JPH0516290B2 - - Google Patents
Info
- Publication number
- JPH0516290B2 JPH0516290B2 JP62114523A JP11452387A JPH0516290B2 JP H0516290 B2 JPH0516290 B2 JP H0516290B2 JP 62114523 A JP62114523 A JP 62114523A JP 11452387 A JP11452387 A JP 11452387A JP H0516290 B2 JPH0516290 B2 JP H0516290B2
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- group
- polyimide
- organic
- acid
- 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.)
- Expired - Lifetime
Links
- 239000012528 membrane Substances 0.000 claims description 50
- 238000000926 separation method Methods 0.000 claims description 22
- 229920001721 polyimide Polymers 0.000 claims description 19
- 239000004642 Polyimide Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
- 238000005373 pervaporation Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000005462 imide group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 description 1
- REJHVSOVQBJEBF-UHFFFAOYSA-N DSD-acid Natural products OS(=O)(=O)C1=CC(N)=CC=C1C=CC1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 aliphatic amines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920001586 anionic polysaccharide Polymers 0.000 description 1
- 150000004836 anionic polysaccharides Chemical class 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000001291 vacuum drying 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
（産業上の利用分野〕
本発明は、新規な選択透過膜に関する。
更に詳しくは、有機物混合溶液を浸透気化法に
よつて、あるいは有機物混合蒸気を蒸気透過法に
よつて分離、濃縮するための膜に関するものであ
る。
（従来技術）
膜を用いた有機物水溶液の濃縮、分離に関して
は、一部の低濃度の有機物水溶液の濃縮に対し
て、逆浸透法が実用化されてきた。しかしなが
ら、逆浸透法は分離液の浸透圧以上の圧力を被分
離液に加える必要があるため、浸透圧が高くなる
高濃度水溶液に対しては、適用不可能であり、従
つて、分離できる溶液の濃度に限界がある。
これに対して、浸透圧の影響を受けない分離法
として浸透気化法および蒸気透過法が新しい分離
法として脚光を浴びつつある。浸透気化法とは膜
の一次側に分離液を供給し、膜の二次側（透過
側）を減圧にするか、又はキヤリヤーガスを通気
することによつて、分離物質を気体状で膜透過さ
せる方法であり、蒸気透過法とは、膜の１次側へ
の供給が混合蒸気である点が浸透気化法と異なる
ものである。膜透過物質は、透過蒸気を冷却、凝
縮する事によつて採取することができる。浸透気
化法については、これまでに多くの研究例が報告
されている。例えば、エタノール水溶液の分離に
関しては、米国特許2953502号にセルロースアセ
テート均一膜を、米国特許3035060号にはポリビ
ニルアルコールの例がある。
又、特公昭54−10548号、54−10549号及び特公
昭59−49041号にはイオン性基を導入した合成高
分子膜を用いて水−有機液体混合物を分離した実
験例が報告されている。
（発明が解決しようとする問題点）
液体や蒸気の膜透過は、溶解と拡散により支配
されているという理論に基づき、自由体積の小さ
な膜を使用し透過分子のサイズの差により分離を
行おうとする試みがなされてきた。
しかし、自由体積の小さな膜は分離係数は大き
いが、透過速度が小さいという欠点があつた。こ
のため、透過速度を増し、さらに選択性を上げる
ために、物質の溶解度の差を利用する試みがあつ
た。例えば、特開昭56−24007号には芳香族ポリ
アミドイミドの分子鎖中にスルホン基を導入する
ことにより透水速度を改善した透過膜が開示され
ているが、ポリマー中にスルホン基の量が増える
のに従つて膜形成能に乏しく、又、得られる膜の
機械的強度の低下と共に膨潤により分子のサイズ
による選択性が失われ、結果として水と有機物分
離の選択性が失われるという欠点があつた。
又、特開昭60−129104号にはアニオン性多糖か
らの膜が記載されているが、耐熱性、耐薬品性な
どの点で問題があり、広範囲にわたる有機物の分
離に適しているとは言えない。
従つて、本発明の目的は、浸透気化法及び蒸気
透過法による有機物水溶液又は、有機物と水の混
合蒸気の分離に於いて、種々の有機物質、及び広
範囲な濃度領域に対して、十分な耐久性、耐熱性
と高い透過速度及び分離係数を有する分離膜を得
ることにある。
（問題点を解決するための手段）
以上の点について鋭意検討した結果、本発明に
到達した。
即ち、本発明は、スルホン酸基及び第１級から
第４級までのアミノ基及び／又はピリジン残基を
同一分子内に有することを特徴とする芳香族系ポ
リイミド選択透過膜である。
有機物水溶液、又は水／有機物の蒸気混合物か
ら水を選択的に透過させるためには、水の配位能
力の大きい官能基を膜に導入するのが好ましい。
そこで、本発明者らは、水の透過性と有機物に対
する分離性能を高めるために、水の配位能力の高
いスルホン酸基を耐溶剤性のある膜素材であるポ
リイミドに導入することを試みた。
しかしながら、スルホン酸基をポリイミド中に
導入すると、膜形成能に乏しくなるのみならず、
膨潤などにより、膜としての選択分離性が著しく
低下する。そこで、スルホン酸基と共にカチオン
性のピリジン残基及び／又は第１級から第４級ま
でのアミノ基を導入することにより、高選択性
で、かつ高い透過性を有する分離膜を得ることが
できた。さらに、該ポリイミドを架橋３次元化さ
せることで、膜の機械的強度を高め、さらに広範
囲の有機混合物へ適用することが可能になつた。
以下に本発明について、さらに詳細に説明する。
本発明におけるポリイミドは一般式
（−Ｘ−R1）l−−−（−Ｘ−R2）n−−−（−Ｘ−R3）
−o
〔ただし、R1は１〜４個の酸型又は塩型のペ
ンダントスルホン酸基を有する芳香族又は脂環族
基、R2はピリジン残基及び／又は第１級から第
４級までのアミノ基を有する有機基、R3はスル
ホン酸基及びアミノ基を含まない芳香族又は脂環
族基、Ｘは一般式
で表わされるイミド基、（ｌ＋ｍ）／ｎ＝20/80〜
１００／０、ｌ／ｍ＝0.1〜10である〕
で示される。
該ポリイミドを製造する方法は、特に限定され
ないが、無水ピロメリト酸と種々のジアミンを反
応させることにより、該ポリイミドの前駆体であ
るポリアミド酸を得た後、加熱及び／又は脱水剤
の作用によりイミド環を形成することにより容易
に目的とするポリイミドを得ることができる。
当該ポリイミド選択透過膜は、スルホン酸基並
びにピリジン残基及び／又は第１級から第４級ま
でのアミノ基を有することを特徴とするが、該ス
ルホン酸基、ピリジン残基、及び／又は第１級か
ら第４級までのアミノ基は、これらの基を有する
モノマーを重合することにより、又は重合後並び
に製膜後、公知の手法により、これらの基を導入
することができる。
例えば、無水ピロメリト酸を用いた場合、ジア
ミン成分として２，４ジアミノベンゼンスルホン
酸、２，５ジアミノベンゼンスルホン酸、４，
4′−ジアミノジフエニルエーテル−２，2′−ジス
ルホン酸、４，4′−ジアミノスチルベン−２，
2′ジスルホン酸、２，６−ジアミノベンゼン−
１，４ジスルホン酸などを使用し、ペンダントス
ルホン酸基を導入することができる。
さらに
(Industrial Application Field) The present invention relates to a novel selectively permeable membrane. More specifically, it is a membrane for separating and concentrating an organic mixed solution by a pervaporation method or an organic mixed vapor by a vapor permeation method. This relates to membranes. (Prior art) Regarding the concentration and separation of organic substance aqueous solutions using membranes, reverse osmosis has been put to practical use for concentrating some low-concentration organic substance aqueous solutions. However, reverse osmosis The osmosis method requires applying pressure to the liquid to be separated that is higher than the osmotic pressure of the separation liquid, so it cannot be applied to highly concentrated aqueous solutions where the osmotic pressure increases. In contrast, pervaporation and vapor permeation methods are attracting attention as new separation methods that are not affected by osmotic pressure.Pervaporation is a method in which the separation liquid is applied to the primary side of the membrane. The vapor permeation method is a method in which the separated substance is passed through the membrane in a gaseous state by supplying the membrane and reducing the pressure on the secondary side (permeation side) of the membrane or by passing a carrier gas through the membrane. This method differs from the pervaporation method in that a mixed vapor is supplied to the next side.The membrane-permeable substance can be collected by cooling and condensing the permeated vapor.The pervaporation method Many research examples have been reported so far.For example, regarding the separation of ethanol aqueous solutions, there is an example of cellulose acetate homogeneous membrane in U.S. Patent No. 2,953,502, and an example of polyvinyl alcohol in U.S. Pat. No. 3,035,060. -10548, No. 54-10549, and Japanese Patent Publication No. 59-49041 report experimental examples in which a water-organic liquid mixture was separated using a synthetic polymer membrane into which ionic groups were introduced. Based on the theory that the permeation of liquids and vapors through membranes is dominated by dissolution and diffusion, attempts have been made to use membranes with small free volumes to perform separation based on the size difference of the permeating molecules. However, membranes with a small free volume have a large separation coefficient, but have the disadvantage of a low permeation rate.Therefore, in order to increase the permeation rate and further increase the selectivity, the difference in solubility of substances has been used to increase the permeation rate and selectivity. For example, JP-A-56-24007 discloses a permeable membrane that improves water permeation rate by introducing sulfone groups into the molecular chain of aromatic polyamideimide. As the amount of sulfonic groups increases, the membrane-forming ability becomes poor, and the resulting membrane loses selectivity based on molecular size due to swelling as well as a decrease in mechanical strength, resulting in a decrease in selectivity in water and organic matter separation. It had the disadvantage of being lost. In addition, JP-A-60-129104 describes a membrane made from anionic polysaccharide, but it has problems in terms of heat resistance, chemical resistance, etc., and although it is not suitable for separating a wide range of organic substances. do not have. Therefore, an object of the present invention is to provide sufficient durability for various organic substances and a wide range of concentration ranges in the separation of organic substance aqueous solutions or mixed vapors of organic substances and water by pervaporation and vapor permeation methods. The object of the present invention is to obtain a separation membrane having high properties, high heat resistance, high permeation rate, and high separation coefficient. (Means for Solving the Problems) As a result of intensive study on the above points, the present invention has been arrived at. That is, the present invention is an aromatic polyimide permselective membrane characterized by having a sulfonic acid group and primary to quaternary amino groups and/or pyridine residues in the same molecule. In order to selectively allow water to permeate from an aqueous organic solution or a water/organic vapor mixture, it is preferable to introduce a functional group having a large ability to coordinate water into the membrane.
Therefore, the present inventors attempted to introduce sulfonic acid groups with high water coordination ability into polyimide, which is a solvent-resistant membrane material, in order to improve water permeability and separation performance for organic substances. . However, when sulfonic acid groups are introduced into polyimide, not only does the film-forming ability become poor,
Due to swelling, etc., the selective separation performance of the membrane is significantly reduced. Therefore, by introducing a cationic pyridine residue and/or a primary to quaternary amino group together with a sulfonic acid group, a separation membrane with high selectivity and high permeability can be obtained. Ta. Furthermore, by crosslinking the polyimide into a three-dimensional structure, the mechanical strength of the membrane is increased, making it possible to apply it to a wider range of organic mixtures.
The present invention will be explained in more detail below. The polyimide in the present invention has the general formula (-X-R 1 ) l ---(-X-R 2 ) n ---(-X-R 3 )
- o [However, R 1 is an aromatic or alicyclic group having 1 to 4 acid-type or salt-type pendant sulfonic acid groups, R 2 is a pyridine residue and/or a primary to quaternary group An organic group having an amino group, R 3 is an aromatic or alicyclic group not containing a sulfonic acid group or an amino group, and X is a general formula Imide group represented by (l+m)/n=20/80~
100/0, l/m=0.1 to 10]. The method for producing the polyimide is not particularly limited, but after obtaining polyamic acid, which is a precursor of the polyimide, by reacting pyromellitic anhydride with various diamines, the imide is produced by heating and/or the action of a dehydrating agent. By forming a ring, the desired polyimide can be easily obtained. The polyimide selectively permeable membrane is characterized by having a sulfonic acid group, a pyridine residue and/or a primary to quaternary amino group; The primary to quaternary amino groups can be introduced by polymerizing monomers having these groups, or by known methods after polymerization and film formation. For example, when pyromellitic anhydride is used, the diamine components include 2,4 diaminobenzenesulfonic acid, 2,5 diaminobenzenesulfonic acid, 4,
4'-diaminodiphenyl ether-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,
2'disulfonic acid, 2,6-diaminobenzene-
Pendant sulfonic acid groups can be introduced using 1,4 disulfonic acid or the like. moreover
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
などで例示される種々の芳香族、脂環族、脂肪族
アミン類（第１級から第４級まで）を有するモノ
マーを用い、目的とするピリジン残基及び／又は
第１級から第４級までのアミノ基を導入すること
ができる。
又、本発明においては、本発明の趣旨を逸脱し
ない範囲で、該膜と相溶性のあるその他の高分子
とブレンド、ブロツク及びグラフトしてもよい。
これらのブレンド、ブロツク及びグラフトに用い
る高分子は、スルホン酸基並びにアミノ基を必ず
しも含まなくとも又、ポリイミドである必要はな
い。
本発明による分離膜は膜強度及び分離性能を改
善するため架橋構造を有することを特徴とする
が、この目的のために共有結合を使用した場合、
例えば、水酸基、第１級アミノ基、第２級アミノ
基等の活性水素を有する高分子化合物とエポキ
シ、酸塩化物、メラミン化合物、イソシアネー
ト、アルデヒド、酸無水物等の活性水素と反応す
る官能基を有する化合物の組みあわせを用いて架
橋することができる。さらに、紫外線照射、電子
線照射、プラズマ処理などによつても架橋するこ
とができる。
かかる架橋は、架橋点となりうる活性点を有す
るモノマーを共重合したり、ポリイミドとする前
のポリアミド酸中のカルボキシル基やアミド結合
を利用して、製膜時、又は製膜後架橋剤を添加並
びに含浸させ、熱処理、紫外線処理などにより行
うことができる。さらに、該ポリイミドに含まれ
るピリジン残基及び／又は第１級から３級までの
アミノ基を、一般式Ｙ−Ａ−Ｙ（Ｙ：ハロゲン原
子など）で示される架橋剤などにより、架橋と同
時に４級化処理もできる。これらの架橋性は単独
で行つてもよく、又は、これらの架橋性を組み合
わせて行つてもよい。この他、水素結合並びにイ
オン結合による架橋なども用いることができる。
この様にして作製された膜は、水／有機物混合
物、例えば、ギ酸、酢酸、プロピオン酸、酪酸等
の有機酸、メタノール、エタノール、１−プロパ
ノール、２−プロパノール、ｎ−ブタノール等の
アルコール類、アセトン、メチルエチルケトン等
のケトン類、テトラヒドロフラン、ジオキサン等
のエーテル類、アルデヒド、プロピオンアルデヒ
ド等のアルデヒド類、ピリジンやピコリン等のア
ミン類の群からなる１又は２以上の化合物を含む
水溶液又は水との蒸気混合物の分離に用いられ
る。
さらに、該ポリイミド膜の特性から広範な水及
びイオン処理用選択透過膜として用いることもで
きる。これには、透析膜、逆浸透膜、限外濾過
膜、イオン交換膜などが含まれる。
本発明になる膜は平膜、チユーブ膜、中空糸膜
のいずれでも可能である。平膜は、そのまま積層
するか、プリーツ型、又は渦巻状に成型してモジ
ユールとすることができる。又、複合膜として多
孔性支持体上に塗布することにより、膜厚を0.1μ
程度まで薄くすることが可能である。
（発明の効果）
本発明によるポリイミド膜は、水／有機物の混
合物の分離に対して、分離係数、透過速度共に優
れた性能を示し、かつ耐溶剤性、耐熱性について
も優れており、膜分離プロセスの実用化に極めて
有効である。
（実施例）
以下に実施例を示して、さらに具体的に本発明
を説明する。
実施例 １
２，５ジアミノベンゼンスルホン酸（0.008モ
ル）、２，６ジアミノピリジン（0.008モル）、３，
５ジアミノ安息香酸（0.004モル）をDMAc50ml
中に溶解し、氷水で外部から冷却しながら固体の
無水ピロメリト酸（0.02モル）を一度に加えて、
撹拌を続ける。５分後に冷却浴を取り去り、さら
に室温で３時間撹拌を続けることにより、前駆体
のポリアミド酸を得た。製膜は、上記ドープを濾
別し、架橋剤として３官能性エポキシ「テピツク
」（日産化学工業社製）をポリマー100重量部に
対し10重量部加え、ガラス板上にキヤストし、
100℃で１時間乾燥した後、ガラス板よりはがし、
さらに200℃で６時間真空乾燥することにより、
ポリイミド架橋膜を得る。80％酢酸を供給液とす
る70℃での浸透気化法による膜の分離性能を表１
に示す。
比較例 １
実施例１におけるジアミン成分として４，4′−
ジアミノジフエニルアミン（0.02モル）を用いて
ポリイミド均一膜を作製した。得られた膜の分離
性能を表１に示す。
比較例 ２
比較例１における４，4′−ジアミノジフエニル
アミンの代りにジアミノジフエニルエーテル
（0.02モル）を用いたポリイミド均一膜を作製し
た。得られた膜の分離性能を表１に示す。[Formula] Using monomers having various aromatic, alicyclic, and aliphatic amines (from primary to quaternary) such as Amino groups up to quaternary can be introduced. Further, in the present invention, the membrane may be blended, blocked, or grafted with other polymers that are compatible with the membrane without departing from the spirit of the present invention.
The polymers used in these blends, blocks and grafts do not necessarily have to contain sulfonic acid groups or amino groups, nor do they need to be polyimides. The separation membrane according to the present invention is characterized by having a crosslinked structure to improve membrane strength and separation performance, but when covalent bonds are used for this purpose,
For example, polymer compounds containing active hydrogen such as hydroxyl groups, primary amino groups, and secondary amino groups, and functional groups that react with active hydrogen such as epoxy, acid chlorides, melamine compounds, isocyanates, aldehydes, and acid anhydrides. can be crosslinked using a combination of compounds having . Furthermore, crosslinking can also be achieved by ultraviolet irradiation, electron beam irradiation, plasma treatment, or the like. Such crosslinking can be achieved by copolymerizing monomers that have active sites that can serve as crosslinking sites, or by using carboxyl groups or amide bonds in polyamic acid before making it into polyimide, or by adding a crosslinking agent during film formation or after film formation. It can also be carried out by impregnation, heat treatment, ultraviolet treatment, etc. Furthermore, pyridine residues and/or primary to tertiary amino groups contained in the polyimide are simultaneously cross-linked using a cross-linking agent represented by the general formula Y-A-Y (Y: halogen atom, etc.). Quaternary processing is also possible. These crosslinking properties may be performed alone or in combination. In addition, crosslinking by hydrogen bonding and ionic bonding can also be used. The membrane prepared in this way can contain water/organic mixtures, such as organic acids such as formic acid, acetic acid, propionic acid, butyric acid, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, etc. Aqueous solution or vapor with water containing one or more compounds from the group of ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, aldehydes such as aldehydes and propionaldehyde, and amines such as pyridine and picoline. Used for separating mixtures. Furthermore, due to the characteristics of the polyimide membrane, it can be used as a selectively permeable membrane for a wide range of water and ion treatments. This includes dialysis membranes, reverse osmosis membranes, ultrafiltration membranes, ion exchange membranes, etc. The membrane of the present invention can be a flat membrane, a tube membrane, or a hollow fiber membrane. The flat membranes can be laminated as they are, or can be formed into a module by forming them into pleats or spirals. In addition, by coating it on a porous support as a composite membrane, the film thickness can be reduced to 0.1μ.
It is possible to make it as thin as possible. (Effects of the Invention) The polyimide membrane according to the present invention exhibits excellent performance in terms of separation coefficient and permeation rate for the separation of water/organic mixtures, and also has excellent solvent resistance and heat resistance. It is extremely effective for practical application of the process. (Example) The present invention will be described in more detail with reference to Examples below. Example 1 2,5 diaminobenzenesulfonic acid (0.008 mol), 2,6 diaminopyridine (0.008 mol), 3,
5 diaminobenzoic acid (0.004 mol) in DMAc50ml
Add solid pyromellitic anhydride (0.02 mol) in one portion while cooling externally with ice water.
Continue stirring. The cooling bath was removed after 5 minutes, and stirring was continued for 3 hours at room temperature to obtain a polyamic acid precursor. For film formation, the above dope was filtered, 10 parts by weight of trifunctional epoxy "Tepik" (manufactured by Nissan Chemical Industries, Ltd.) was added as a crosslinking agent to 100 parts by weight of the polymer, and the mixture was cast on a glass plate.
After drying at 100℃ for 1 hour, peel it off from the glass plate.
By further vacuum drying at 200℃ for 6 hours,
A polyimide crosslinked membrane is obtained. Table 1 shows the separation performance of the membrane by pervaporation method at 70℃ using 80% acetic acid as the feed liquid.
Shown below. Comparative Example 1 4,4′- as the diamine component in Example 1
A uniform polyimide film was prepared using diaminodiphenylamine (0.02 mol). Table 1 shows the separation performance of the obtained membrane. Comparative Example 2 A uniform polyimide film was prepared using diaminodiphenyl ether (0.02 mol) in place of 4,4'-diaminodiphenylamine in Comparative Example 1. Table 1 shows the separation performance of the obtained membrane.
Claims (1)
−o 〔ただし、R1は１〜４個の酸型又は塩型のペ
ンダントスルホン酸基を有する芳香族又は脂環族
基、R2はペリジン残基及び／又は第１級から第
４級までのアミノ基を有する有機基、R3はスル
ホン酸基及びアミノ基を含まない芳香族又は、脂
環族基Ｘは で表されるイミド基、（ｌ＋ｍ）／ｎ＝20/80〜10
０／０、ｌ／ｍ＝0.1〜10である。〕で示される繰り
返し単位を有し、さらに架橋により３次元構造を
有することを特徴とするポリイミド選択透過膜。 ２ 該膜が浸透気化並びに蒸気透過用水／有機物
分離膜である特許請求の範囲第１項記載のポリイ
ミド選択透過膜。[Claims] 1 General formula (-X-R 1 ) l ---(-X-R 2 ) n ---(-X-R 3 )
- o [However, R 1 is an aromatic or alicyclic group having 1 to 4 acid-type or salt-type pendant sulfonic acid groups, R 2 is a peridine residue and/or a primary to quaternary group R 3 is an organic group having an amino group, R 3 is an aromatic group not containing a sulfonic acid group and an amino group, or X is an alicyclic group Imide group represented by (l+m)/n=20/80~10
0/0, l/m=0.1-10. ] A polyimide permselective membrane characterized by having a repeating unit represented by the following and further having a three-dimensional structure due to crosslinking. 2. The polyimide permselective membrane according to claim 1, wherein the membrane is a water/organic separation membrane for pervaporation and vapor permeation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114523A JPS63283704A (en) | 1987-05-13 | 1987-05-13 | Selective semipermeable membrane of polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62114523A JPS63283704A (en) | 1987-05-13 | 1987-05-13 | Selective semipermeable membrane of polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63283704A JPS63283704A (en) | 1988-11-21 |
| JPH0516290B2 true JPH0516290B2 (en) | 1993-03-04 |
Family
ID=14639885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62114523A Granted JPS63283704A (en) | 1987-05-13 | 1987-05-13 | Selective semipermeable membrane of polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63283704A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5550199A (en) * | 1994-12-02 | 1996-08-27 | Exxon Research And Engineering Company | Diepoxide crosslinked/esterified polyimide-aliphatic polyester copolymers |
| JP5380852B2 (en) * | 2008-02-13 | 2014-01-08 | 宇部興産株式会社 | Method for producing molded body with improved solvent resistance |
| CN101785977A (en) * | 2010-03-22 | 2010-07-28 | 北京化工大学 | Preparation method of solvent resistant polyimide nanofiltration film |
| US8614288B2 (en) * | 2011-06-17 | 2013-12-24 | Uop Llc | Polyimide gas separation membranes |
| JP2015160166A (en) * | 2014-02-26 | 2015-09-07 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separator, and gas separation method |
-
1987
- 1987-05-13 JP JP62114523A patent/JPS63283704A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63283704A (en) | 1988-11-21 |
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