JPS60216810A - Preparation of dry polyetherimide permselective membrane - Google Patents
Preparation of dry polyetherimide permselective membraneInfo
- Publication number
- JPS60216810A JPS60216810A JP59071877A JP7187784A JPS60216810A JP S60216810 A JPS60216810 A JP S60216810A JP 59071877 A JP59071877 A JP 59071877A JP 7187784 A JP7187784 A JP 7187784A JP S60216810 A JPS60216810 A JP S60216810A
- Authority
- JP
- Japan
- Prior art keywords
- liquid
- membrane
- polyetherimide
- compatible
- coagulating
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 239000004697 Polyetherimide Substances 0.000 title claims abstract description 24
- 229920001601 polyetherimide Polymers 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 8
- 230000015271 coagulation Effects 0.000 claims description 6
- 238000005345 coagulation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 18
- 235000019441 ethanol Nutrition 0.000 abstract description 13
- 230000001112 coagulating effect Effects 0.000 abstract description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000007605 air drying Methods 0.000 abstract description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract 3
- 230000035699 permeability Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- -1 carphocyclyl groups Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 101100328519 Caenorhabditis elegans cnt-2 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000017879 Nasturtium officinale Nutrition 0.000 description 1
- 240000005407 Nasturtium officinale Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- B01D71/643—Polyether-imides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は芳香族ポリエーテルイミド乾燥膜の製造方法に
関し、詳しく線高い透水量を有する乾燥限外濾過膜の製
造および乾燥工程の短縮化に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an aromatic polyetherimide dry membrane, and more particularly, to a method for producing a dry ultrafiltration membrane having a high water permeability and shortening the drying process. It is something.
芳香族ポリエーテルイミド鉱床いｐＨ領域で安定でめシ
、かつ耐熱性、耐有機溶剤性にも優れている事から、限
外濾過膜として有用である。湿式製膜によシ容易に製膜
出来る事も利点の１つとなっている。しかし、他のレジ
ンについても言える事であるが、湿式製膜によシ鯛脱さ
れた膜は、従来はとんどが湿潤状態で取シ扱かわれてお
シ、モジュール化、衛生、輸送、保存の面で間醜を有し
ている。また、Ｈ膜後、膜表面をスルホン化、らるい扛
グ、７７ト重合等で修飾する場合、膜は乾燥している必
要のある場合が多い。It is useful as an ultrafiltration membrane because it is stable in a pH range similar to aromatic polyetherimide ore deposits, and has excellent heat resistance and organic solvent resistance. Another advantage is that it can be easily formed into a film by wet film formation. However, as can be said about other resins, membranes that have been removed by wet membrane formation have conventionally been handled in a wet state for the most part, leading to problems such as modularization, hygiene, and transportation. , has a poor quality in terms of preservation. Further, when the membrane surface is modified by sulfonation, lubrication, polymerization, etc. after the H membrane, the membrane often needs to be dry.
その為、乾燥膜の製造方法、使用方法が種々検討されて
いるが、製造時の作業性、膜の透水量の点で未だ満足の
いくものは得られていない。すなわち、単に湿式製膜し
た膜を乾燥させたのでは著るしく透水量鉱低下し、例え
ば逆浸透膜の支持体として用いる場合、不利となる。For this reason, various methods of producing and using dry membranes have been studied, but none have yet been found that are satisfactory in terms of workability during production and water permeability of the membrane. That is, simply drying a wet-formed membrane significantly reduces water permeability, which is disadvantageous when used as a support for a reverse osmosis membrane, for example.
そこで従来よシ乾燥膜の透水量向上に関し、乾燥工程の
前後に検討が加えられている。Therefore, studies have been conducted before and after the drying process to improve the water permeability of dry membranes.
たとえば界面活性剤水溶液に浸漬する方法が特願昭５６
−１１０６１３号公報に開示されているが、これは界面
活性剤が処理後も残存する為、長時間の洗浄が必要であ
シ、また乾燥のままでは残存する界面活性剤の為に、前
記の膜界面の修飾が困難となる。For example, a method of immersion in an aqueous surfactant solution was proposed in a patent application published in 1983.
This method is disclosed in Japanese Patent No. 110613, but since the surfactant remains even after treatment, a long period of cleaning is required. Modification of the membrane interface becomes difficult.
特開昭５７−７１６０６号公報には湿式製膜後、乾燥工
程に入る前に８０℃以上の温水による浸漬工程を加える
方法が提唱されている。しかしこの方法は、アルコール
水溶液による乾燥膜の再湿潤化を行なっても、透水量は
乾燥前の２０〜８０％に回復するにとどまっている。Japanese Unexamined Patent Publication No. 57-71606 proposes a method of adding a dipping step in hot water of 80 DEG C. or higher before entering the drying step after wet film formation. However, in this method, even if the dried membrane is rewetted with an aqueous alcohol solution, the amount of water permeation is only restored to 20 to 80% of the amount before drying.
特開昭５８−４９４０３号公報にも、アルコール水溶液
による再湿肖化が、ポリスルホンの場合に対し、述べら
れているが、この場合も、乾燥前の透水量に回復するに
とどまっている。アルコール、ケトン等の蒸気による処
理も提示されている（Ｕ、Ｓ、Ｐ、 ３，６３２，４０
４ ）が、膜の変形、劣化に注意する必要がある為、作
業はｆｎ〕易ではない。JP-A-58-49403 also describes rewetting with an aqueous alcohol solution for polysulfone, but in this case as well, the water permeability is only restored to the level before drying. Treatment with vapors of alcohols, ketones, etc. has also been proposed (U, S, P, 3,632,40
4) However, the work is not easy as it is necessary to be careful about deformation and deterioration of the membrane.
本発明者らは、上記に鑑み、湿式製膜後の芳香族ポリエ
ーテルイミド膜が乾燥によシ透水量の低下を示す原因と
して乾燥による撥水化とともに、水の蒸発に伴う膜の収
縮も考えられるとの観点から検討を進めた結果、本発明
を完成するに至ったものである。In view of the above, the present inventors have found that the reason why the aromatic polyetherimide membrane after wet film formation exhibits a decrease in water permeability upon drying is not only water repellency due to drying but also shrinkage of the membrane due to water evaporation. As a result of further investigation from the viewpoint of possible possibilities, the present invention has been completed.
本発明は、湿式製膜した芳香族ポリエーテルイミド選択
透過膜を該樹脂の貧溶媒で且つ凝固液と相溶する液体［
Ｉ）に浸漬し、さらに該液体［１］と相溶しかつ凝固液
と相溶性のない液体〔■〕に浸漬して後乾燥する事を特
徴とする乾燥ポリエーテルイミド選択透過膜の製造法で
ある。The present invention uses a wet-formed aromatic polyetherimide permselective membrane with a liquid that is a poor solvent for the resin and is compatible with the coagulating liquid [
A method for producing a dry polyetherimide selectively permeable membrane, characterized by immersing it in I), and then immersing it in a liquid [■] that is compatible with the liquid [1] and incompatible with the coagulating liquid, and then drying it. It is.
ここに芳香族ポリエーテルイミドとは繰シ返し単位の一
般式が
で表わされる重合体である。Here, the aromatic polyetherimide is a polymer whose repeating unit is represented by the general formula:
（但しＡｒｌ 、 Ａｒ２は２価の芳香族基を示す）。(However, Arl and Ar2 represent a divalent aromatic group).
本発明で用いられるポリエーテルイミドは、製膜性、耐
熱性の点から、重合体としての熱変形温度は１８．６
Ｋｇ／ｃｎｔ２荷亜で１５０℃を越えるのに必要な恵合
匿があれに１本合度については特に限定されるものでは
ない。The polyetherimide used in the present invention has a heat distortion temperature of 18.6 as a polymer from the viewpoint of film formability and heat resistance.
There is no particular limitation on the degree of heating required to exceed 150° C. at Kg/cnt2.
好適にＦ１重量平均分子量３０，０００以上のものが用
いられる。主飴牛の芳香環おるいはアルキル基が一部ア
ルキル基、ノ・ロゲン、水敵基、チオアルコール、アル
デヒド基、カルホキクル基、ビニル基、アリル基、アリ
ール基、アミン基、アミド基。F1 weight average molecular weight of 30,000 or more is preferably used. Some of the aromatic rings or alkyl groups of the main candy are alkyl groups, norogens, water groups, thioalcohols, aldehyde groups, carphocyclyl groups, vinyl groups, allyl groups, aryl groups, amine groups, and amide groups.
スルホン基、ニトロ基、酸アミド、ケトキシム。Sulfone group, nitro group, acid amide, ketoxime.
エポキシあるいはシラノール基等の官能基またはこれら
の官能基を含む化合物で置換されたものも利用する事が
出来る。またこれらの官能基を架橋反応に利用し膜特性
を向上させる事も可能でおる。Those substituted with functional groups such as epoxy or silanol groups, or compounds containing these functional groups can also be used. It is also possible to improve membrane properties by utilizing these functional groups in crosslinking reactions.
他のポリイミド重合体等の他の重合体との混合物も用い
る事が出来る。相溶性の良い重合体との混合の他に相溶
性の悪い、例えば室温から８０℃の付近で混合比に制限
のある重合体との混合物を用い製膜する事によシ、特殊
な膜組織を作る事も可能である。相溶性の不充分な重合
体として例えばポリスルホン、ポリエーテルスルホンを
あげる事が出来る。架１ａ、被稙層形成の為に他の化合
物と混合しておく事も出来る。Mixtures with other polymers such as other polyimide polymers can also be used. By forming a film using a mixture with a polymer with good compatibility and a polymer with poor compatibility, for example, whose mixing ratio is limited between room temperature and around 80°C, a special film structure can be created. It is also possible to create Examples of polymers with insufficient compatibility include polysulfone and polyethersulfone. The frame 1a can also be mixed with other compounds to form a grained layer.
また本発明で用いられるポリエーテルイミドは、上記構
造以外の成分とのグラフト、ブロックあるいはランダム
な共重合体も利用する事が出来る。Furthermore, the polyetherimide used in the present invention can also be used as a graft, block or random copolymer with components other than those having the above structure.
共重合成分として架橋反応らるい鉱脱離反応可能なもの
を利用する事も出来る。It is also possible to use as a copolymerization component a substance capable of cross-linking reaction and linte elimination reaction.
本発明のポリエーテルイミド選択透過膜は、鞘ｆｆｉ濾
過、限外濾過、ルースＲＯ、逆浸透濾過、ノく一ペーパ
レー５ｙｖｓｙ、Ａ−エクストラク７ヨン等、いずれの
用途の膜でもよいが好適には前２者の製造に利用される
。また形状について平膜、中空糸状膜、また他のシート
基材あるい線条孔体を支持体とする複合膜さらにポリエ
ーテルイミド膜を支持体とする複合膜のいずれにも利用
出来る。The polyetherimide selectively permeable membrane of the present invention may be used for any purpose, such as sheath ffi filtration, ultrafiltration, loose RO, reverse osmosis filtration, Nokuichi paper layer 5yvsy, A-extra 7yon, etc., but is preferably is used to manufacture the first two. Regarding the shape, it can be used in any of flat membranes, hollow fiber membranes, composite membranes using other sheet substrates or linear pores as a support, and composite membranes using a polyetherimide membrane as a support.
膜組織についても、表層が電子顕微鏡でも孔が認められ
ない程緻密ないわゆるスキン層で覆われた膜あるいは榎
われていない膜、また内部が多孔体状であるものも指状
構造であるものも用いる事が出来る。既に膜表面に他の
官能基や化合物が結合していたｂｉ表面層上で架橋反応
させであるものでもよい。Regarding the membrane structure, there are membranes whose surface layer is covered with a so-called skin layer so dense that no pores can be seen even under an electron microscope, membranes which are not covered, and membranes whose interior is porous or has a finger-like structure. It can be used. A crosslinking reaction may be carried out on the bi surface layer to which other functional groups or compounds have already been bonded to the membrane surface.
その他、多孔性選択透過膜を作成するのに、後工程で溶
解抽出する為の物質をレジンに混入しておく方法が知ら
れているが、このものも利用出来る。In addition, a method is known in which a material for dissolving and extracting in a subsequent step is mixed into the resin in order to create a porous permselective membrane, and this method can also be used.
本発明て利用される湿式製膜法についても、なんら制限
されない。すなわち基本的にはレジン溶液を流延し、レ
ジンの非溶媒で且クレソン溶液の溶媒とは相溶する凝固
液に浸漬し、選択透過膜を得る方法であり、レジン溶液
や凝固液組成、＠度等の凝固条件は、設計する膜によシ
釉々あるが、そのいずれの方法で得られた膜についても
、本発明の方法を適用する事が出来る。例えはレジン溶
液に金属塩を添加したシ、凝固液中に一部レジンを溶解
また線膨潤させる化合物を混入する事によシ、透水１分
画が種に！１１節される。The wet film forming method used in the present invention is not limited at all. That is, basically, it is a method to obtain a selectively permeable membrane by casting a resin solution and immersing it in a coagulation liquid that is a non-solvent of the resin and compatible with the solvent of the watercress solution. Coagulation conditions such as degree of glaze depend on the designed membrane, but the method of the present invention can be applied to membranes obtained by any of these methods. For example, by adding a metal salt to the resin solution, or by mixing a compound that partially dissolves the resin or causes linear swelling in the coagulation solution, the 1 fraction of water permeation becomes a seed! Verse 11 is given.
本発明において用いられる液体ＣＩ）はポリエーテルイ
ミドの貧溶媒で且つ凝固液と相溶性のあるものであれは
特に限定されない。単一液状物でも、また混合液でもよ
く、一部凝固液と同一組成のものを含んでいてもよい。The liquid CI) used in the present invention is not particularly limited as long as it is a poor solvent for polyetherimide and is compatible with the coagulating liquid. It may be a single liquid or a mixed liquid, and may partially contain a liquid having the same composition as the coagulating liquid.
融点等についても制限されるものではないが當温付近に
融点あるいは沸点がなく、化学的に安定。There are no restrictions on melting point, etc., but there is no melting point or boiling point near this temperature, and it is chemically stable.
低毒性のものを用いるのが実際的である。ポリエーテル
イミドの場合、凝固液として水あるいは水溶液を利用す
ることが出来、その場合液体〔夏〕として杖例えばアル
コール類、アルコールとエーテルの混合溶液をあげる事
が出来る。液体（ＩＩ） ａ液体ＣＩ）によって決まシ
、液体ＩＩＩ）としてアルコール、とくにエチルアルコ
ールを利用する場合には、例えにシクロヘキサン、メチ
ルエチルケト７、ジエチルエーテル等をあげる事が出来
る。液体［ＩＩ）についても、液体ＣＩ］と同様、単一
でも混合溶液でもよい。It is practical to use a substance with low toxicity. In the case of polyetherimide, water or an aqueous solution can be used as the coagulating liquid, and in that case, the liquid (summer) can be an alcohol, for example, or a mixed solution of alcohol and ether. Liquid (II) (a) Depends on the liquid CI). When alcohol, especially ethyl alcohol, is used as the liquid III), examples include cyclohexane, methyl ethyl keto7, diethyl ether, etc. Liquid [II] may also be a single solution or a mixed solution, similar to liquid CI].
液体〔■〕、液体〔■〕ともに、それぞれ凝固液。Both liquid [■] and liquid [■] are solidified liquids.
液体［Ｉ］との膜内での置換が容易に行なわれる事、ま
た液体［ＩＩ）の乾燥が容易に行なわれる事が望ましく
、低沸点、低粘度の溶媒が好適に用いられる。It is desirable that the liquid [I] be easily replaced within the membrane, and that the liquid [II] be easily dried, and a solvent with a low boiling point and low viscosity is preferably used.
膜を液体［Ｉ）および液体（ＩＩ）に浸漬する工程は、
膜の変質、破損がない事および凝固液液体〔ｌ〕との置
換が行なえる事に注怠し、温度、液量を決足すれば良く
、特に限定されない。従って膜を各浸漬槽に浸漬する方
法あるいは膜の浸漬に成体〔Ｉ〕。The step of immersing the membrane in liquid [I) and liquid (II) is
There are no particular limitations, as long as the temperature and amount of liquid are determined while taking care that there is no deterioration or damage to the membrane and that the coagulating liquid can be replaced with the liquid [l]. Therefore, the method of immersing the membrane in each dipping tank or the immersion of the membrane [I].
液体［ＩＩ］を段階的に導入する方＠等、いずれも利用
可能である。また本発明で用いられるＭは湿式製膜直後
のもの、湿式Ｍ換後熱処理等の加工をｔよどこしたもの
、るるいはモジュール化したもののいずれもオリ用する
事が出来る。実施例に示す様に液体〔Ｉ〕の浸漬条件に
よって膜の透水量を高くする事が出来る。すなわち液体
［Ｉ］がポリエーテルイミドに対して全くの非溶媒で社
なく、膨潤性を有する貧溶媒の場合、液体ＣＩ）に浸漬
する事によシ、膜の透水量を増加する事が出来る。Any method such as introducing liquid [II] in stages can be used. Further, the M used in the present invention can be used either immediately after wet film formation, after undergoing processing such as heat treatment after wet M conversion, or after being made into a module. As shown in the examples, the water permeability of the membrane can be increased by adjusting the immersion conditions of liquid [I]. In other words, if liquid [I] is not a complete non-solvent for polyetherimide, but is a poor solvent with swelling properties, the water permeability of the membrane can be increased by immersing it in liquid CI). .
液体［ＩＩ）の乾燥には、加熱、減圧、風乾のいずれを
用いてもよいが、風乾の後加熱乾燥するのが工業的には
好適である。風乾のみだと液体（ＩＩ）が残存する可能
性がらり、好ましくない場合もある。Although heating, reduced pressure, or air drying may be used to dry the liquid [II], it is industrially preferable to air dry and then heat dry. If only air drying is performed, there is a possibility that liquid (II) may remain, which may be undesirable.
本発明方法に従うと、単に乾燥工程により透水量が低下
する事を防ぐだけでなく、湿式ａｍ後の後工程で種々の
透水量の膜が得られるので、工業的に有利である。すな
わち、透水量のａｈ異なる膜を得んとする時これをレジ
ン溶液、凝固液組成るるいは湿式製膜条件等によシ調節
しようとすると、かなル煩雑なものとなるのに対し、本
発明方法では乾燥の前工程が一見増す様であるが、凝集
力の強い水やアルコールを乾燥させるのに比較し、シク
ロヘキサンの様に凝集力の弱い液体を乾燥するのは容易
でらシ、全体とすれは作業は容易である。The method of the present invention is industrially advantageous because it not only prevents the water permeation from decreasing due to the drying process, but also allows membranes with various water permeability to be obtained in the post-wet AM process. In other words, when trying to obtain membranes with different water permeability, it would be very complicated to adjust them by adjusting the resin solution, coagulation liquid composition, wet membrane forming conditions, etc. Although the inventive method seems to require more pre-drying steps, it is easier to dry a liquid with a weak cohesive force such as cyclohexane compared to drying water or alcohol with a strong cohesive force, and overall The work is easy.
ポリエーテルイミド紘特定の極性溶媒に溶解する。従っ
て湿式製膜に於いて凝固液としては該極性溶媒と容易に
置換する水等の液体が選はれる。Polyetherimide gel dissolves in certain polar solvents. Therefore, in wet film formation, a liquid such as water that easily replaces the polar solvent is selected as the coagulating liquid.
この様な液体は凝集力がきわめて強く、そのまま乾燥し
たのでは、透水量の低下の一原因として考えられる膜の
収縮を伴う。Such a liquid has an extremely strong cohesive force, and if it is dried as it is, the membrane will shrink, which is considered to be one of the reasons for the decrease in water permeability.
凝集力の充分弱い液体（液体〔■〕）は一般に凝集力の
強い溶媒とは相容性がない。そこで一旦両者と相溶性の
ある適度の凝集力を示す液体（液体〔ｌ〕）と置換した
後さらに低凝集力の液体（液体〔■〕）と置換しこれを
乾燥する事によシ、乾燥時の膜の収縮を防ぐ事が出来た
ものと考えられる。Liquids with sufficiently weak cohesive forces (liquids [■]) are generally incompatible with solvents with strong cohesive forces. Therefore, by first replacing the liquid with a liquid (liquid [L]) that is compatible with both of them and showing an appropriate cohesive force, and then replacing it with a liquid with a low cohesive force (liquid [■]) and drying it, the drying process is performed. It is thought that this was able to prevent the contraction of the membrane of time.
また液体ＣＤがポリエーテルイミドに対し漸干膨潤性を
示す場合に−は、液体［，１］への浸漬によシ、膜レジ
ンが膨潤あるいは一部溶解し、透水が増加したと考えら
れる。In addition, in the case where liquid CD exhibits a gradual swelling property with respect to polyetherimide, it is considered that the membrane resin swells or partially dissolves due to immersion in liquid [, 1], resulting in increased water permeation.
以下実施例を挙けて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例１〜３
芳香族ポリエーテルイミドウルテム１０００ （ゼネラ
ル・エレクトリック社製）１６恵九部をＮ−メチル−２
ピロリドン８４重量部に加熱溶解させ、レジン溶液を作
成する。脱泡彼室温にてガラス板上に流延し、さらに２
０℃の水に浸漬して厚さ１１０−１３０μの選択透過膜
を得た（透水２８０〜２９０１７ｍ２ｈｒ ａｔｍ ）
。この膜を乾燥せずそのまま１８℃のエチルアルコール
に浸漬する。Examples 1 to 3 Aromatic polyetherimide Ultem 1000 (manufactured by General Electric Company) 16 Keku part to N-methyl-2
A resin solution is prepared by heating and dissolving 84 parts by weight of pyrrolidone. Defoamed and cast onto a glass plate at room temperature, and then
A permselective membrane with a thickness of 110-130μ was obtained by immersing it in water at 0°C (water permeability 280-29017 m2hr atm).
. This membrane is immersed in ethyl alcohol at 18° C. without drying.
所定時間浸漬した後、１８℃のシクロヘキサン（沸点８
０．７℃）に３０分浸漬する。次にこの膜を８０℃３０
分乾燥し、乾燥膜を得た。透水量の測定は１８℃〜２０
℃のエチルアルコール７０重量％水溶液に１０分間浸漬
し、次いで水に３０分浸漬した後行なった。測定結果を
第１衣に示す。After soaking for a predetermined time, cyclohexane at 18°C (boiling point 8
0.7℃) for 30 minutes. Next, this film was heated at 80℃30
The mixture was dried for several minutes to obtain a dry film. Measurement of water permeability is from 18℃ to 20℃
The test was carried out after being immersed in a 70% by weight aqueous solution of ethyl alcohol at 10°C for 10 minutes, and then in water for 30 minutes. The measurement results are shown in the first garment.
これらの膜は８０℃の乾燥工程が与えられたものでおる
が、風乾だけでも、若干透水月が下る傾向は見られるが
＃！は同様の結果が僧られる、比較例１〜４
シクロヘキサン浸漬以外Ｌ１それぞれ実施例１〜３と全
く同じ処理をし、乾燥膜とした。結果を■
にまとめて示す。These membranes have been subjected to a drying process at 80°C, but even with air drying alone, there is a tendency for the water permeability to decrease slightly. Similar results were obtained. Comparative Examples 1 to 4 L1 was treated in exactly the same manner as in Examples 1 to 3, except for cyclohexane immersion, and dried films were obtained. The results are summarized in ■.
第１表 乾燥膜の透水量
比較例５
実施例１と同様に芳香族ポリエーテルイミドの選択透過
膜を作成し、これを乾燥せずそのまま１８℃のエチルア
ルコールに３０分浸漬した。次に１８℃のシクロヘキサ
ンに３０分、６０分、１２０分。Table 1 Comparative example 5 of water permeability of dry membrane A selectively permeable membrane of aromatic polyetherimide was prepared in the same manner as in Example 1, and the membrane was immersed in ethyl alcohol at 18° C. for 30 minutes without drying. Next, soak in cyclohexane at 18°C for 30 minutes, 60 minutes, and 120 minutes.
１８０分それぞれ浸漬さセ、さらに８０Ｃ３０分乾燥器
にて乾燥し乾燥膜ｔ−得た。これらの膜の透水量を測定
したＢ目よとんど差が誌められず実施例１と同様の値で
あった。この事から透水量の駒整は第１の液の浸漬時間
のコントロールのみで行い得る事が判る。The samples were immersed for 180 minutes and then dried in a dryer at 80C for 30 minutes to obtain a dry film. The water permeability of these membranes was measured and the values were similar to those of Example 1, with no noticeable difference in the amount of water permeation B. This shows that the amount of water permeation can be adjusted only by controlling the immersion time of the first liquid.
実施例４〜６
実施例１〜３と同様に芳香族ポリエーテルイミドの選択
透過膜を作成し、さらに実施例１〜３と同様の方法で１
８℃のエチルアルコールにＢ１定時間浸漬した後、１８
℃のジエチルエーテル（沸点３４．６℃）ｔｃ３０分浸
漬する。次にこの膜を４０℃１５分乾燥器にて乾燥膜を
得た。透水量の測定は実施例１〜３と同様の方法で行な
った。結果を第２表に示す。Examples 4 to 6 A selectively permeable membrane of aromatic polyetherimide was prepared in the same manner as in Examples 1 to 3, and 1 was further prepared in the same manner as in Examples 1 to 3.
After immersing B1 in ethyl alcohol at 8°C for a certain period of time, 18
℃ diethyl ether (boiling point 34.6℃) tc 30 minutes immersion. Next, this film was dried in a dryer at 40°C for 15 minutes. The water permeation amount was measured in the same manner as in Examples 1 to 3. The results are shown in Table 2.
第２災 乾燥膜の透水量Second disaster: Water permeability of dry membrane
Claims (1)
該樹脂の貧溶媒で且つ凝固液と相溶する液体〔１〕に浸
漬し、さらに該液体〔１〕と相溶しかつ凝固液 と相溶
性のない液体〔１１〕に浸漬して後乾燥する乾燥ポリエ
ーテルイミド選択透過膜において該芳香族ポ リエーテ
ルイミドが繰り返し単位の一般式が （但しＡｒ、、 、Ａｒ２は２価の芳香族基を示す、、
）で表わされる重合体であることを特徴とする乾燥ポ
リエーテルイミド選択透過膜の製造方法。[Claims] A wet-formed aromatic polyetherimide permselective membrane,
It is immersed in a liquid [1] that is a poor solvent for the resin and is compatible with the coagulation liquid, and further immersed in a liquid [11] that is compatible with the liquid [1] but not compatible with the coagulation liquid, and then dried. In the dry polyetherimide selectively permeable membrane, the general formula of the repeating unit of the aromatic polyetherimide is (where Ar, , Ar2 represents a divalent aromatic group,
) A drying pot characterized by being a polymer represented by
A method for producing a rietherimide selectively permeable membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59071877A JPS60216810A (en) | 1984-04-12 | 1984-04-12 | Preparation of dry polyetherimide permselective membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59071877A JPS60216810A (en) | 1984-04-12 | 1984-04-12 | Preparation of dry polyetherimide permselective membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60216810A true JPS60216810A (en) | 1985-10-30 |
| JPH0451219B2 JPH0451219B2 (en) | 1992-08-18 |
Family
ID=13473184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59071877A Granted JPS60216810A (en) | 1984-04-12 | 1984-04-12 | Preparation of dry polyetherimide permselective membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60216810A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5598229A (en) * | 1978-12-06 | 1980-07-26 | Gen Electric | Thermoplastic organic polymer |
| JPS583603A (en) * | 1981-07-01 | 1983-01-10 | Ube Ind Ltd | Production of dried separating membrane made of polyimide |
-
1984
- 1984-04-12 JP JP59071877A patent/JPS60216810A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5598229A (en) * | 1978-12-06 | 1980-07-26 | Gen Electric | Thermoplastic organic polymer |
| JPS583603A (en) * | 1981-07-01 | 1983-01-10 | Ube Ind Ltd | Production of dried separating membrane made of polyimide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0451219B2 (en) | 1992-08-18 |
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