JPS62247808A - Production of semipermeable composite membrane - Google Patents
Production of semipermeable composite membraneInfo
- Publication number
- JPS62247808A JPS62247808A JP61088241A JP8824186A JPS62247808A JP S62247808 A JPS62247808 A JP S62247808A JP 61088241 A JP61088241 A JP 61088241A JP 8824186 A JP8824186 A JP 8824186A JP S62247808 A JPS62247808 A JP S62247808A
- Authority
- JP
- Japan
- Prior art keywords
- acid chloride
- aromatic
- composite membrane
- membrane
- semipermeable composite
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 4
- 229920000620 organic polymer Polymers 0.000 claims abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 3
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- -1 polybenzimidacylon Polymers 0.000 description 5
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- MEQCXWDKLOGGRO-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarbonyl chloride Chemical compound ClC(=O)C1OC(C(Cl)=O)C(C(Cl)=O)C1C(Cl)=O MEQCXWDKLOGGRO-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SWRRWODUBVHJBC-UHFFFAOYSA-N 1-(2-piperidin-1-ylpropan-2-yl)piperidine Chemical compound N1(CCCCC1)C(C)(C)N1CCCCC1 SWRRWODUBVHJBC-UHFFFAOYSA-N 0.000 description 1
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical group CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UONVFNLDGRWLKF-UHFFFAOYSA-N 2,5-diaminobenzoic acid Chemical compound NC1=CC=C(N)C(C(O)=O)=C1 UONVFNLDGRWLKF-UHFFFAOYSA-N 0.000 description 1
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- PMAPIPPKZXGDFA-UHFFFAOYSA-N 2-[(2-carboxyanilino)methylamino]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1NCNC1=CC=CC=C1C(O)=O PMAPIPPKZXGDFA-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
- DMEPVFSJYHJGCD-UHFFFAOYSA-N 3,5-dimethylbenzene-1,2-diamine Chemical compound CC1=CC(C)=C(N)C(N)=C1 DMEPVFSJYHJGCD-UHFFFAOYSA-N 0.000 description 1
- OMIOAPDWNQGXED-UHFFFAOYSA-N 3-amino-n-(3-aminophenyl)benzamide Chemical compound NC1=CC=CC(NC(=O)C=2C=C(N)C=CC=2)=C1 OMIOAPDWNQGXED-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- TYXZKNUOZATAAZ-UHFFFAOYSA-N 5-(3,5-dicarbonochloridoylphenyl)benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C=2C=C(C=C(C=2)C(Cl)=O)C(Cl)=O)=C1 TYXZKNUOZATAAZ-UHFFFAOYSA-N 0.000 description 1
- JPPYSPAXPNNOBC-UHFFFAOYSA-N 5-chlorosulfonylbenzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(S(Cl)(=O)=O)=C1 JPPYSPAXPNNOBC-UHFFFAOYSA-N 0.000 description 1
- DFWXYHZQNLIBLY-UHFFFAOYSA-N 5-nitrobenzene-1,3-diamine Chemical compound NC1=CC(N)=CC([N+]([O-])=O)=C1 DFWXYHZQNLIBLY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- RUOKPLVTMFHRJE-UHFFFAOYSA-N benzene-1,2,3-triamine Chemical compound NC1=CC=CC(N)=C1N RUOKPLVTMFHRJE-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LTEKQAPRXFBRNN-UHFFFAOYSA-N piperidin-4-ylmethanamine Chemical compound NCC1CCNCC1 LTEKQAPRXFBRNN-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、液状混合物の成分を選択透過分離するための
新規な半透膜の製造方法に関するものであり、特に海水
やカン水を脱塩して淡水化することができ、また、染色
廃水や電着染料廃水などの公害発生原因である汚水など
から、その中に含まれる汚染源あるいは有効物質を選択
的に除去あるいは回収し、ひいては、廃水のクローズド
化に寄与しつる半透膜に関する。より具体的には、多孔
性支持体と、この上に積層された特定構造の架橋ポリア
ミドを主成分とする超薄膜層から成る半透性複合膜の製
造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a novel semipermeable membrane for selectively permeating components of a liquid mixture, and in particular for desalinating seawater or canned water. It can also be used to selectively remove or recover pollutants or effective substances contained in sewage that causes pollution, such as dyeing wastewater and electrocoating dye wastewater, and furthermore, it can desalinate wastewater. Concerning semipermeable membranes that contribute to the closure of More specifically, the present invention relates to a method for producing a semipermeable composite membrane comprising a porous support and an ultra-thin film layer laminated thereon, the main component of which is crosslinked polyamide with a specific structure.
（従来の技術〕
従来、工業的に利用されている半透膜には、酢酸セルロ
ーズから作った非対称膜として、例えば米国特許第３，
１３３．１３２号明細書及び同第３．１３３，１３７号
明細書等に記載されたロブ型の膜がある。しかし、この
膜は、耐加水分解性、耐微生物性、耐薬品性などに問題
があり、特に透過性を向上しようとすると耐圧性、耐久
性を兼ね備えた膜が製造できず、一部使用されているが
広範囲の用途に実用化されるに至っていない。これらの
酢酸セルローズ非対称膜の欠点をなくした新しい素材に
対する研究は、米国、日本を中心に盛んに行なわれてい
るが、芳香族ポリアミド、ポリアミドヒドラジド（米国
特許第３，５６７．６３２号明細書）、ポリアミド酸（
特公昭５０−１２１１６８号公報）、架橋ポリアミド酸
（特公昭５２−１５２８７９号公報）、ポリイミダゾピ
ロロン、ポリスルホンアミド、ポリベンズイミダゾール
、ポリベンズイミダシロン、ポリアリーレンオキシドな
ど、その一部の欠点を改良する素材は得られているもの
の、選択分離性あるいは透過性等の面では酢酸セルロー
ズ膜より劣っている。(Prior art) Conventionally, semipermeable membranes that have been used industrially include asymmetric membranes made from cellulose acetate, such as those disclosed in U.S. Patent No. 3,
There are lob-type membranes described in Patent No. 133.132 and Patent No. 3.133,137. However, this membrane has problems with hydrolysis resistance, microbial resistance, chemical resistance, etc. In particular, when trying to improve permeability, it is not possible to manufacture a membrane that has both pressure resistance and durability, so it is not used in some cases. However, it has not yet been put to practical use in a wide range of applications. Research into new materials that eliminate these drawbacks of cellulose acetate asymmetric membranes is being actively conducted mainly in the United States and Japan, but aromatic polyamides and polyamide hydrazides (U.S. Pat. No. 3,567,632) are being actively researched into new materials. , polyamic acid (
(Japanese Patent Publication No. 50-121168), crosslinked polyamic acid (Japanese Patent Publication No. 52-152879), polyimidazopyrrolone, polysulfonamide, polybenzimidazole, polybenzimidacylon, polyarylene oxide, etc. Although an improved material has been obtained, it is inferior to cellulose acetate membranes in terms of selective separation and permeability.
一方、ロブ型とは型を異にする半透膜として多孔性支持
体上に実質的に膜性能を司どる活性層を被覆した複合膜
が開発されている。複合膜においては、活性層と多孔性
支持体を各々用途に最適な素材を選ぶことが可能となり
、製膜技術の自由度が増す。また常温湿潤状態で保存し
なければならないロブ型膜とは異なり、乾燥状態での保
存が可能であるなどの利点がある。On the other hand, a composite membrane has been developed as a semipermeable membrane of a type different from the lobe type, in which a porous support is coated with an active layer that substantially controls membrane performance. In composite membranes, it is possible to select the optimal materials for the active layer and porous support for each application, increasing the degree of freedom in membrane manufacturing technology. Also, unlike the lobe-type membrane, which must be stored in a humid state at room temperature, it has the advantage of being able to be stored in a dry state.
これらの複合膜には多孔性支持体上に直接活性層を被覆
した型のものと、多孔性支持体上にゲル化層を介して活
性層を被覆した型のものとの２種類がある。前者の具体
例は米国特許第３．７４．４゜６４２号明細書、同第３
，９２６．７９８号明細書、特開昭５５−１４７’１０
６号公報、同５３−１４０４６号公報、特開昭５８−２
４３０３号公報などがあり、前者の具体例としては、特
開昭４９−１３３２８２号公報、特公昭５５−４９５２
４号公報、特公昭５５−３８１６４号公報、Ｐａレポー
ト８０−１８２０９０．特公昭５９−２７２０２号公報
、特開昭５６−４０４０３号公報などが知られている。There are two types of these composite membranes: one in which the active layer is directly coated on a porous support, and one in which the active layer is coated on the porous support through a gelling layer. Specific examples of the former are described in U.S. Patent No. 3.74.4゜642,
, No. 926.798, JP-A-55-147'10
Publication No. 6, Publication No. 53-14046, JP-A-58-2
4303, and specific examples of the former include JP-A-49-133282 and JP-A-55-4952.
4 Publication, Special Publication No. 55-38164, Pa Report 80-182090. Japanese Patent Publication No. 59-27202, Japanese Unexamined Patent Publication No. 56-40403, etc. are known.
これらの複合膜は、従来、耐加水分解性、耐塩素性、耐
久性、耐熱性、耐薬品性、耐圧性に欠けるといった欠点
があった。また、これらの膜においては、水中の塩素、
過酸化水素などの酸化性物質によって超薄膜層が酸化を
受けて、その優れた性質を失うものが多い。Conventionally, these composite membranes have had drawbacks such as lacking in hydrolysis resistance, chlorine resistance, durability, heat resistance, chemical resistance, and pressure resistance. In addition, in these membranes, chlorine in water,
In many cases, ultra-thin film layers are oxidized by oxidizing substances such as hydrogen peroxide and lose their excellent properties.
［発明が解決しようとする問題点］
従来から種々の反応性アミノ基を有する化合物が検討さ
れてきたが、形成された複合膜は、耐塩素性、耐久性、
耐熱性、耐薬品性、耐圧性の点で問題があった。本発明
者らは、２官能以上のアミノ基を有するアミン化合物と
、４官能性酸クロリド化合物を主体とする酸クロリド化
合物の混合物とを、多孔性支持体上で反応させて得られ
る半透性複合膜が、従来提案されている素材が有してい
た上記欠点を解消することができることを見い出し、本
発明に到達した。[Problems to be solved by the invention] Conventionally, various compounds having reactive amino groups have been studied, but the composite membranes formed have excellent chlorine resistance, durability,
There were problems with heat resistance, chemical resistance, and pressure resistance. The present inventors have developed a semi-permeable material obtained by reacting an amine compound having two or more functional amino groups with a mixture of acid chloride compounds mainly consisting of a tetrafunctional acid chloride compound on a porous support. We have discovered that a composite membrane can overcome the above-mentioned drawbacks of conventionally proposed materials, and have arrived at the present invention.
［問題点を解決するための手段］ 本発明は次の構成を有する。[Means for solving problems] The present invention has the following configuration.
［（１）多孔性支持体上に、下記成分（ａ）、（ｂ）の
反応生成物からなる架橋重合体を主成分とする超薄膜層
を設けることを特徴とするする半透性複合膜の製造法。[(1) A semipermeable composite membrane characterized by providing on a porous support an ultra-thin film layer mainly composed of a crosslinked polymer made of the reaction product of the following components (a) and (b) manufacturing method.
（ａ）芳香族または脂環族多官能アミンであって、１分
子中に２個以上の１級または／および２級アミン基を有
するもの、または／および分子鎖末端および／または側
鎖に反応性のアミノ基を有する水溶性有機重合体。(a) Aromatic or alicyclic polyfunctional amines having two or more primary or/and secondary amine groups in one molecule, and/or reacting at the end of the molecular chain and/or side chain. A water-soluble organic polymer having a chemical amino group.
（ｂ）次式で示される２種類の化合物より選ばれた少な
くとも１種以上の４官能酸クロリド単独、およびくまた
は）
または芳香族多官能酸塩化物であって、３個以下の芳香
族環上に、２または３個の酸クロリド基を有するものと
の混合物。」
本発明における多孔性支持体としては、その片面の表面
の微細孔の孔径が約１００〜１０００人であるような構
造の支持体が好ましい。上記の微細孔性支持体の素材と
しては、ポリスルホン、ポリエーテルスルホン、ポリ塩
化ビニル、ポリカーボネート、酢酸セルロース、硝酸セ
ルロースなどを例示することができる。なお多孔性支持
体のさらに具体的な製造法は、″オフィス・オブ・ザラ
イン・つＡ−夕−・リザーチ・アンド・デベロップメン
ト・プログレス中レポート”Ｎ、３５９（１９６８）に
述べられている。(b) At least one or more tetrafunctional acid chlorides selected from two types of compounds represented by the following formula, or aromatic polyfunctional acid chlorides, which have 3 or less aromatic rings. Mixtures with those having 2 or 3 acid chloride groups on top. The porous support used in the present invention preferably has a structure in which the micropores on one surface have a pore size of about 100 to 1000 pores. Examples of the material for the above-mentioned microporous support include polysulfone, polyethersulfone, polyvinyl chloride, polycarbonate, cellulose acetate, and cellulose nitrate. A more specific method for producing the porous support is described in "Office of the Line Research and Development Progress Report" N, 359 (1968).
本発明の半透性複合膜の製造法としては、Ｐ、唱Ｍｏｒ
ｇａｎが“コンデンセーション・ボリマーズ・パイ・イ
ンターフエーシャル・アンド・ソリューション・メリッ
ト″（インターサイエンス、１９６５）に詳）ホしてい
る界面重縮合反応が利用される。The method for producing the semipermeable composite membrane of the present invention includes P. Mor.
The interfacial polycondensation reaction described in "Condensation Polymers, Interfacial and Solution Benefits" (Interscience, 1965) by John G. Gan is used.
すなわち前述の芳香族または脂環族多官能アミンの水溶
液を多孔性支持体の表面に塗布後、必要に応じて過剰の
溶液を液切りし、しかる後に多官能アミンに対して反応
性を有する多官能試薬を水に対して非混和性の溶剤に溶
解した溶液と接触させ、界面重縮合反応を行なわせるこ
とにより容易に製造することができる。That is, after applying an aqueous solution of the above-mentioned aromatic or alicyclic polyfunctional amine to the surface of a porous support, excess solution is drained off as necessary, and then a polyfunctional amine reactive with polyfunctional amines is applied. It can be easily produced by bringing an interfacial polycondensation reaction into contact with a solution of a functional reagent dissolved in a water-immiscible solvent.
本発明で使用される芳香族多官能アミン化合物としては
、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、
１，３．５−トリアミノベンゼン、ベンジジン、４，４
゛−ジアミノジフェニルエーテル、３，３°−ジアミノ
ジフェニルエーテル、３，４°−ジアミノジフェニルエ
ーテル、４，４°−ジアミノベンゾフェノン、４，４°
−ジアミノジフェニルメタン、３，５−ジアミノ安息香
酸、２，５−ジアミノベンゼンスルホン酸、メヂレンビ
スアンスラニル酸、５−ニトロ−ｍ−フェニレンジアミ
ン、２．５−ジアミノ安息香酸、トリレンジアミン、４
，６−シメチルー■−フェニレンジアミン、２，４−ジ
アミノメシチレン、４−クロル−ｍ−フェニレンジアミ
ン、２，５−ジアミノ−テレフタル酸、３．３゛−ジア
ミノベンズアニリドが例として挙げられる。The aromatic polyfunctional amine compounds used in the present invention include m-phenylenediamine, p-phenylenediamine,
1,3,5-triaminobenzene, benzidine, 4,4
゛-Diamino diphenyl ether, 3,3°-diaminodiphenyl ether, 3,4°-diaminodiphenyl ether, 4,4°-diaminobenzophenone, 4,4°
-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 2,5-diaminobenzenesulfonic acid, methylenebisanthranilic acid, 5-nitro-m-phenylenediamine, 2,5-diaminobenzoic acid, tolylenediamine, 4
, 6-dimethyl--phenylenediamine, 2,4-diaminomesitylene, 4-chloro-m-phenylenediamine, 2,5-diamino-terephthalic acid, and 3,3'-diaminobenzanilide.
本発明で使用される脂環族多官能アミン化合物としては
、ピペラジン、２，５−ジメチルピペラジン、ジピペリ
ジルプロパン、４−アミノメチルピペリジンなどが挙げ
られる。Examples of the alicyclic polyfunctional amine compound used in the present invention include piperazine, 2,5-dimethylpiperazine, dipiperidylpropane, and 4-aminomethylpiperidine.
本発明において使用される分子鎖末端および／または側
鎖に反応性のアミノ基を有する水溶性有機重合体として
は、アミン変性ポリエピハロヒドリン、ポリエチレンイ
ミン、ポリプロピレンイミン、ポリエピアミノヒドリン
などを挙げることができる。これらの重合体は、多官能
アミン類と均一に混和し、多官能インシアネート化合物
の単独または芳香族多官能酸塩化物との混合物との反応
により均一な組成の欠陥のない架橋重合体膜を形成する
。本発明においてはアミン変性ポリエピハロヒドリン、
特に下記一般式で示されるポリエピハロヒドリンと多官
能アミンから誘導されるアミン変性ポリマーが申越した
性能を有する半透性複合膜を与えるので好ましい。Examples of the water-soluble organic polymer having a reactive amino group at the molecular chain terminal and/or side chain used in the present invention include amine-modified polyepihalohydrin, polyethyleneimine, polypropyleneimine, polyepiamininohydrin, and the like. I can do it. These polymers are uniformly miscible with polyfunctional amines and can be reacted with polyfunctional incyanate compounds alone or in mixtures with aromatic polyfunctional acid chlorides to form defect-free crosslinked polymer films of uniform composition. Form. In the present invention, amine-modified polyepihalohydrin,
In particular, an amine-modified polymer derived from a polyepihalohydrin represented by the following general formula and a polyfunctional amine is preferable because it provides a semipermeable composite membrane having excellent performance.
（ただし上式中Ｘはハロゲン、ｉおよびｊはモル比分立
であって次の関係を満す）。(However, in the above formula, X is a halogen, i and j are molar ratio separations, and satisfy the following relationship).
ｉ＋ｊ＝１
Ｑ＜ｉ≦１
０≦ｊ≦０．８
本発明で使用される４官能性酸クロリド化合物としては
、ビフェニル−３，３’、５．５’−テトラカルボン酸
クロリド、テトラヒドロフラン−２，３，４，５−テト
ラカルボン酸クロリドの２種類の化合物が挙げられる。i+j=1 Q<i≦1 0≦j≦0.8 The tetrafunctional acid chloride compound used in the present invention includes biphenyl-3,3', 5,5'-tetracarboxylic acid chloride, tetrahydrofuran-2 , 3,4,5-tetracarboxylic acid chloride.
前者は、５−アミノ−インフタル酸（日本化薬社）より
、下記反応経路により合成することができる。The former can be synthesized from 5-amino-inphthalic acid (Nippon Kayaku Co., Ltd.) by the following reaction route.
５ＯＣＩ１２／ＤＭＦ
後者の化合物はテトラヒドロフラン−２，３，４，５−
テトラカルボン酸（Ａｌｄｒｉｃｈ社）と塩化チオニル
の反応により合成することができる。5OCI12/DMF The latter compound is tetrahydrofuran-2,3,4,5-
It can be synthesized by the reaction of tetracarboxylic acid (Aldrich) and thionyl chloride.
本発明において、架橋剤成分として４官能性酸りロリド
化合物と併用される芳香族多官能酸塩化物としては、ト
リメシン酸クロリド、イソフタル酸クロリド、テレフタ
ル酸クロリド、５−クロルスルホニルイソフタル酸クロ
リドなどが挙げられ、なかでも好ましい例は、トリメシ
ン酸クロリド、イソフタル酸クロリド、テレフタル酸ク
ロリドである。In the present invention, the aromatic polyfunctional acid chloride used in combination with the tetrafunctional acid loride compound as a crosslinking agent component includes trimesic acid chloride, isophthalic acid chloride, terephthalic acid chloride, 5-chlorosulfonylisophthalic acid chloride, etc. Preferred examples include trimesic acid chloride, isophthalic acid chloride, and terephthalic acid chloride.
以下の実施例において、選択分離性能として、食塩の排
除率は電気伝導度の測定による通常の手段によって決定
された。In the following examples, the rejection rate of common salt as selective separation performance was determined by conventional means by measuring electrical conductivity.
また、透過性能として、水運過速度は単位面積、中位時
間当りの水の透過量で決定した。In addition, as permeation performance, water transport overspeed was determined by the amount of water permeation per unit area and medium time.
参考例
タテ３Ｑｃｍヨコ２０ｃｍの大きさのポリエステル繊維
からなるタック（タテ糸、ヨコ糸とも１５０デニールの
マルチフィラメント糸、織密度タテ９０本／インチ、ヨ
コ６７本／インチ、厚さ１６０μ）をガラス板上に固定
し、その上にポリスルホン（ユニオン・カーバイト社製
のＵｄｅｌ−Ｐ ３５００）の１６重量％ジメヂルホル
ムアミド（ＤＭＦ＞溶液を２００μの厚みで室温（２０
℃）でキャストし、ただちに純水中に浸漬して５分間放
置することによって繊維補強ポリスルホン支持体（以下
ＦＲ−ＰＳ支持体と略す）を作製する。このようにして
得られたＦＲ−ＰＳ支持体（厚さ２１０〜２１５μ）の
純水透過係数は、圧力１ｋｉ／ｃｄ、温度２５°Ｃで測
定して０．００５〜０．０１ ｇ／ｃｎｆ・ｓｅｃ／ａ
ｔｍでおった。Reference example A tack made of polyester fibers with a length of 3Qcm and a width of 20cm (multifilament yarn of 150 denier in both warp and weft, weaving density of 90 pieces/inch in length, 67 pieces/inch in width, thickness 160μ) was attached to a glass plate. A 16 wt.
A fiber-reinforced polysulfone support (hereinafter abbreviated as FR-PS support) is prepared by casting the support at a temperature of 10.degree. The pure water permeability coefficient of the FR-PS support (thickness 210-215μ) thus obtained is 0.005-0.01 g/cnf・ measured at a pressure of 1 ki/cd and a temperature of 25°C. sec/a
It was on tm.
実施例１
参考例によって得られたＦＲ−ＰＳ支持体上に１．３．
５−トリアミノベンゼンの２型組％水溶液を塗布量１５
０ｍＪ２／ｍ２となるように均一に塗布した。Example 1 1.3.
Coating amount of 2% aqueous solution of 5-triaminobenzene was 15%.
It was applied uniformly so that it was 0 mJ2/m2.
しかる後に、ビフェニル−３，３°、５．５’−テトラ
カルボン酸クロリドを０．０２３重量％含むトリフルオ
ロトリクロロエタン溶液を６０ｍα／Ｔｒ１２塗布した
。このようにして得られた複合膜を圧力１５ｋｇ／ｃｄ
、１５００１）ｌ）ＩＩＩ Ｎａ（４水溶液、２５°Ｃ
の条件下で逆浸透テストを行なった。その結果、脱塩率
９７．３％、造水量０．２４ｍ”／ｍ２・日の性能を示
した。Thereafter, a trifluorotrichloroethane solution containing 0.023% by weight of biphenyl-3,3°,5,5'-tetracarboxylic acid chloride was applied at 60 mα/Tr12. The composite membrane thus obtained was heated to a pressure of 15 kg/cd.
, 15001) l) III Na (4 aqueous solution, 25 °C
Reverse osmosis tests were conducted under these conditions. As a result, the salt removal rate was 97.3%, and the water production amount was 0.24 m''/m2·day.
−１３＝
実施例２
実施例１で使用したＦＲ−ＰＳ支持体上に、１゜３．５
−トリアミノベンゼンの２重量％水溶液を、塗布１ｉ１
５０ｍＤ、／ｍ２となるように均一に塗布した。-13= Example 2 On the FR-PS support used in Example 1, 1°3.5
- Apply 2% by weight aqueous solution of triaminobenzene 1i1
It was applied uniformly at a density of 50 mD/m2.
しかる後に、テトラヒドロフラン−２，３，４，５−テ
トラカルボン酸クロリドを０．０５１重量％含むトリフ
ルオロトリクロロエタン溶液を６０ｒｒｌ／ｍ２塗布し
た。このようにして得られた複合膜を実施例１と同一の
条件で評価したところ、脱塩率８８゜２％、造水量０．
７２ｍ’ｚ”〜２・日の性能が得られた。Thereafter, a trifluorotrichloroethane solution containing 0.051% by weight of tetrahydrofuran-2,3,4,5-tetracarboxylic acid chloride was applied at 60 rrl/m2. When the composite membrane thus obtained was evaluated under the same conditions as in Example 1, the salt removal rate was 88.2%, and the amount of water produced was 0.2%.
A performance of 72 m'z'' to 2 days was obtained.
実施例３
実施例１で使用したＦＲ−ＰＳ支持体上に、ｍ−フェニ
レンジアミンを１．４５＠量％、１，３．５−トリアミ
ノベンゼンを０．５５重量％含む水溶液を、塗布量１５
０ｒｒｌ／ｍ２となるように均一に塗布した。しかる後
に、テトラヒドロフラン−２，３，４，５−テトラカル
ボン酸クロリドを０．０５１重量％含むトリフルオロト
リクロロエタン溶液を６０ｍＱ／１Ｔ１２塗布した。こ
のようにして得られた複合膜を、実施例１と同様の条イ
１で評価したところ、脱塩率８５．４％、造水ｆｉＮｏ
、 ３２Ｔｎ９／ＴｒＩ２・日の性能が得られた。Example 3 On the FR-PS support used in Example 1, an aqueous solution containing 1.45% by weight of m-phenylenediamine and 0.55% by weight of 1,3.5-triaminobenzene was applied in a coating amount. 15
It was applied uniformly so that it was 0rrl/m2. Thereafter, a trifluorotrichloroethane solution containing 0.051% by weight of tetrahydrofuran-2,3,4,5-tetracarboxylic acid chloride was applied at 60 mQ/1T12. When the composite membrane thus obtained was evaluated using the same strip 1 as in Example 1, the desalination rate was 85.4%, and the water generation fiNo.
, a performance of 32Tn9/TrI2·day was obtained.
比較例
実施例１で使用したＦＲ−ＰＳ支持体上に、ｍ−フェニ
レンジアミンを２．０！ｆｆｉ％含む水溶液を塗布量１
５０ｍα／Ｔ１１２となるように均一に塗布した。しか
る後に、ビフェニル−３，３°、５，５“−テトラカル
ボン酸クロリドを０．０２３重量％服はトリフルオロ１
〜リクロロエタン溶液を６０ｍｆｆ／ｍ２塗布した。こ
のようにしてｊｑられた複合膜を、実施例１と同一の条
件で評価したところ、脱塩率３０゜２％、造水量１．２
２１／和２・日の性能を示した。Comparative Example On the FR-PS support used in Example 1, m-phenylenediamine was added at 2.0! Application amount 1 of aqueous solution containing ffi%
It was applied uniformly so that it was 50 mα/T112. Thereafter, 0.023% by weight of biphenyl-3,3°,5,5"-tetracarboxylic acid chloride was added to trifluoro1.
-A solution of 60 mff/m2 of dichloroethane was applied. When the composite membrane prepared in this manner was evaluated under the same conditions as in Example 1, it was found that the desalination rate was 30°2% and the amount of water produced was 1.2%.
It showed a performance of 21/2 days.
［発明の効果コ
従来提案されている素材に代えて、新しい特定構造を有
する４官能性酸クロリド化合物を使用して形成された超
薄膜層を用いることにより、耐加水分解性、耐微生物性
、耐薬品性、耐塩素性、機械的性質に優れ、ＰＨ変化並
びに乾燥に対しても選択透過性が失われることがない、
卓越した選択分離性能を有する複合半透膜を得ることが
できた。[Effects of the invention] Hydrolysis resistance, microbial resistance, and It has excellent chemical resistance, chlorine resistance, and mechanical properties, and does not lose its selective permselectivity even when subjected to pH changes or drying.
A composite semipermeable membrane with excellent selective separation performance was obtained.
Claims (3)
応生成物からなる架橋重合体を主成分とする超薄膜層を
設けることを特徴とするする半透性複合膜の製造法。 （ａ）芳香族または脂環族多官能アミンであって、１分
子中に２個以上の１級または／および２級アミノ基を有
するもの、または／および分子鎖末端および／または側
鎖に反応性のアミノ基を有する水溶性有機重合体。 （ｂ）次式で示される２種類の化合物より選ばれた少な
くとも１種以上の４官能酸クロリド単独、▲数式、化学
式、表等があります▼ および（または） ▲数式、化学式、表等があります▼ または芳香族多官能酸塩化物であって、３個以下の芳香
族環上に、２または３個の酸クロリド基を有するものと
の混合物。(1) A semipermeable composite membrane characterized by providing on a porous support an ultra-thin film layer mainly composed of a crosslinked polymer made of the reaction products of components (a) and (b) below. Manufacturing method. (a) Aromatic or alicyclic polyfunctional amines having two or more primary or/and secondary amino groups in one molecule, or/and reacting with the terminal and/or side chain of the molecular chain. A water-soluble organic polymer having a chemical amino group. (b) At least one type of tetrafunctional acid chloride alone selected from the two types of compounds shown by the following formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (or) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or a mixture with an aromatic polyfunctional acid chloride having two or three acid chloride groups on three or less aromatic rings.
能アミンが、ｍ−フェニレンジアミン、ｐ−フェニレン
ジアミン、１，３，５−トリアミノベンゼンより選ばれ
た少なくとも１種または２種以上の混合物から成ること
を特徴とする半透性複合膜の製造法。(2) In claim (1), the aromatic polyfunctional amine is at least one or two selected from m-phenylenediamine, p-phenylenediamine, and 1,3,5-triaminobenzene. A method for producing a semipermeable composite membrane comprising the above mixture.
能酸塩化物が、トリメシン酸クロリド、イソフタル酸ク
ロリド、テレフタル酸クロリドより選ばれた少なくとも
１種または２種以上の混合物から成ることを特徴とする
半透性複合膜の製造法。(3) In claim (1), the aromatic polyfunctional acid chloride consists of at least one type or a mixture of two or more selected from trimesic acid chloride, isophthalic acid chloride, and terephthalic acid chloride. A method for producing a semipermeable composite membrane characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61088241A JPS62247808A (en) | 1986-04-18 | 1986-04-18 | Production of semipermeable composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61088241A JPS62247808A (en) | 1986-04-18 | 1986-04-18 | Production of semipermeable composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62247808A true JPS62247808A (en) | 1987-10-28 |
Family
ID=13937361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61088241A Pending JPS62247808A (en) | 1986-04-18 | 1986-04-18 | Production of semipermeable composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62247808A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01132630A (en) * | 1987-10-08 | 1989-05-25 | E I Du Pont De Nemours & Co | Multilayer reverse osmosis membrane |
| US5254261A (en) * | 1991-08-12 | 1993-10-19 | Hydranautics | Interfacially synthesized reverse osmosis membranes and processes for preparing the same |
-
1986
- 1986-04-18 JP JP61088241A patent/JPS62247808A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01132630A (en) * | 1987-10-08 | 1989-05-25 | E I Du Pont De Nemours & Co | Multilayer reverse osmosis membrane |
| US5254261A (en) * | 1991-08-12 | 1993-10-19 | Hydranautics | Interfacially synthesized reverse osmosis membranes and processes for preparing the same |
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