JPH02174924A - Preparation of conjugate film - Google Patents
Preparation of conjugate filmInfo
- Publication number
- JPH02174924A JPH02174924A JP29446589A JP29446589A JPH02174924A JP H02174924 A JPH02174924 A JP H02174924A JP 29446589 A JP29446589 A JP 29446589A JP 29446589 A JP29446589 A JP 29446589A JP H02174924 A JPH02174924 A JP H02174924A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- membrane
- dense layer
- film
- anisotropic
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 229920001721 polyimide Polymers 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000009719 polyimide resin Substances 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims description 91
- 238000004519 manufacturing process Methods 0.000 claims description 11
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 13
- 238000004132 cross linking Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000926 separation method Methods 0.000 description 21
- 238000000108 ultra-filtration Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 230000004907 flux Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000004642 Polyimide Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- JUYIUHMASUKIFJ-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol 1-methylpyrrolidin-2-one Chemical compound CN1C(CCC1)=O.C(COCCO)O JUYIUHMASUKIFJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は複合膜の製造方法に関し、詳しくは、特に分子
量が数十乃至数千程度の比較的小さい溶質を含有する有
機溶液の膜分離処理や、気体の濃縮分離に好適に用いる
ことができる複合膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a composite membrane, and more specifically, to a method for producing a composite membrane, particularly for membrane separation treatment of organic solutions containing relatively small solutes with molecular weights ranging from several tens to several thousand, and for concentrating and separating gases. The present invention relates to a method for manufacturing a composite membrane that can be suitably used.
一般に溶液やエマルジョン、サスペンションのような液
体混合物中の特定の成分を選択的に除去するに際して、
近年、半透膜を用いる分離方法が注目され、既に一部で
は実用化されるに至っているが、しかし、従来、かかる
半透膜による分離処理は、主として水性の液体混合物の
分離に限られている。よく知られているように、セロハ
ン、酢酸セルロース等を素材とする半透膜は、有機溶剤
に対する抵抗性が殆どなく、また、ポリ塩化ビニル、ポ
リアクリロニトリル、ポリスルホン等の合成樹脂からな
る半透膜も通常の有機溶剤の多くに溶解若しくは膨潤す
るために、有機性の液体混合物の分離には使用できない
からであ企。しかしながら、膜分離は、水性の液体混合
物のみならず、有機性の液体混合物、代表的には有機溶
液についても必要性が高く、このため、従来より耐有機
溶剤性の半透膜の開発が要請されている。In general, when selectively removing specific components in liquid mixtures such as solutions, emulsions, and suspensions,
In recent years, separation methods using semipermeable membranes have attracted attention, and have already been put into practical use in some cases. However, conventionally, separation processes using such semipermeable membranes have been mainly limited to the separation of aqueous liquid mixtures. There is. As is well known, semipermeable membranes made of materials such as cellophane and cellulose acetate have almost no resistance to organic solvents, and semipermeable membranes made of synthetic resins such as polyvinyl chloride, polyacrylonitrile, and polysulfone have almost no resistance to organic solvents. However, it cannot be used to separate organic liquid mixtures because it dissolves or swells in many common organic solvents. However, membrane separation is highly necessary not only for aqueous liquid mixtures but also for organic liquid mixtures, typically organic solutions, and for this reason, there has been a demand for the development of semipermeable membranes that are resistant to organic solvents. has been done.
このような要請に応えるために、既に芳香族ポリイミド
樹脂からなる半透膜や、１，２．３．４−ブタンテトラ
カルボン酸又はその誘導体と芳香族ジアミンとを縮合さ
せて得られるポリイミド樹脂からなる半透膜が提案され
、また、一部実用化もされているが、これらポリイミド
樹脂半透膜が分離し得る溶質は従来、分子量が数千又は
それ以上に限られており、分子量が数十乃至数千程度の
比較的低分子量の溶質を分離し得る逆浸透、又は逆浸透
と限外濾過の中間領域の膜分離には適用することができ
ない。In order to meet these demands, we have already developed semipermeable membranes made of aromatic polyimide resins and polyimide resins obtained by condensing 1,2,3,4-butanetetracarboxylic acid or its derivatives with aromatic diamines. Semipermeable membranes have been proposed and some have been put into practical use, but the solutes that can be separated by these polyimide resin semipermeable membranes have conventionally been limited to molecular weights of several thousand or more; It cannot be applied to reverse osmosis, which can separate relatively low-molecular-weight solutes on the order of ten to several thousand, or to membrane separation in the intermediate range between reverse osmosis and ultrafiltration.
また、逆浸透領域において膜分離を実用的に行なうには
、用いる半透膜が低分子量の溶質に対して十分に大きい
排除率を有すると共に、溶剤について十分に大きい透過
流束を有することが要求されるが、一般に溶剤の透過流
束は主として膜の緻密層の厚さによって規制される。こ
のような観点から、溶質除去性能を有する表面の緻密層
がこれに連続する多孔質層によって一体的に支持されて
いる異方性構造を有する所謂異方性膜又は非対称膜に代
わって、最近、限外濾過性能を有するこのような異方性
膜を含む多孔性基材上に、更に半透性を有する一層緻密
な薄膜を新たに形成した複合半透膜が提案されている。In addition, in order to practically perform membrane separation in the reverse osmosis region, the semipermeable membrane used must have a sufficiently high rejection rate for low molecular weight solutes and a sufficiently high permeation flux for solvents. However, in general, the permeation flux of the solvent is mainly regulated by the thickness of the dense layer of the membrane. From this point of view, in place of so-called anisotropic membranes or asymmetric membranes, which have an anisotropic structure in which a dense layer on the surface with solute removal performance is integrally supported by a continuous porous layer, new membranes have been recently developed. A composite semipermeable membrane has been proposed in which a denser thin membrane having semipermeability is newly formed on a porous substrate containing such an anisotropic membrane having ultrafiltration performance.
しかし、このような複合半透膜も、多孔性基材としてポ
リスルホンやポリアクリロニトリル等からなる限外濾過
膜を用いているため、依然として有機溶液の分離処理に
は使用することができず、更に、限外濾過膜上に緻密層
を形成する場合にも、基材である限外濾過膜が耐有機溶
剤性に乏しいところから、緻密層を形成するための重合
体又はその前駆体物質の溶液として水性の溶液を用いざ
るを得す、従って、用いる重合体又はその前駆体物質が
制約され、この結果、必要な膜性能に応じて、緻密層を
形成するための素材を選択することができない。However, such composite semipermeable membranes still cannot be used for separation treatment of organic solutions because they use ultrafiltration membranes made of polysulfone, polyacrylonitrile, etc. as porous base materials. When forming a dense layer on an ultrafiltration membrane, since the ultrafiltration membrane as a base material has poor organic solvent resistance, it is necessary to use a solution of a polymer or its precursor substance to form a dense layer. It is necessary to use an aqueous solution, and therefore the polymer or its precursor substance to be used is restricted, and as a result, the material for forming the dense layer cannot be selected depending on the required membrane performance.
一方、分子量が数十以下の低分子量の溶質に対して有効
な排除能を有する半透膜は、気体間の分離や気体の濃縮
に有効であることが知られているが、気体分離を膜によ
って行なう場合、高温における程、気体の透過流束が大
きいために、高温で気体の膜分離処理を行なう方が有利
である。特に、近年、所謂Ｃ１化学の展開に伴い、合成
ガスのための分離膜が要求されるに至っており、特に、
このような目的のための気体分離膜は１００〜３００°
Ｃ１或いはそれ以上の高温で使用し得ることが望ましく
、極めて高い耐熱性が要求される。また、有機混合ガス
の分離には、当然に耐有機溶剤性も要求される。On the other hand, semipermeable membranes, which have an effective exclusion ability for low molecular weight solutes with a molecular weight of several dozen or less, are known to be effective in separating gases and concentrating gases. In this case, it is more advantageous to perform the gas membrane separation treatment at a higher temperature because the higher the temperature, the higher the gas permeation flux. In particular, in recent years, with the development of so-called C1 chemistry, separation membranes for synthesis gas have come to be required.
Gas separation membranes for such purposes are 100-300°
It is desirable that it can be used at high temperatures of C1 or higher, and extremely high heat resistance is required. Furthermore, organic solvent resistance is naturally required for the separation of organic mixed gases.
本発明は上記した種々の問題を解決するためになされた
ものであって、特に、分子量が数十乃至数千程度の低分
子量の溶質を含有する有機溶液の膜分離や、高温を含む
広い温度範囲における気体分離に好適に用いることがで
きる複合膜の製造方法を提供することを目的とする。The present invention has been made to solve the various problems described above, and is particularly applicable to membrane separation of organic solutions containing low molecular weight solutes with a molecular weight of several tens to several thousand, and a wide temperature range including high temperatures. It is an object of the present invention to provide a method for manufacturing a composite membrane that can be suitably used for gas separation in a wide range of areas.
本発明による複合膜の製造方法は、ポリイミド樹脂より
なり、表面の緻密層がこれに連続する多孔質層に一体に
支持されている異方性構造を有する膜の緻密層の表面に
、この膜の分画分子量と同等若しくはこれよりも大きい
平均分子量を有する架橋性樹脂の有機溶液を接触させ、
次に、上記樹脂を架橋させて、上記異方性膜の緻密層上
に有機溶剤に不溶性の樹脂よりなる薄膜を形成する複合
膜の製造方法であって、架橋性樹脂が分子内に２つ以上
の反応性基を有し、この反応性基が相互に架橋されて、
有機溶剤に不溶性の樹脂を形成する樹脂である複合膜の
製造方法において、架橋性樹脂がヒドロキシアルキルア
クリレ−１・及び／又はヒドロキシアルキルメタクリレ
ートを単量体成分とする共重合体樹脂であって、水酸基
と反応し得る官能基を分子内に２つ以上有する多官能性
化合物を架橋剤として架橋される樹脂であることを特徴
とする。The method for producing a composite membrane according to the present invention is to apply this membrane to the surface of a dense layer of a membrane made of polyimide resin and having an anisotropic structure in which a dense layer on the surface is integrally supported by a continuous porous layer. contact with an organic solution of a crosslinkable resin having an average molecular weight equivalent to or larger than the molecular weight cut-off,
Next, a method for producing a composite membrane in which the resin is crosslinked to form a thin film made of a resin insoluble in an organic solvent on the dense layer of the anisotropic membrane, the method comprising: two crosslinkable resins in the molecule; It has the above reactive groups, and these reactive groups are crosslinked with each other,
In the method for producing a composite membrane, which is a resin that forms a resin insoluble in an organic solvent, the crosslinkable resin is a copolymer resin containing hydroxyalkyl acrylate-1 and/or hydroxyalkyl methacrylate as a monomer component; , is characterized in that it is a resin that is crosslinked using a polyfunctional compound having two or more functional groups in the molecule that can react with hydroxyl groups as a crosslinking agent.
即ち、本発明によれば、架橋前は有機溶剤に可溶性であ
る架橋性樹脂を有機）容剤に溶解して、比較的希薄な有
機溶液となし、これをポリイミド樹脂の緻密層表面に接
触させて、樹脂溶液の薄膜を形成した後、この有機溶剤
を蒸発させ、更に架橋性樹脂を架橋させて、有機溶剤に
不溶性の樹脂からなる薄膜を形成させるもので、従来は
前記したように用いることが困難であった有機性の樹脂
溶液を用いて、樹脂薄膜を形成することができ、この結
果、基材ポリイミド樹脂限外濾過膜のすぐれた耐有機溶
剤性及び耐熱性と相俟って、特に有機溶液及び有機ガス
の分離濃縮、特に高温におけるこれら操作に好適に用い
ることができる複合膜の製造を可能とするものである。That is, according to the present invention, before crosslinking, a crosslinkable resin that is soluble in an organic solvent is dissolved in an organic container to form a relatively dilute organic solution, and this is brought into contact with the surface of a dense layer of polyimide resin. After forming a thin film of resin solution, this organic solvent is evaporated and the crosslinkable resin is further crosslinked to form a thin film of resin insoluble in the organic solvent. Conventionally, this method was used as described above. It is possible to form a resin thin film using an organic resin solution, which was difficult to use, and as a result, this, together with the excellent organic solvent resistance and heat resistance of the base polyimide resin ultrafiltration membrane, In particular, it is possible to produce a composite membrane that can be suitably used for separation and concentration of organic solutions and organic gases, particularly for these operations at high temperatures.
本発明において用いるポリイミド樹脂からなる異方性膜
は、好ましくは、次の一般式で表わされる繰返し単位か
らなる。The anisotropic film made of polyimide resin used in the present invention preferably consists of repeating units represented by the following general formula.
（但し、Ｒは２価の有機基を示す。）
このポリイミド樹脂からなる異方性膜は既に知られてい
るように、表面の緻密層がこれに連続する多孔質層によ
って一体的に支持されている異方性構造を有し、例えば
、特開昭５５−１５２５０７号や特開昭５６−１３９１
０４号公報に記載されている方法に従って限外濾過性を
有する異方性膜とすることができる。(However, R represents a divalent organic group.) As is already known, this anisotropic film made of polyimide resin has a dense layer on the surface that is integrally supported by a continuous porous layer. For example, JP-A-55-152507 and JP-A-56-1391
An anisotropic membrane having ultrafiltration properties can be obtained according to the method described in Japanese Patent No. 04.
また、次の一般式で表わされる繰返し単位からなるポリ
イミド樹脂からなる異方性限外濾過膜（）好適に用いる
ことができる。Further, an anisotropic ultrafiltration membrane () made of a polyimide resin made of repeating units represented by the following general formula can be suitably used.
（■）
（ＩＶ）
（但し、Ｒはいずれも２価の有機基を示す。）これらの
ポリイミド樹脂からなる異方性構造を有する限外濾過膜
も既に知られており、例えば、ＩＩ、 Ｓｔｒａｔｈｍ
ａｎｎ、 Ｄｅｓａｌｉｎａｔｉｏｒ＋、 ２６ 、８
５ （１９７Ｂ）や米国特許第３，９２５．２１１号明
細書等に記載されている方法に従って製造することがで
きる。(■) (IV) (However, each R represents a divalent organic group.) Ultrafiltration membranes having an anisotropic structure made of these polyimide resins are already known, for example, II, Strathm
ann, Desalination+, 26, 8
5 (197B) and US Pat. No. 3,925.211.
尚、本発明においては、上記したようなポリイミド樹脂
からなる異方性構造を有する限外濾過膜がすぐれた耐有
機溶剤性を有するように、前記−形式において、Ｒは芳
香族基を含むことが望ましい。かかる芳香族基を含む有
機基の好ましい具体例として、例えば、
等を挙げることができ、ここに、Ｘは２価の有機基であ
り、その好ましい具体例として、例えば、Ｃ０Ｚ−１−
Ｃ（Ｃ１４ゴ）２−１−〇−１−５Ｏ２−１−５−１−
ＣＯ−１Ｓｉ （Ｃ）Ｉ３） ２−等を挙げることがで
きる。In addition, in the present invention, in order that the ultrafiltration membrane having an anisotropic structure made of polyimide resin as described above has excellent organic solvent resistance, R in the above-mentioned - type may contain an aromatic group. is desirable. Preferred specific examples of such an aromatic group-containing organic group include, for example, where X is a divalent organic group, and preferred specific examples thereof include, for example, C0Z-1-
C (C14go)2-1-〇-1-5O2-1-5-1-
Examples include CO-1Si (C)I3) 2-.
本発明においては、上記のようなポリイミド樹脂半透膜
は、その分画分子量が２０００〜１０００００であるこ
とが好ましい。分画分子量が２０００よりも小さい異方
性膜の場合には、得られる複合膜の透過流束が十分に大
きくなく、一方、分画分子量が１ｏｏｏｏｏよりも大き
いときは、後述する緻密層の形成時に架橋性樹脂が膜内
に浸透して、膜内でも三次元網状構造を有する緻密層を
形成し、膜の透過流束を小さくするおそれがあるからで
ある。In the present invention, the polyimide resin semipermeable membrane as described above preferably has a molecular weight cut-off of 2,000 to 100,000. In the case of an anisotropic membrane with a molecular weight cut-off of less than 2000, the permeation flux of the resulting composite membrane is not sufficiently large; on the other hand, when the molecular weight cut-off is larger than 1ooooo, a dense layer is formed as described below. This is because the crosslinkable resin sometimes permeates into the membrane and forms a dense layer having a three-dimensional network structure within the membrane, which may reduce the permeation flux of the membrane.
ここに、分画分子量は、分子量が既知の溶質に対する異
方性膜の排除率を測定することにより求めることができ
、本発明においては、分子量分布が単分散性であるポリ
エチレングリコールを溶質として５０００ ｐｐｍ濃度
で含有するトルエン溶液を温度２５°Ｃ１圧力２ ｋｇ
／ ｃＪで１１り簡に供給し、排除率が少なくとも９
０％であるポリエチレングリコールの分子量をその膜の
分画分子量とする。このような分画分子量を有する異方
性膜は一般に液体分離において、限外濾過膜と称される
ので、本発明においても、異方性膜の代わりに限外濾過
膜ということがある。Here, the molecular weight fraction can be determined by measuring the exclusion rate of an anisotropic membrane for a solute with a known molecular weight, and in the present invention, polyethylene glycol having a monodisperse molecular weight distribution is used as a solute and Toluene solution containing ppm concentration at 25°C and 2 kg pressure
/cJ easily delivers 11 liters and has a rejection rate of at least 9
The molecular weight of polyethylene glycol, which is 0%, is taken as the molecular weight cutoff of the membrane. Since an anisotropic membrane having such a molecular weight cut-off is generally called an ultrafiltration membrane in liquid separation, it may also be referred to as an ultrafiltration membrane instead of an anisotropic membrane in the present invention.
本発明の方法は、代表的には、このようなポリイミド樹
脂からなる異方性膜の緻密層表面に架橋性樹脂の有機溶
液を接触させて、緻密層表面に架橋性樹脂の均一な有機
溶液の薄層を形成し、次いで、この樹脂溶液薄層から溶
剤を蒸発させ、更に必要な場合により高温に加熱するこ
とにより、架橋性樹脂を架橋させ、こうして、ポリイミ
ド限外濾過膜の緻密層表面上に有機溶剤に不溶性の３次
元硬化樹脂よりなる薄膜を形成させる。Typically, the method of the present invention involves bringing an organic solution of a crosslinkable resin into contact with the surface of a dense layer of an anisotropic film made of such a polyimide resin, thereby depositing a uniform organic solution of a crosslinkable resin on the surface of the dense layer. The crosslinkable resin is then crosslinked by forming a thin layer of the resin solution, then evaporating the solvent from this thin layer of resin solution and further heating to a high temperature if necessary, thus forming a dense layer surface of the polyimide ultrafiltration membrane. A thin film made of a three-dimensionally cured resin insoluble in an organic solvent is formed thereon.
ここに、本発明において、架橋性樹脂とは、架橋前は有
機溶剤に可溶性であるが、架橋後には有機溶剤に不溶性
の樹脂を与える樹脂をいい、本発明においては、水酸基
を有するアクリル酸エステルやメタクリル酸エステルを
単量体成分として含有する共重合体樹脂が用いられる。Here, in the present invention, the crosslinkable resin refers to a resin that is soluble in organic solvents before crosslinking, but becomes insoluble in organic solvents after crosslinking, and in the present invention, acrylic esters having hydroxyl groups A copolymer resin containing ester or methacrylic acid ester as a monomer component is used.
このような共重合体樹脂は、上記水酸基と反応する多官
能性架橋剤と反応して、３次元架橋樹脂を与える。例え
ば、上記共重合体樹脂は、ポリイソシアネートを架橋剤
として反応させることにより、架橋樹脂を形成する。Such a copolymer resin reacts with the polyfunctional crosslinking agent that reacts with the hydroxyl group to give a three-dimensionally crosslinked resin. For example, the copolymer resin described above forms a crosslinked resin by reacting with polyisocyanate as a crosslinking agent.
上記ポリイソシアネートとしては、例えば、トリレンジ
イソシアネート、ｍ−キシリレンジイソシアネート、４
．４’−ジフェニルメタンジイソシアネート、ポリテト
ラメチレングリコールジイソシアネート、ポリプロピレ
ングリコールジイソシアネート、トリイソシアネート「
コロネート」 （日本ポリウレタン工業■）等を用いる
ことができる。Examples of the polyisocyanate include tolylene diisocyanate, m-xylylene diisocyanate,
．． 4'-diphenylmethane diisocyanate, polytetramethylene glycol diisocyanate, polypropylene glycol diisocyanate, triisocyanate
"Coronate" (Nippon Polyurethane Industries ■), etc. can be used.
本発明においては、上記のような架橋性樹脂の有機溶液
を前記したポリイミド樹脂からなる異方性膜の緻密層の
表面に接触させ、樹脂溶液の薄層を形成した後、加熱し
て有機溶剤を蒸発させ、更に必要に応じてより高温に加
熱することにより、架橋性樹脂を架橋させて、有機溶剤
に不溶性の樹脂薄膜を形成するが、ここに、この樹脂薄
膜はできる躍り薄いことが望ましい。即ち、前記したよ
うに、得られる複合膜の液体又はガスの透過流束は、実
質的にこの樹脂薄膜の厚みによって支配され、薄膜が薄
い程、液体やガスの透過流束が大きくなるからである。In the present invention, an organic solution of the crosslinkable resin as described above is brought into contact with the surface of the dense layer of the anisotropic film made of the polyimide resin described above to form a thin layer of the resin solution, and then heated to form an organic solvent. The crosslinkable resin is crosslinked by evaporating the resin and heating to a higher temperature if necessary to form a thin resin film that is insoluble in organic solvents, but it is desirable that this thin resin film be as thin as possible. . That is, as mentioned above, the permeation flux of liquid or gas through the resulting composite membrane is substantially controlled by the thickness of this resin thin film, and the thinner the thin film, the larger the permeation flux of liquid or gas. be.
従って、本発明においては、上記架橋性樹脂の有機溶液
は比較的希薄であることが望ましく、通常は、樹脂濃度
が０．０１−１０重量％、好ましくは、０．１〜５重量
％となるように調製される。しかし、樹脂濃度が０．０
１重量％よりも小さいときは、形成される薄膜にピンホ
ール等の膜欠陥が生じやすいので好ましくなく、一方、
１０重量％よりも高いときは、形成される薄膜の厚みが
大きすぎて、実用上、その透過流束が小さすぎるので好
ましくない。Therefore, in the present invention, it is desirable that the organic solution of the crosslinkable resin is relatively dilute, and the resin concentration is usually 0.01-10% by weight, preferably 0.1-5% by weight. It is prepared as follows. However, the resin concentration is 0.0
When it is less than 1% by weight, it is not preferable because film defects such as pinholes are likely to occur in the thin film formed.
When it is higher than 10% by weight, the thickness of the formed thin film is too large and the permeation flux is too small for practical use, which is not preferable.
更に、重要な点は、架橋性樹脂の有機溶液をポリイミド
樹脂からなる異方性膜の緻密層表面に接触させるに際し
て、樹脂が異方性膜内部に浸透すると、これを架橋させ
た場合に、膜内部にも緻密な樹脂層が形成され、この結
果として、緻密層の厚みが実質的に大きくなる。従って
、本発明においては、架橋性樹脂の平均分子量が、用い
るポリイミド樹脂異方性膜の分画分子量と同等若しくは
これよりも大きいことが必要であって、上記した架橋性
樹脂は、用いるポリイミド樹脂異方性膜の分画分子量を
考慮して、上記条件を満足するように選ばれる。Furthermore, an important point is that when an organic solution of a crosslinkable resin is brought into contact with the surface of a dense layer of an anisotropic membrane made of polyimide resin, when the resin permeates inside the anisotropic membrane, when crosslinked, A dense resin layer is also formed inside the membrane, and as a result, the thickness of the dense layer becomes substantially large. Therefore, in the present invention, it is necessary that the average molecular weight of the crosslinkable resin is equal to or larger than the molecular weight cutoff of the polyimide resin anisotropic membrane used, and the above-mentioned crosslinkable resin is It is selected so as to satisfy the above conditions in consideration of the molecular weight cutoff of the anisotropic membrane.
また、本発明においては、前記したポリイミド樹脂がい
ずれもすぐれた耐有機溶剤性を有するので、架橋性樹脂
の有機溶液を形成するための有機溶剤は、特に制限され
ず、樹脂に応じて適宜に選ばれ、例えば、脂肪族及び芳
香族炭化水素溶剤、アルコール系溶剤、カルボン酸系溶
剤、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、
ハロゲン化炭化水素系溶剤等が用いられる。より具体的
には、例えば、ヘキサン、ヘプタン、ベンゼン、トルエ
ン、キシレン、メタノール、エタノール、プロパツール
、ブタノール、酢酸、アクリル酸、酢酸エチル、酢酸ブ
チル、アセトン、メチルエチルケトン、メチルイソブチ
ルケトン、テトラヒドロフラン、ジオキサン、塩化メチ
レン、クロロホルム、四塩化炭素、１，１．１−トリク
ロロエタン、りｕロベンゼン又はこれらの２以上の混合
物が用いられるが、しかし７、これらに限定されるもの
ではない。Furthermore, in the present invention, since all of the polyimide resins described above have excellent organic solvent resistance, the organic solvent for forming the organic solution of the crosslinkable resin is not particularly limited, and may be used as appropriate depending on the resin. For example, aliphatic and aromatic hydrocarbon solvents, alcohol solvents, carboxylic acid solvents, ester solvents, ketone solvents, ether solvents,
A halogenated hydrocarbon solvent or the like is used. More specifically, for example, hexane, heptane, benzene, toluene, xylene, methanol, ethanol, propatool, butanol, acetic acid, acrylic acid, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, Methylene chloride, chloroform, carbon tetrachloride, 1,1.1-trichloroethane, lilobenzene or mixtures of two or more thereof may be used, but are not limited thereto.
このような有機溶剤に前記架橋性樹脂を溶解した比較的
Ｓ３な溶液をポリイミド樹脂異方性膜の緻密層表面に接
触させるが、実用的には、緻密層表面に樹脂溶液を塗布
するか、又は緻密層表面を樹脂溶液に浸漬すればよい。A relatively S3 solution prepared by dissolving the crosslinkable resin in such an organic solvent is brought into contact with the surface of the dense layer of the polyimide resin anisotropic film.Practically, however, it is necessary to apply the resin solution to the surface of the dense layer, or Alternatively, the surface of the dense layer may be immersed in a resin solution.
この後、溶剤に応じて適宜温度、通常、４０〜８０°Ｃ
程度に加熱し７て溶剤を除去し、更に前記したように、
必要に応じてより高い温度に加熱して架橋性樹脂を架橋
させ一乙有機溶剤不溶性の３次元網状構造に架橋硬化さ
せる。この架橋に要する温度は、架橋性樹脂の種類や架
橋剤の種類によっても異なるが、通常、５０〜２５０
”Ｃの範囲、好ましくは、１００〜２００ ’Ｃの範囲
であって、１〜６０分、好ましくは３〜３０分間加熱処
理する。After this, the temperature is appropriate depending on the solvent, usually 40 to 80°C.
The solvent was removed by heating to a certain degree, and then as described above,
If necessary, the resin is heated to a higher temperature to crosslink and cure the crosslinkable resin into a three-dimensional network structure that is insoluble in organic solvents. The temperature required for this crosslinking varies depending on the type of crosslinkable resin and the type of crosslinking agent, but is usually 50 to 250℃.
The heat treatment is carried out in the range of 100 to 200'C, preferably in the range of 100 to 200'C, for 1 to 60 minutes, preferably 3 to 30 minutes.
このようにしてポリイミド樹脂異方性膜の緻密層表面上
に形成される架橋樹脂からなる薄膜は、架橋性樹脂溶液
の濃度や緻密層上に形成された溶液の薄層の厚みにもよ
るが、通常、１０〜５０００人、好ましくは、１００〜
２０００人の範囲の厚みを有する。この薄膜が余りに薄
い場合は、膜に欠陥が生じやすく、一方、余りに大きい
ときは、液体又はガスの透過流束が実用上手さすぎるか
らである。The thin film made of cross-linked resin formed on the surface of the dense layer of the anisotropic polyimide resin film in this way depends on the concentration of the cross-linked resin solution and the thickness of the thin layer of solution formed on the dense layer. , usually 10-5000 people, preferably 100-5000 people
It has a thickness in the range of 2000 people. If this membrane is too thin, it is likely to be defective, whereas if it is too large, the liquid or gas permeation flux is too low for practical use.
本発明の方法によれば、以上のように、複合膜の基材と
してポリイミド樹脂異方性膜を用いるので、架橋性樹脂
の有機溶液を薄膜形成材料として用いることができ、用
いる架橋性樹脂の選択範囲が広いと共に、かかる架橋性
樹脂を架橋させてなる薄膜もまた、有機溶剤に溶解膨潤
せず、従って、種々の有機溶剤や有機ガスの分離処理に
好適に用いることができる。According to the method of the present invention, as described above, since a polyimide resin anisotropic membrane is used as the base material of the composite membrane, an organic solution of a crosslinkable resin can be used as a thin film forming material, and the crosslinkable resin used can be The selection range is wide, and thin films formed by crosslinking such crosslinkable resins do not dissolve or swell in organic solvents, and therefore can be suitably used for separation treatments of various organic solvents and organic gases.
また、本発明の方法によって得られる複合膜は、分子量
数十乃至数千程度の低分子量の溶質に対して有効な排除
能を有し、従来、膜分離が困難であった有機性の工場排
水の処理、食品、医薬品、発酵、醸造、化学工業の分野
における逆浸透、又は逆浸透と限外濾過の中間領域での
有機性液体の濃縮や分離操作の膜分離において広範囲に
用いることができる。In addition, the composite membrane obtained by the method of the present invention has an effective ability to remove low molecular weight solutes with a molecular weight of several tens to several thousand, and can be used to remove organic industrial wastewater, which was previously difficult to separate with a membrane. It can be widely used in reverse osmosis in the fields of food, pharmaceutical, fermentation, brewing, and chemical industries, or in membrane separation for concentration and separation operations of organic liquids in the intermediate region between reverse osmosis and ultrafiltration.
更に、本発明による複合膜は、基材ポリイミド限夕■濾
過膜が耐熱性、耐有機溶剤性にすぐれるので、空気中の
酸素富化ほか、高温におけるガス分＾１１、例えば、合
成ガスの分離濃縮等にも好適に用いることができる。例
えば、本発明による複合膜は、ベンゼン、トルエン、キ
シレン、ニトロヘンゼン等の芳香族炭化水素、エチルエ
ーテル、テトラヒドロフラン、ジオキサン等のエーテル
、アセトン、メチルエチルケトン、メチルイソブチルケ
トン、シクロへキシルケトン等のケトン、メタノール、
エタノール、プロパツール、ブタノール、シクロヘキサ
ノール等のアルコール、エチレングリコール、プロピレ
ングリコール、ジエチレングリコール、ジプロピレング
リコール、ブタンジオール等のグリコール、メチルセロ
ソルブ、ジエチレングリコールモノメチルエーテル、ジ
エチレングリコールジメヂルエーテル等の多価アルコー
ルエーテル、酢酸エチル、酢酸ブチル、プロピオン酸エ
チル、エチレングリコールモノ及びジ酢酸エステル等の
エステル、ジクロルメタン、１．２−ジクロルエタン、
トリクレン、クロロホルム、ブロモホルム、クロルベン
ゼン等のハロゲン化炭化水素等を含有する有機溶液や、
有機ガスの分ｉ％ｉｉ濃縮に好適に用いることができる
。Furthermore, the composite membrane according to the present invention has excellent heat resistance and organic solvent resistance because the base polyimide limited filtration membrane has excellent heat resistance and organic solvent resistance. It can also be suitably used for separation and concentration. For example, the composite membrane according to the present invention can contain aromatic hydrocarbons such as benzene, toluene, xylene, and nitrohenzene, ethers such as ethyl ether, tetrahydrofuran, and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexyl ketone, methanol,
Alcohols such as ethanol, propatool, butanol, cyclohexanol, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, polyhydric alcohol ethers such as methyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol dimedyl ether, acetic acid Ethyl, butyl acetate, ethyl propionate, esters such as ethylene glycol mono- and diacetate, dichloromethane, 1,2-dichloroethane,
Organic solutions containing halogenated hydrocarbons such as trichlene, chloroform, bromoform, and chlorobenzene,
It can be suitably used for concentrating organic gas by 1%.
また、メタン、エタン、プロパン、エチレン、プロピレ
ン、ブテン、ブタジェン、イソプレン、水素、ヘリウム
、酸素、窒素、ネオン、アルゴン、−酸化炭素、６−酸
化炭素、硫化水素、アンモニア等のガス混合物の分離濃
縮にも好適に用いることができる。We also separate and concentrate gas mixtures such as methane, ethane, propane, ethylene, propylene, butene, butadiene, isoprene, hydrogen, helium, oxygen, nitrogen, neon, argon, -carbon oxide, 6-carbon oxide, hydrogen sulfide, and ammonia. It can also be suitably used.
しかし、本発明の複合膜は、その用途において何ら制限
されるものではなく、勿論、水性の液体混合物の分離処
理に使用することができるのはいうまでもない。However, the composite membrane of the present invention is not limited in its use, and it goes without saying that it can be used for separation treatment of aqueous liquid mixtures.
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。尚、以
下の実施例において、排除率及び透過流束は次式によっ
て定義される値である。The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the following examples, the rejection rate and the permeation flux are values defined by the following equations.
排除率（％）＝ （Ｌ−（膜透過液中の溶質濃度／原液
中の溶質濃度））Ｘ１００
透過流束（Ｉｌ／イ・時）＝溶剤の膜透過量（Ｉ！、）
／（有効膜面積（ホ）・透過時間（時間））実施例１
繰返し単位が前記−形式（１）においてＲがであるポリ
イミド（３０℃においてＮ−メチル−２−ピロリドン溶
液として測定した極限粘度〔η〕は０．９１）２２重量
％と、ジエチレングリコール２２重量％とを含有するＮ
−メチル−２−ピロリドン溶液を、特開昭５５−１５２
５０７号公報に記載されている常法の相転換法に従って
製膜し、厚さ２００ａｍの前記したような異方性構造を
有する限外濾過膜を調製した。Rejection rate (%) = (L - (Solute concentration in membrane permeate solution / Solute concentration in stock solution))
/(Effective membrane area (E)/Permeation time (hours)) Example 1 Polyimide in which the repeating unit is R in the above-mentioned form (1) (intrinsic viscosity measured as an N-methyl-2-pyrrolidone solution at 30°C [η] is 0.91) N containing 22% by weight and 22% by weight of diethylene glycol
-Methyl-2-pyrrolidone solution, JP-A-55-152
An ultrafiltration membrane having a thickness of 200 am and an anisotropic structure as described above was prepared by forming a membrane according to the conventional phase transformation method described in Japanese Patent No. 507.
この限外濾過膜の純トルエンの透過流束は、温度２０℃
、圧力２ ｋｇ ／ ｃｊにおいて１５５１／ポ・時で
あった。また、平均分子量２００００のポリエチレング
リコールを５０００ ｐｐｍ含有するトルエン溶液で評
価したポリエチレングリコールの排除率は９５．７％で
あった。The permeation flux of pure toluene through this ultrafiltration membrane is at a temperature of 20°C.
, 1551/po-hour at a pressure of 2 kg/cj. Further, the rejection rate of polyethylene glycol evaluated using a toluene solution containing 5000 ppm of polyethylene glycol having an average molecular weight of 20000 was 95.7%.
別に、メタクリル酸ブチル８０重量％とヒドロキシエチ
ルメタクリレート２０重量％とからなる共重合体であっ
て、平均分子量が４５０００であるアクリル樹脂０．８
重量部を３官能性イソシアネート「コロネートしく日本
ポリウレタン工業■製）０゜５重量部と共にトルエン１
００重量部に溶解してなるアクリル樹脂の希薄溶液を調
製した。Separately, acrylic resin 0.8 is a copolymer consisting of 80% by weight of butyl methacrylate and 20% by weight of hydroxyethyl methacrylate and has an average molecular weight of 45,000.
0.5 parts by weight of a trifunctional isocyanate (manufactured by Coronat Shikuni Nippon Polyurethane Industries) and 1 part by weight of toluene.
A dilute solution of acrylic resin was prepared by dissolving 00 parts by weight of the acrylic resin.
上記ポリイミド限外濾過膜の緻密層表面を室温にてこの
溶液に約３０秒間浸漬した後、約６０℃に加熱してトル
エンを完全に蒸発させた。次に、この膜を１２０°Ｃの
温度で１０分間加熱して、アクリル樹脂をイソシアネー
ト架橋させ、かくして、ポリイミド限外濾過膜の緻密層
表面に有機溶剤に不溶性の樹脂薄膜を形成させ、本発明
による複合膜を得た。The surface of the dense layer of the polyimide ultrafiltration membrane was immersed in this solution for about 30 seconds at room temperature, and then heated to about 60° C. to completely evaporate toluene. Next, this membrane is heated at a temperature of 120°C for 10 minutes to crosslink the acrylic resin with isocyanate, thus forming a thin resin film insoluble in organic solvents on the surface of the dense layer of the polyimide ultrafiltration membrane. A composite membrane was obtained.
この複合膜を加圧バッチ型セルに取付け、平均分子１４
００のポリエチレングリコールの５０００ｐｐｒａのア
セトン溶液を原液として、温度２５°Ｃ１圧力４２ｋｇ
／ｃｄの条件で膜性能を評価したところ、排除率９８．
８％、溶剤透過流束４．８ｆ／ボ・時であった。This composite membrane was installed in a pressurized batch cell, and the average molecular weight of 14
A 5000ppra acetone solution of 00 polyethylene glycol was used as a stock solution at a temperature of 25°C and a pressure of 42kg.
When the membrane performance was evaluated under the condition of /cd, the rejection rate was 98.
8%, and the solvent permeation flux was 4.8 f/voh.
Claims (2)
連続する多孔質層に一体に支持されている異方性構造を
有する膜の緻密層の表面に、この膜の分画分子量と同等
若しくはこれよりも大きい平均分子量を有する架橋性樹
脂の有機溶液を接触させ、次に、上記樹脂を架橋させて
、上記異方性膜の緻密層上に有機溶剤に不溶性の樹脂よ
りなる薄膜を形成する複合膜の製造方法であつて、架橋
性樹脂が分子内に２つ以上の反応性基を有し、この反応
性基が相互に架橋されて、有機溶剤に不溶性の樹脂を形
成する樹脂である複合膜の製造方法において、架橋性樹
脂がヒドロキシアルキルアクリレート及び／又はヒドロ
キシアルキルメタクリレートを単量体成分とする共重合
体樹脂であつて、水酸基と反応し得る官能基を分子内に
２つ以上有する多官能性化合物を架橋剤として架橋され
る樹脂であることを特徴とする複合膜の製造方法。(1) On the surface of the dense layer of a membrane made of polyimide resin and having an anisotropic structure in which the dense layer on the surface is integrally supported by a continuous porous layer, An organic solution of a crosslinkable resin having an average molecular weight larger than this is contacted, and then the resin is crosslinked to form a thin film made of a resin insoluble in an organic solvent on the dense layer of the anisotropic film. A method for producing a composite membrane, wherein the crosslinkable resin has two or more reactive groups in its molecule, and the reactive groups are mutually crosslinked to form a resin insoluble in organic solvents. In the method for producing a composite membrane, the crosslinkable resin is a copolymer resin containing hydroxyalkyl acrylate and/or hydroxyalkyl methacrylate as a monomer component, and has two or more functional groups in the molecule that can react with hydroxyl groups. A method for producing a composite membrane, characterized in that the resin is crosslinked using a polyfunctional compound as a crosslinking agent.
する特許請求の範囲第１項記載の複合膜の製造方法。(2) The method for producing a composite membrane according to claim 1, wherein the crosslinking agent is a polyisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29446589A JPH02174924A (en) | 1989-11-13 | 1989-11-13 | Preparation of conjugate film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29446589A JPH02174924A (en) | 1989-11-13 | 1989-11-13 | Preparation of conjugate film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP448083A Division JPS59130505A (en) | 1983-01-14 | 1983-01-14 | Production of composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02174924A true JPH02174924A (en) | 1990-07-06 |
| JPH0426889B2 JPH0426889B2 (en) | 1992-05-08 |
Family
ID=17808129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29446589A Granted JPH02174924A (en) | 1989-11-13 | 1989-11-13 | Preparation of conjugate film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02174924A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068100A1 (en) * | 2001-02-27 | 2002-09-06 | Gradipore Limited | Polymeric membranes and uses thereof |
-
1989
- 1989-11-13 JP JP29446589A patent/JPH02174924A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002068100A1 (en) * | 2001-02-27 | 2002-09-06 | Gradipore Limited | Polymeric membranes and uses thereof |
| US7169847B2 (en) | 2001-02-27 | 2007-01-30 | Life Therapeutics, Inc. | Polymeric membranes and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0426889B2 (en) | 1992-05-08 |
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