 42 ⁇ m (Product 12 of the present invention).
  • Example 6 A composite film was obtained in the same manner as in Example 3 except that 300 mg (0.30 mol) of 3GMA6OHTA obtained in Synthesis Example 7 was used instead of 4GMAP, and the film thickness was changed to 52 ⁇ m (Product 13 of the present invention).
  • Example 7 A composite membrane was obtained in the same manner as in Example 3 except that 300 mg (0.25 mol) of 4GMA4OHP obtained in Synthesis Example 8 was used instead of 4GMAP, and the thickness was changed to 21 ⁇ m (Product 14 of the present invention).
  • Example 8 A polymer film was obtained in the same manner as in Example 1 except that 300 mg (1.17 ⁇ 10 ⁇ 4 mol) of 8GMAP obtained in Synthesis Example 2 was used instead of 4GMAP and the film thickness was changed to 340 ⁇ m (Invention Product 15 ).
  • Example 9 A polymer membrane was obtained in the same manner as in Example 1 except that 3 wt% of FITC-PEGMA obtained in Synthesis Example 9 was added in addition to 4GMAP (Product 16 of the present invention).
  • TMPTMA trimethylolpropane trimethacrylate
  • 4GMAP 3 mg (0.89 mmol) of trimethylolpropane trimethacrylate
  • 4 g of ethanol was used as a polymerization solvent
  • IRGACURE 2959 was used as a polymerization initiator.
  • a polymer membrane was obtained in the same manner as in Example 1 except that 10 mg of 1-hydroxycyclohexyl phenyl ketone (manufactured by Sigma-Aldrich) was used (Comparative product 1).
  • the obtained polymer film had a TMPTMA content of 15 wt%.
  • Example 1 Separation test of carbon dioxide and hydrogen Using the polymer membrane obtained in Example 1 (Product 1 of the present invention), CO 2 separation ability was measured using the apparatus shown schematically in FIG. That is, the polymer membrane is placed in contact with the supply gas, and a mixed gas of carbon dioxide gas and hydrogen gas having a partial pressure of CO 2 shown in Table 2 is supplied to the polymer membrane and permeates the polymer membrane.
  • the gas permeation rate Q CO2 (m 3 (STP) / m 2 Pas) was measured using a gas chromatography and a flow meter under the following conditions, and selectivity ⁇ was calculated according to the following equation.
  • the polymer film used for the test was 0.8 cm 2 .
  • the polymer membrane of the present invention has strength to withstand a pressure difference and has excellent carbon dioxide selectivity.
  • Example 2 Using the polymer membrane obtained in Example 2 (products 2 to 4 of the present invention), the gas permeation rate and selectivity of the polymer membrane were measured using the apparatus shown schematically in FIG. That is, a gas mixture of carbon dioxide gas having a partial pressure of CO 2 and hydrogen gas shown in Table 3 is supplied to the polymer membrane, and Q H2 , Q CO2 (m 3 (STP) of the gas permeated through the polymer membrane or the composite membrane. ) / M 2 Pas) was measured using a gas chromatography and a flow meter under the following conditions, and selectivity ⁇ was calculated in the same manner as in Test Example 1. The polymer film used for the test was 0.8 cm 2 . Further, the same test was performed using the polymer film obtained in Comparative Example 3 (Comparative products 3 to 5). The results are shown in Table 3.
  • Example 3 Using the composite membrane (Products 5 to 10 of the present invention) obtained in Example 3, the gas permeation rate and selectivity of the composite membrane were measured using the apparatus shown schematically in FIG. That is, the polymer membrane layer was placed in contact with the supply gas, measured under the same conditions as in Test Example 2, and the selectivity ⁇ was calculated in the same manner as in Test Example 1. In addition, the same test was performed using the polymer films obtained in Comparative Example 4 (Comparative products 6 and 7). The results are shown in Table 3.
  • FIG. 4 shows a scanning electron microscope (Hitachi S-4800) image of the polymer matrix after immersion.
  • the product 15 of the present invention no vacancies were observed and a compatible state was maintained, whereas in the comparative product 1, many vacancies were observed, and phase separation was confirmed. From this, it was confirmed that the product of the present invention did not cause phase separation and could maintain excellent gas separation performance of Q CO2 > 10 ⁇ 12 (m 3 / m 2 Pa s) and ⁇ > 10.
  • Example 5 The product 16 of the present invention obtained in Example 9 and the comparative product 8 obtained in Comparative Example 5 were observed with a confocal scan laser (LSM700 manufactured by Carl Zeiss).
  • FIG. 5 is a fluorescent image 10 ⁇ m inside from the surface (resolution 200 nm, scale bar represents 5 ⁇ m).
  • the bright part represents a high molecular polymer colored with FITC-PEGMA, and the dark part represents a dendrimer (amine compound (B)).
  • the product 16 of the present invention containing 4GMAP (amine compound (A)) shows no phase separation structure
  • the comparative product 8 containing no 4GMAP shows a phase separation structure of about several microns (macrophase separation). It was confirmed. From this, it was confirmed that the product of the present invention does not cause phase separation and can maintain excellent gas separation performance.
  • Example 6 The X-ray small angle scattering of the product 1 of the present invention obtained in Example 1 was measured using a Nano viewer manufactured by Rigaku Corporation. The optical path length is 1,250 mm, and scatterers of 200 nm or less can be detected. The results are shown in FIG. The vertical axis represents the scattering intensity, and the horizontal axis represents the scattering vector q ( ⁇ ⁇ 1 ). No peak due to scattering was observed, and it was confirmed that there was no structure due to a phase separation structure of 200 nm or less. From this, it was confirmed that the product of the present invention does not cause phase separation and can maintain excellent gas separation performance.
  • the polymer membrane of the present invention is used in applications for separating carbon dioxide from other gases, and is useful for, for example, CO 2 separation from combustion exhaust gas generated in thermal power plants, steel plants, etc. It is.

Abstract

L'invention concerne un nouveau composé amine réticulable pour produire une membrane polymère permettant de séparer le dioxyde de carbone d'un autre gaz avec une sélectivité élevée ; une membrane polymère utilisant ledit composé ; un procédé permettant de produire ladite membrane polymère ; et un procédé de séparation de gaz utilisant la membrane polymère. Ledit composé amine réticulable se caractérise en ce qu'il possède au moins trois groupes acryloyle et/ou des groupes méthacryloyle dans chaque molécule, lesdits groupes acryloyle et/ou groupes méthacryloyle se situant respectivement aux extrémités des branches.
PCT/JP2012/058521 2011-03-31 2012-03-30 Composé amine réticulable, membrane polymère utilisant un composé amine réticulable, et procédé de production de membrane polymère WO2012133737A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011080427 2011-03-31
JP2011-080427 2011-03-31

Publications (1)

Publication Number Publication Date
WO2012133737A1 true WO2012133737A1 (fr) 2012-10-04

Family

ID=46931435

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/058521 WO2012133737A1 (fr) 2011-03-31 2012-03-30 Composé amine réticulable, membrane polymère utilisant un composé amine réticulable, et procédé de production de membrane polymère

Country Status (1)

Country Link
WO (1) WO2012133737A1 (fr)

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014179562A1 (fr) * 2013-05-01 2014-11-06 Massachusetts Institute Of Technology Dérivés de 1,3,5-triazinane-2,4,6-trione et leurs utilisations
US9181321B2 (en) 2013-03-14 2015-11-10 Shire Human Genetic Therapies, Inc. CFTR mRNA compositions and related methods and uses
US9193827B2 (en) 2010-08-26 2015-11-24 Massachusetts Institute Of Technology Poly(beta-amino alcohols), their preparation, and uses thereof
US9227917B2 (en) 2012-08-13 2016-01-05 Massachusetts Institute Of Technology Amine-containing lipidoids and uses thereof
US9238716B2 (en) 2011-03-28 2016-01-19 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US9308281B2 (en) 2011-06-08 2016-04-12 Shire Human Genetic Therapies, Inc. MRNA therapy for Fabry disease
US9512073B2 (en) 2011-10-27 2016-12-06 Massachusetts Institute Of Technology Amino acid-, peptide-and polypeptide-lipids, isomers, compositions, and uses thereof
US9522176B2 (en) 2013-10-22 2016-12-20 Shire Human Genetic Therapies, Inc. MRNA therapy for phenylketonuria
US9556110B2 (en) 2008-11-07 2017-01-31 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US9629804B2 (en) 2013-10-22 2017-04-25 Shire Human Genetic Therapies, Inc. Lipid formulations for delivery of messenger RNA
EP3046956A4 (fr) * 2013-09-19 2017-05-17 Microvention, Inc. Films polymères
US9840479B2 (en) 2014-07-02 2017-12-12 Massachusetts Institute Of Technology Polyamine-fatty acid derived lipidoids and uses thereof
US9850269B2 (en) 2014-04-25 2017-12-26 Translate Bio, Inc. Methods for purification of messenger RNA
WO2018008580A1 (fr) * 2016-07-06 2018-01-11 セメダイン株式会社 Composition durcissable et produit
US9907880B2 (en) 2015-03-26 2018-03-06 Microvention, Inc. Particles
US9938367B2 (en) 2013-09-19 2018-04-10 Terumo Corporation Polymer particles
US9957499B2 (en) 2013-03-14 2018-05-01 Translate Bio, Inc. Methods for purification of messenger RNA
US10022455B2 (en) 2014-05-30 2018-07-17 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10118980B1 (en) 2013-11-08 2018-11-06 Terumo Corporation Polymer particles
US10138213B2 (en) 2014-06-24 2018-11-27 Translate Bio, Inc. Stereochemically enriched compositions for delivery of nucleic acids
US10201632B2 (en) 2016-09-28 2019-02-12 Terumo Corporation Polymer particles
US10201618B2 (en) 2015-06-19 2019-02-12 Massachusetts Institute Of Technology Alkenyl substituted 2,5-piperazinediones, compositions, and uses thereof
NO20180619A1 (en) * 2018-04-30 2019-10-31 Sintef Tto As Surface modified membranes
CN110799492A (zh) * 2017-04-28 2020-02-14 爱康泰生治疗公司 用于递送核酸的新型羰基脂质和脂质纳米颗粒制剂
US10576166B2 (en) 2009-12-01 2020-03-03 Translate Bio, Inc. Liver specific delivery of messenger RNA
US11135556B2 (en) 2019-03-04 2021-10-05 Saudi Arabian Oil Company Crosslinked polyethylene glycol polymer membranes for gas separation
US11173190B2 (en) 2017-05-16 2021-11-16 Translate Bio, Inc. Treatment of cystic fibrosis by delivery of codon-optimized mRNA encoding CFTR
US11174500B2 (en) 2018-08-24 2021-11-16 Translate Bio, Inc. Methods for purification of messenger RNA
US11224642B2 (en) 2013-10-22 2022-01-18 Translate Bio, Inc. MRNA therapy for argininosuccinate synthetase deficiency
US11253605B2 (en) 2017-02-27 2022-02-22 Translate Bio, Inc. Codon-optimized CFTR MRNA
US11254936B2 (en) 2012-06-08 2022-02-22 Translate Bio, Inc. Nuclease resistant polynucleotides and uses thereof
CN114656714A (zh) * 2022-03-01 2022-06-24 山东清田塑工有限公司 高强易回收地膜及其制备方法
US11524932B2 (en) 2017-08-17 2022-12-13 Acuitas Therapeutics, Inc. Lipids for use in lipid nanoparticle formulations
US11542225B2 (en) 2017-08-17 2023-01-03 Acuitas Therapeutics, Inc. Lipids for use in lipid nanoparticle formulations
US11951181B2 (en) 2023-04-03 2024-04-09 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010070751A (ja) * 2008-08-19 2010-04-02 Kawamura Inst Of Chem Res 有機ポリマー多孔質体、及びその製造方法
JP2010070753A (ja) * 2008-08-19 2010-04-02 Kawamura Inst Of Chem Res 有機無機複合体、及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010070751A (ja) * 2008-08-19 2010-04-02 Kawamura Inst Of Chem Res 有機ポリマー多孔質体、及びその製造方法
JP2010070753A (ja) * 2008-08-19 2010-04-02 Kawamura Inst Of Chem Res 有機無機複合体、及びその製造方法

Cited By (106)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11414393B2 (en) 2008-11-07 2022-08-16 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US10844028B2 (en) 2008-11-07 2020-11-24 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US10189802B2 (en) 2008-11-07 2019-01-29 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US9556110B2 (en) 2008-11-07 2017-01-31 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US10576166B2 (en) 2009-12-01 2020-03-03 Translate Bio, Inc. Liver specific delivery of messenger RNA
US9193827B2 (en) 2010-08-26 2015-11-24 Massachusetts Institute Of Technology Poly(beta-amino alcohols), their preparation, and uses thereof
US10933139B2 (en) 2011-03-28 2021-03-02 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US9238716B2 (en) 2011-03-28 2016-01-19 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US10117934B2 (en) 2011-03-28 2018-11-06 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US11052159B2 (en) 2011-06-08 2021-07-06 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US11338044B2 (en) 2011-06-08 2022-05-24 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US11547764B2 (en) 2011-06-08 2023-01-10 Translate Bio, Inc. Lipid nanoparticle compositions and methods for MRNA delivery
US9597413B2 (en) 2011-06-08 2017-03-21 Shire Human Genetic Therapies, Inc. Pulmonary delivery of mRNA
US10507249B2 (en) 2011-06-08 2019-12-17 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US9308281B2 (en) 2011-06-08 2016-04-12 Shire Human Genetic Therapies, Inc. MRNA therapy for Fabry disease
US10413618B2 (en) 2011-06-08 2019-09-17 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US10350303B1 (en) 2011-06-08 2019-07-16 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US11185595B2 (en) 2011-06-08 2021-11-30 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US10888626B2 (en) 2011-06-08 2021-01-12 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US11730825B2 (en) 2011-06-08 2023-08-22 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US11291734B2 (en) 2011-06-08 2022-04-05 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US10238754B2 (en) 2011-06-08 2019-03-26 Translate Bio, Inc. Lipid nanoparticle compositions and methods for MRNA delivery
US11458158B2 (en) 2011-10-27 2022-10-04 Massachusetts Institute Of Technology Amino acid-, peptide- and polypeptide-lipids, isomers, compositions, and uses thereof
US10086013B2 (en) 2011-10-27 2018-10-02 Massachusetts Institute Of Technology Amino acid-, peptide- and polypeptide-lipids, isomers, compositions, and uses thereof
US9512073B2 (en) 2011-10-27 2016-12-06 Massachusetts Institute Of Technology Amino acid-, peptide-and polypeptide-lipids, isomers, compositions, and uses thereof
US10682374B2 (en) 2011-10-27 2020-06-16 Massachusetts Intstitute Of Technology Amino acid-, peptide- and polypeptide-lipids, isomers, compositions, and uses thereof
US11254936B2 (en) 2012-06-08 2022-02-22 Translate Bio, Inc. Nuclease resistant polynucleotides and uses thereof
US9439968B2 (en) 2012-08-13 2016-09-13 Massachusetts Institute Of Technology Amine-containing lipidoids and uses thereof
US9227917B2 (en) 2012-08-13 2016-01-05 Massachusetts Institute Of Technology Amine-containing lipidoids and uses thereof
US11510937B2 (en) 2013-03-14 2022-11-29 Translate Bio, Inc. CFTR MRNA compositions and related methods and uses
US11820977B2 (en) 2013-03-14 2023-11-21 Translate Bio, Inc. Methods for purification of messenger RNA
US10876104B2 (en) 2013-03-14 2020-12-29 Translate Bio, Inc. Methods for purification of messenger RNA
US11692189B2 (en) 2013-03-14 2023-07-04 Translate Bio, Inc. Methods for purification of messenger RNA
US9181321B2 (en) 2013-03-14 2015-11-10 Shire Human Genetic Therapies, Inc. CFTR mRNA compositions and related methods and uses
US9957499B2 (en) 2013-03-14 2018-05-01 Translate Bio, Inc. Methods for purification of messenger RNA
US10420791B2 (en) 2013-03-14 2019-09-24 Translate Bio, Inc. CFTR MRNA compositions and related methods and uses
US9713626B2 (en) 2013-03-14 2017-07-25 Rana Therapeutics, Inc. CFTR mRNA compositions and related methods and uses
US20140329884A1 (en) * 2013-05-01 2014-11-06 Massachusetts Institute Of Technology 1,3,5-triazinane-2,4,6-trione derivatives and uses thereof
US9315472B2 (en) * 2013-05-01 2016-04-19 Massachusetts Institute Of Technology 1,3,5-triazinane-2,4,6-trione derivatives and uses thereof
WO2014179562A1 (fr) * 2013-05-01 2014-11-06 Massachusetts Institute Of Technology Dérivés de 1,3,5-triazinane-2,4,6-trione et leurs utilisations
US11135167B2 (en) 2013-09-19 2021-10-05 Terumo Corporation Polymer particles
EP3046956A4 (fr) * 2013-09-19 2017-05-17 Microvention, Inc. Films polymères
US10144793B2 (en) 2013-09-19 2018-12-04 Terumo Corporation Polymer particles
US10227463B2 (en) 2013-09-19 2019-03-12 Microvention, Inc. Polymer films
US11786630B2 (en) 2013-09-19 2023-10-17 Terumo Corporation Polymer particles
US9938367B2 (en) 2013-09-19 2018-04-10 Terumo Corporation Polymer particles
US11104772B2 (en) 2013-09-19 2021-08-31 Microvention, Inc. Polymer films
US10493031B2 (en) 2013-10-22 2019-12-03 Translate Bio, Inc. Lipid formulations for delivery of messenger RNA
US11224642B2 (en) 2013-10-22 2022-01-18 Translate Bio, Inc. MRNA therapy for argininosuccinate synthetase deficiency
US9629804B2 (en) 2013-10-22 2017-04-25 Shire Human Genetic Therapies, Inc. Lipid formulations for delivery of messenger RNA
US10959953B2 (en) 2013-10-22 2021-03-30 Translate Bio, Inc. Lipid formulations for delivery of messenger RNA
US9522176B2 (en) 2013-10-22 2016-12-20 Shire Human Genetic Therapies, Inc. MRNA therapy for phenylketonuria
US11890377B2 (en) 2013-10-22 2024-02-06 Translate Bio, Inc. Lipid formulations for delivery of messenger RNA
US10208295B2 (en) 2013-10-22 2019-02-19 Translate Bio, Inc. MRNA therapy for phenylketonuria
US11377642B2 (en) 2013-10-22 2022-07-05 Translate Bio, Inc. mRNA therapy for phenylketonuria
US10052284B2 (en) 2013-10-22 2018-08-21 Translate Bio, Inc. Lipid formulations for delivery of messenger RNA
US11261274B2 (en) 2013-11-08 2022-03-01 Terumo Corporation Polymer particles
US10519264B2 (en) 2013-11-08 2019-12-31 Terumo Corporation Polymer particles
US10118980B1 (en) 2013-11-08 2018-11-06 Terumo Corporation Polymer particles
US11059841B2 (en) 2014-04-25 2021-07-13 Translate Bio, Inc. Methods for purification of messenger RNA
US11884692B2 (en) 2014-04-25 2024-01-30 Translate Bio, Inc. Methods for purification of messenger RNA
US10155785B2 (en) 2014-04-25 2018-12-18 Translate Bio, Inc. Methods for purification of messenger RNA
US9850269B2 (en) 2014-04-25 2017-12-26 Translate Bio, Inc. Methods for purification of messenger RNA
US10493166B2 (en) 2014-05-30 2019-12-03 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10912844B2 (en) 2014-05-30 2021-02-09 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US11433144B2 (en) 2014-05-30 2022-09-06 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10286083B2 (en) 2014-05-30 2019-05-14 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10293057B2 (en) 2014-05-30 2019-05-21 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10022455B2 (en) 2014-05-30 2018-07-17 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10286082B2 (en) 2014-05-30 2019-05-14 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US11104652B2 (en) 2014-06-24 2021-08-31 Translate Bio, Inc. Stereochemically enriched compositions for delivery of nucleic acids
US10138213B2 (en) 2014-06-24 2018-11-27 Translate Bio, Inc. Stereochemically enriched compositions for delivery of nucleic acids
US9840479B2 (en) 2014-07-02 2017-12-12 Massachusetts Institute Of Technology Polyamine-fatty acid derived lipidoids and uses thereof
US10543295B2 (en) 2015-03-26 2020-01-28 Microvention, Inc. Particles
US10155064B2 (en) 2015-03-26 2018-12-18 Microvention, Inc. Particles
US10792390B2 (en) 2015-03-26 2020-10-06 Microvention, Inc. Particles
US9907880B2 (en) 2015-03-26 2018-03-06 Microvention, Inc. Particles
US11857694B2 (en) 2015-03-26 2024-01-02 Microvention, Inc. Particles
US10201618B2 (en) 2015-06-19 2019-02-12 Massachusetts Institute Of Technology Alkenyl substituted 2,5-piperazinediones, compositions, and uses thereof
US10695444B2 (en) 2015-06-19 2020-06-30 Massachusetts Institute Of Technology Alkenyl substituted 2,5-piperazinediones, compositions, and uses thereof
WO2018008580A1 (fr) * 2016-07-06 2018-01-11 セメダイン株式会社 Composition durcissable et produit
JPWO2018008580A1 (ja) * 2016-07-06 2019-04-25 セメダイン株式会社 硬化性組成物、及び製品
US11617814B2 (en) 2016-09-28 2023-04-04 Terumo Corporation Methods of treatment comprising administering polymer particles configured for intravascular delivery of pharmaceutical agents
US11110198B2 (en) 2016-09-28 2021-09-07 Terumo Corporation Polymer particles
CN109789239A (zh) * 2016-09-28 2019-05-21 泰尔茂株式会社 聚合物颗粒
US10729805B2 (en) 2016-09-28 2020-08-04 Terumo Corporation Drug delivery polymer particles with hydrolytically degradable linkages
US10632226B2 (en) 2016-09-28 2020-04-28 Terumo Corporation Polymer particles
CN109789239B (zh) * 2016-09-28 2021-01-22 泰尔茂株式会社 聚合物颗粒
US10201632B2 (en) 2016-09-28 2019-02-12 Terumo Corporation Polymer particles
US11759545B2 (en) 2016-09-28 2023-09-19 Terumo Corporation Polymer particles
US10328175B2 (en) 2016-09-28 2019-06-25 Terumo Corporation Polymer particles
US11253605B2 (en) 2017-02-27 2022-02-22 Translate Bio, Inc. Codon-optimized CFTR MRNA
US11820728B2 (en) 2017-04-28 2023-11-21 Acuitas Therapeutics, Inc. Carbonyl lipids and lipid nanoparticle formulations for delivery of nucleic acids
CN110799492A (zh) * 2017-04-28 2020-02-14 爱康泰生治疗公司 用于递送核酸的新型羰基脂质和脂质纳米颗粒制剂
CN110799492B (zh) * 2017-04-28 2023-06-27 爱康泰生治疗公司 用于递送核酸的新型羰基脂质和脂质纳米颗粒制剂
US11173190B2 (en) 2017-05-16 2021-11-16 Translate Bio, Inc. Treatment of cystic fibrosis by delivery of codon-optimized mRNA encoding CFTR
US11542225B2 (en) 2017-08-17 2023-01-03 Acuitas Therapeutics, Inc. Lipids for use in lipid nanoparticle formulations
US11524932B2 (en) 2017-08-17 2022-12-13 Acuitas Therapeutics, Inc. Lipids for use in lipid nanoparticle formulations
US11679356B2 (en) 2018-04-30 2023-06-20 Sintef Tto As Surface modified membranes for gas separation, and a method for preparing thereof
NO20180619A1 (en) * 2018-04-30 2019-10-31 Sintef Tto As Surface modified membranes
US11174500B2 (en) 2018-08-24 2021-11-16 Translate Bio, Inc. Methods for purification of messenger RNA
US11135556B2 (en) 2019-03-04 2021-10-05 Saudi Arabian Oil Company Crosslinked polyethylene glycol polymer membranes for gas separation
CN114656714A (zh) * 2022-03-01 2022-06-24 山东清田塑工有限公司 高强易回收地膜及其制备方法
US11951181B2 (en) 2023-04-03 2024-04-09 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US11951180B2 (en) 2023-04-03 2024-04-09 Translate Bio, Inc. Lipid nanoparticle compositions and methods for MRNA delivery
US11951179B2 (en) 2023-04-03 2024-04-09 Translate Bio, Inc. Lipid nanoparticle compositions and methods for MRNA delivery

Similar Documents

Publication Publication Date Title
WO2012133737A1 (fr) Composé amine réticulable, membrane polymère utilisant un composé amine réticulable, et procédé de production de membrane polymère
JP5314291B2 (ja) 高分子膜およびその製造方法
JP5945478B2 (ja) 分離膜、複合分離膜及び分離膜の製造方法
JP5526055B2 (ja) ガス分離膜、ガス分離膜の製造方法、ガス混合物の分離方法、ガス分離膜モジュール及び気体分離装置
US10336873B2 (en) Functional polymer membrane, manufacturing method therefor, ion exchange membrane and proton conductive membrane equipped with functional polymer membrane, and ion exchange device
US8992668B2 (en) Gas separation membrane and method for producing the same, and method for separating gas mixture, gas separation membrane module and gas separation apparatus using the same
KR101136943B1 (ko) 내오염성이 향상된 친수성 분리막의 제조방법 및 상기 방법으로 제조된 친수성 분리막
JP6235479B2 (ja) Ｃｏ２ガス分離膜及びその製造方法
US9238204B2 (en) Gas separation composite membrane and gas separating module, gas separation apparatus and gas separation method using the same
US9272248B2 (en) Gas separation composite membrane, and gas separating module, gas separation apparatus and gas separation method using the same
JP2009241006A (ja) 複合膜およびその製造方法
CN111542384B (zh) 用于酸气分离的聚合物共混膜
US9764293B2 (en) Gas separation composite membrane, method of producing the same, gas separating module using the same, and gas separation apparatus and gas separation method
JP5969169B2 (ja) 複合分離膜
JP2011041938A (ja) ガス分離膜及び複合膜、それらの製造方法、それらを用いたモジュール、分離装置
JP5893578B2 (ja) 機能性複合膜及びその製造方法、並びに機能性複合膜を具備したイオン交換膜及びプロトン伝導膜
JP5459205B2 (ja) 複合半透膜およびその製造方法
WO2018030114A1 (fr) Membrane de séparation de gaz, module de membranes de séparation de gaz et dispositif de séparation de gaz
WO2018020949A1 (fr) Membrane de séparation de gaz, module de membrane de séparation de gaz et dispositif de séparation de gaz
WO2011122560A1 (fr) Membrane composite semi-perméable
WO2013080890A1 (fr) Membrane de séparation de gaz, procédé de fabrication de celle-ci, et module de membranes de séparation de gaz mettant en œuvre celle-ci
JPH0523820B2 (fr)

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: 12765391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12765391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP