WO2013047265A1 - 気体分離膜 - Google Patents
気体分離膜 Download PDFInfo
- Publication number
- WO2013047265A1 WO2013047265A1 PCT/JP2012/073817 JP2012073817W WO2013047265A1 WO 2013047265 A1 WO2013047265 A1 WO 2013047265A1 JP 2012073817 W JP2012073817 W JP 2012073817W WO 2013047265 A1 WO2013047265 A1 WO 2013047265A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas separation
- separation membrane
- polyacetal
- carbon atoms
- trioxane
- Prior art date
Links
- 238000000926 separation method Methods 0.000 title claims abstract description 50
- 239000012528 membrane Substances 0.000 title claims abstract description 41
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 40
- 229930182556 Polyacetal Natural products 0.000 claims abstract description 39
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 21
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- -1 cyclic acetals Chemical class 0.000 claims description 18
- 229920005992 thermoplastic resin Polymers 0.000 claims description 16
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 7
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- LMTDPKYREUZYAO-UHFFFAOYSA-N 1,4-dioxepane Chemical compound C1COCCOC1 LMTDPKYREUZYAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- JPEGUDKOYOIOOP-UHFFFAOYSA-N 2-(hexoxymethyl)oxirane Chemical compound CCCCCCOCC1CO1 JPEGUDKOYOIOOP-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- B01D71/52—Polyethers
- B01D71/521—Aliphatic polyethers
- B01D71/5211—Polyethylene glycol or polyethyleneoxide
-
- 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
- B01D71/52—Polyethers
-
- 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
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
-
- 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
- B01D2053/221—Devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/22—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- 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
Definitions
- the present invention relates to a gas separation membrane containing a specific polyacetal as a main component.
- Polyacetal is excellent in mechanical strength, chemical resistance, wear resistance, etc., and has good molding processability. Therefore, it is an engineering plastics that forms machine industrial parts, automotive parts, electrical equipment parts, and other industrial products. Widely used as a material. However, while other thermoplastic resins have expanded their use in the field of films, polyacetal is rarely used as a film.
- One of the expected applications is a gas separation membrane of polyacetal, and it has been shown in the past that polyacetal has high separation ability (ratio of gas permeability coefficient) of CO 2 , NO 2 , SO 2 to N 2 . (For example, refer to Patent Document 1, Non-Patent Documents 1 and 2).
- An object of the present invention is to provide a gas separation membrane made of polyacetal having high CO 2 separation ability and high permeation rate.
- the present invention is as follows: [1] A gas separation membrane mainly composed of polyacetal having 1.5 to 10 mol of oxyalkylene units having 2 or more carbon atoms per 100 mol of oxymethylene units. [2] Gas separation according to the above [1], wherein the polyacetal is a copolymer obtained from trioxane and a compound capable of copolymerizing with trioxane to give an oxyalkylene unit having two or more carbon atoms. film.
- the compound giving an oxyalkylene unit having two or more carbon atoms copolymerizable with trioxane is at least one selected from cyclic acetal, cyclic ether, vinyl ether and allyl ether, The gas separation membrane according to the above [2].
- the compound that gives an oxyalkylene unit having two or more carbon atoms copolymerizable with trioxane is at least selected from 1,3-dioxolane, 1,4-dioxepane, alkyl glycidyl ether, vinyl ether and allyl ether
- thermoplastic resin is polyester or polyether resin.
- thermoplastic resin is at least one selected from polylactic acid, polyhydroxybutyric acid, polyglycolic acid, polydioxolane, polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
- the gas separation membrane as described.
- thermoplastic resin is contained in an amount of 1 to 80 parts by mass with respect to 100 parts by mass of the main component polyacetal.
- the present invention it is possible to provide a gas separation membrane having an excellent ability to selectively separate carbon dioxide gas (CO 2 ) as compared with a conventional polymer gas separation membrane.
- the gas separation membrane of the present invention is particularly suitable as a carbon dioxide separation membrane in exhaust gas discharged in large quantities from thermal power plants and factories.
- the polyacetal used as a main component in the gas separation membrane of the present invention is a copolymer containing an oxymethylene unit and an oxyalkylene unit having two or more carbon atoms, and two or more carbons per 100 mol of the oxymethylene unit.
- polyacetal according to the present invention such polyacetal is referred to as “polyacetal according to the present invention”.
- the oxyalkylene unit having 2 or more carbon atoms in the polyacetal according to the present invention is preferably an oxyalkylene unit having 2 to 6 carbon atoms, more preferably an oxyalkylene unit having 2 to 4 carbon atoms. Particularly preferred are oxyalkylene units having 2 or 3 carbon atoms.
- the oxyalkylene unit having two or more carbon atoms may be one type or two or more types.
- the polyacetal according to the present invention includes, for example, a compound that gives an oxyalkylene unit having two or more carbon atoms that can be copolymerized with 1,3,5-trioxane as a monomer and with 1,3,5-trioxane. It can be obtained by a bulk polymerization method in which a cationic polymerization initiator such as boron trifluoride may be added as necessary. Examples of such comonomers include cyclic acetals, cyclic ethers, vinyl ethers, and allyl ethers.
- Examples of the cyclic acetal include 1,3-dioxolane, 1,4-dioxepane and derivatives thereof, and 1,3-dioxolane is particularly preferable.
- Examples of the cyclic ether include alkylene oxides having 2 to 6 carbon atoms such as ethylene oxide and propylene oxide, epoxy compounds, glycidyl ether compounds and the like, and particularly 4 to 10 such as butyl glycidyl ether and hexyl glycidyl ether. Alkyl glycidyl ethers having the following carbon atoms are preferred.
- Vinyl ether and allyl ether mean compounds having a vinyl ether structure (CH 2 ⁇ CH—O—) or an allyl ether structure (CH 2 ⁇ CH—CH 2 —O—), for example, mono, di, tri or poly ( Ethylene glycol) vinyl ether or allyl ether of monoalkyl ether.
- One or more of these comonomers are selected and introduced into the polyacetal so that the oxyalkylene unit having two or more carbon atoms falls within a predetermined range.
- a unit different from the oxymethylene unit and the oxyalkylene unit may be introduced as long as the CO 2 separation ability and the permeation rate are not impaired.
- Additional comonomers that provide such different units include, for example, cyclic siloxanes such as decamethylsiloxane.
- the amount of comonomer introduced into the polyacetal according to the present invention is 1 oxyalkylene unit having 2 or more carbon atoms (derived from the comonomer) when the oxymethylene unit (derived mainly from trioxane) is 100 mol. It is preferably 5 to 10 mol, particularly 2 to 6 mol. It is preferred to use 1,3-dioxolane or 1,4-dioxepane as the comonomer.
- the introduction amount of the comonomer can be calculated from the charged amount of the monomer and comonomer, or from the NMR spectrum data of the obtained copolymer.
- the polyacetal according to the present invention preferably has a melt index in the range of 0.5 to 50 g / 10 min.
- the gas separation membrane of the present invention can be obtained by forming a film of the polyacetal according to the present invention or a composition containing it as a main component.
- a composition may contain other thermoplastic resins, and may contain a small amount of an antioxidant, a heat stabilizer and other necessary additives.
- main component means that the composition (or the gas separation membrane of the present invention) contains at least 50% by mass, preferably 60% by mass or more of the polyacetal according to the present invention. To do.
- thermoplastic resin that can be contained in such a composition (or the gas separation membrane of the present invention), the heat resistance of the gas separation membrane is not significantly reduced, and the CO 2 separation ability and permeation rate of the polyacetal according to the present invention are increased.
- polyester, polyether resin, etc. are mentioned.
- polyester resin include polylactic acid, polyhydroxybutyric acid, and polyglycolic acid.
- polyether resins include polydioxolane, polyethylene glycol, polypropylene glycol and polytetramethylene glycol. It is preferable to use polylactic acid and / or polydioxolane as the thermoplastic resin.
- the blending amount of the thermoplastic resin is preferably in the range of 1 to 80 parts by mass with respect to 100 parts by mass of the polyacetal according to the present invention.
- the gas separation membrane of the present invention can be produced from the polyacetal according to the present invention or a composition containing the same as a main component by a production method known to those skilled in the art.
- the polyacetal according to the present invention or a composition comprising the same as a main component is formed into a film by hot pressing or a melt extrusion molding method, or a uniaxially or biaxially stretched one. Preferably used.
- a film obtained by dissolving the polyacetal according to the present invention or a composition containing the polyacetal as a main component in an appropriate solvent, casting, and drying may be used.
- the solvent include hexafluoroisopropanol, high-boiling solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and benzyl alcohol (dissolved at a temperature higher than 100 ° C.).
- the shape of the gas separation membrane of the present invention is not limited to a film, and can be used as a known shape such as a tube or a hollow fiber.
- the monomers, comonomers, catalysts, thermoplastic resins, solvents and the like used in the present invention are all available from reagent suppliers or can be prepared by methods known to those skilled in the art.
- Examples 1 to 12 and Comparative Examples 1 and 2 A polyacetal was produced by batch polymerization using a desktop biaxial kneader having an internal volume of 1000 cc having a Z-shaped blade inside and a jacket structure capable of circulating hot water. 70 ° C. warm water was circulated through the jacket, and the inside of the mixer was heated and dried with a heat gun with the lid removed, and then the lid was attached and the system was purged with nitrogen.
- the measurement of gas permeability was performed by a differential pressure method based on JIS K7126. Specifically, a gas chromatograph was used as a detector, and a differential pressure gas / vapor permeability measuring device (GTR-30XAD, G6800T • F (S)) [GTR Tech Co., Ltd., Yanaco Technical Science Co., Ltd.] was used. The test differential pressure was 1 atm, and a dry gas was used. The test temperature was 23 ⁇ 2 ° C., and the transmission area was 1.52 ⁇ 10 ⁇ 3 m 2 ( ⁇ 4.4 ⁇ 10 ⁇ 2 m). The results are shown in Table 1.
- thermoplastic resin in Examples 10 to 12 was produced as follows.
- As the polymerization apparatus an apparatus similar to that used for the production of polyacetal was used. Hot water at 50 ° C. was circulated through the jacket, and the inside of the mixer was heated and dried with a heat gun with the lid removed, and then the lid was attached and the system was purged with nitrogen. 200 g of 1,3-dioxolane was injected from the raw material inlet, 0.003 parts by mass of phosphotungstic acid was added to 100 parts by mass of 1,3-dioxolane charged, and the polymerization was continued for 20 minutes. went.
- the reaction was stopped by adding a triethylamine / benzene solution.
- the solid content was filtered off, washed with acetone and vacuum dried at room temperature. The yield calculated from the obtained solid was 75%. Further, the melt index (MI value) was measured by ASTM-D1238 (under 2.16 kg load) and the measurement temperature was changed to 100 ° C., and it was 1.6.
- Gas separation membranes (Examples 1 to 12) containing polyacetal as a main component according to the present invention and containing a predetermined amount of an oxyalkylene unit having two or more carbon atoms derived from a comonomer are conventional polymer gas separation membranes ( Compared with Comparative Examples 1 and 2, the permeation rate was high, and the ability to selectively separate carbon dioxide (CO 2 ) from oxygen gas and nitrogen gas, particularly nitrogen gas, was excellent. Therefore, the gas separation membrane of the present invention is expected to be useful as a carbon dioxide separation membrane in exhaust gas discharged in large quantities from thermal power plants and factories.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
[1]オキシメチレンユニット100molに対して2個以上の炭素原子を有するオキシアルキレンユニットが1.5~10molであるポリアセタールを主成分とする気体分離膜。
[2]ポリアセタールが、トリオキサン、及びトリオキサンと共重合可能な、2個以上の炭素原子を有するオキシアルキレンユニットを与える化合物より得られるコポリマーであることを特徴とする、上記[1]記載の気体分離膜。
[3]トリオキサンと共重合可能な、2個以上の炭素原子を有するオキシアルキレンユニットを与える化合物が、環状アセタール、環状エーテル、ビニルエーテル及びアリルエーテルから選ばれる少なくとも1種であることを特徴とする、上記[2]記載の気体分離膜。
[4]トリオキサンと共重合可能な、2個以上の炭素原子を有するオキシアルキレンユニットを与える化合物が、1,3-ジオキソラン、1,4-ジオキセパン、アルキルグリシジルエーテル、ビニルエーテル及びアリルエーテルから選ばれる少なくとも1種であることを特徴とする、上記[2]記載の気体分離膜。
[5]さらに熱可塑性樹脂を含有することを特徴とする、上記[1]記載の気体分離膜。
[6]熱可塑性樹脂が、ポリエステル又はポリエーテル樹脂であることを特徴とする、上記[5]記載の気体分離膜。
[7]熱可塑性樹脂が、ポリ乳酸、ポリヒドロキシ酪酸、ポリグリコール酸、ポリジオキソラン、ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレングリコールから選ばれる少なくとも1種であることを特徴とする、上記[5]記載の気体分離膜。
[8]主成分であるポリアセタール100質量部に対し、熱可塑性樹脂を1~80質量部で含有することを特徴とする、上記[5]記載の気体分離膜。
重合装置として、内部にZ型翼を有し、温水循環が可能なジャケット構造をする内容積1000ccの卓上型二軸混練機を用い、バッチ式の重合によりポリアセタールの製造を実施した。
ジャケットに70℃の温水を循環させ、蓋を取り外した状態で混線機内部をヒートガンで加熱乾燥した後、蓋を取り付け、系内を窒素置換した。原料投入口より1,3,5-トリオキサン200g及び下記表1に記載のコモノマーの所定量を注入し、高速運転しながら攪拌後、三フッ化ホウ素ジエチルエーテラートを触媒量(1,3,5-トリオキサン 1molに対して0.04mmol)添加し、重合を20分間行った。その後、トリエチルアミン/ベンゼン溶液を加え反応を停止し、系内よりポリアセタールを採り出しミキサーで粉砕してポリアセタール粗共重合体を得た。得られたポリアセタール粗共重合体中の固形分率を収率として計算したところ、いずれも90%以上であった。
結果を表1に合わせて示す。
実施例10~12で熱可塑性樹脂として用いたポリジオキソランは、以下のようにして製造した。
重合装置としてはポリアセタールの製造と同様の装置を用いた。
ジャケットに50℃の温水を循環させ、蓋を取り外した状態で混線機内部をヒートガンで加熱乾燥した後、蓋を取り付け、系内を窒素置換した。原料投入口より1,3-ジオキソラン200gを注入し、高速で攪拌しながら、仕込みの1,3-ジオキソラン100質量部に対して0.003質量部のリンタングステン酸を添加し、重合を20分間行った。その後、トリエチルアミン/ベンゼン溶液を加え反応を停止した。次に、ミキサーへ水:メタノール=4:1(容積比)に対して1wt%のトリエチルアミンを添加した溶液、更にポリジオキソランを投入し、混合しながら完全に反応を停止させるとともに残存するモノマーを除去した。固形分はろ別後、アセトンで洗浄後に常温で真空乾燥させた。得られた固形分から収率を計算したところ、75%であった。またASTM-D1238(2.16kg荷重下)で測定温度を100℃に変更して溶融指数(MI値)を測定したところ、1.6であった。
Claims (8)
- オキシメチレンユニット100molに対して2個以上の炭素原子を有するオキシアルキレンユニットが1.5~10molであるポリアセタールを主成分とする気体分離膜。
- ポリアセタールが、トリオキサン、及びトリオキサンと共重合可能な、2個以上の炭素原子を有するオキシアルキレンユニットを与える化合物より得られるコポリマーであることを特徴とする、請求項1記載の気体分離膜。
- トリオキサンと共重合可能な、2個以上の炭素原子を有するオキシアルキレンユニットを与える化合物が、環状アセタール、環状エーテル、ビニルエーテル及びアリルエーテルから選ばれる少なくとも1種であることを特徴とする、請求項2記載の気体分離膜。
- トリオキサンと共重合可能な、2個以上の炭素原子を有するオキシアルキレンユニットを与える化合物が、1,3-ジオキソラン、1,4-ジオキセパン、アルキルグリシジルエーテル、ビニルエーテル及びアリルエーテルから選ばれる少なくとも1種であることを特徴とする、請求項2記載の気体分離膜。
- さらに熱可塑性樹脂を含有することを特徴とする、請求項1記載の気体分離膜。
- 熱可塑性樹脂が、ポリエステル又はポリエーテル樹脂であることを特徴とする、請求項5記載の気体分離膜。
- 熱可塑性樹脂が、ポリ乳酸、ポリヒドロキシ酪酸、ポリグリコール酸、ポリジオキソラン、ポリエチレングリコール、ポリプロピレングリコール及びポリテトラメチレングリコールから選ばれる少なくとも1種であることを特徴とする、請求項5記載の気体分離膜。
- 主成分であるポリアセタール100質量部に対し、熱可塑性樹脂を1~80質量部で含有することを特徴とする、請求項4記載の気体分離膜。
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EP12835746.4A EP2762224B1 (en) | 2011-09-27 | 2012-09-18 | Use of gas separation membrane for carbon dioxide separation |
CN201280047275.XA CN103842061B (zh) | 2011-09-27 | 2012-09-18 | 气体分离膜 |
KR1020147011102A KR101885362B1 (ko) | 2011-09-27 | 2012-09-18 | 기체 분리막 |
JP2013536188A JP6070562B2 (ja) | 2011-09-27 | 2012-09-18 | 気体分離膜 |
US14/347,148 US9295951B2 (en) | 2011-09-27 | 2012-09-18 | Gas separation membrane |
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EP2762224A4 (en) | 2015-05-27 |
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