JPH03284333A - Liquid separating material and separation of liquid - Google Patents
Liquid separating material and separation of liquidInfo
- Publication number
- JPH03284333A JPH03284333A JP8230690A JP8230690A JPH03284333A JP H03284333 A JPH03284333 A JP H03284333A JP 8230690 A JP8230690 A JP 8230690A JP 8230690 A JP8230690 A JP 8230690A JP H03284333 A JPH03284333 A JP H03284333A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- liquid
- alkylene oxide
- water
- liquid separation
- 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
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 title claims description 48
- 238000000926 separation method Methods 0.000 title claims description 44
- 229920002647 polyamide Polymers 0.000 claims abstract description 56
- 239000004952 Polyamide Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 12
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 9
- 229920001778 nylon Polymers 0.000 abstract description 8
- 239000004677 Nylon Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 5
- -1 sheets Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical group C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 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
- B01D71/56—Polyamides, e.g. polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルキレンオキサイドグラフトポリアミドを
用いた液分離材に関し、また水、アルコール、塩素化炭
化水素及びアミン類を含有する液体混合物からその含有
物の分離方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a liquid separation material using alkylene oxide grafted polyamide, and also relates to a liquid separation material using alkylene oxide grafted polyamide, and also relates to a liquid separation material containing water, alcohol, chlorinated hydrocarbons, and amines. Concerning methods of separating objects.
従来から各種の高分子膜が機能性膜として提案され、従
来の化学工業における多量のエネルギーを要する蒸留、
精留等に代わり膜分離を適用したり、またバイオテクノ
ロジー分野の液液分離での適用、医療分野での適用等液
体混合物の分離技術への高分子膜の適用はますます盛ん
となり、その応用も広がりつつある。Various polymer membranes have been proposed as functional membranes in the past, and they have been used in the conventional chemical industry for distillation, which requires a large amount of energy.
The application of polymer membranes to liquid mixture separation technology is becoming more and more popular, such as applying membrane separation instead of rectification, liquid-liquid separation in the biotechnology field, and application in the medical field. is also expanding.
しかしながら、高分子膜の透過選択性は特異的であり、
適用分野により用いられる膜も種々であり、各種の高分
子膜技術は現在も未だ開発段階にある。However, the permselectivity of polymer membranes is specific;
Various membranes are used depending on the field of application, and various polymer membrane technologies are still in the development stage.
発明者らは、従来ナイロンの改質を目的になされたアル
キレンオキサイドのグラフトポリアミドについて、その
機能性を中心に検討をした結果、液液分離能を有するこ
とを知見し、本発明に至った。The inventors have studied the functionality of alkylene oxide graft polyamides, which have conventionally been made for the purpose of modifying nylon, and have found that they have liquid-liquid separation ability, leading to the present invention.
アルキレンオキサイドグラフトポリアミドは、ポリアミ
ドと、エチレンオキサイド、1.2−プロピレンオキサ
イド、1.2−ブチレンオキサイド等のC2−1の1,
2−アルキレンオキサイドとをグラフト反応させて得る
ことができ、例えば特開開47−897号公報等で既に
知られている。Alkylene oxide graft polyamide is a combination of polyamide and C2-1 1, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, etc.
It can be obtained by grafting reaction with 2-alkylene oxide, and is already known, for example, in JP-A No. 47-897.
これらアルキレンオキサイドグラフトポリアミドは、上
記のようにナイロンの改質を目的になされ、主にポリア
ミドの親水性、帯電防止性等の向上を図るためのもので
、液体混合物の液分離の機能面に言及したものはない。These alkylene oxide graft polyamides are made for the purpose of modifying nylon as mentioned above, and are mainly used to improve the hydrophilicity, antistatic properties, etc. of polyamides, and refer to the functional aspect of liquid separation of liquid mixtures. There is nothing I did.
本発明は、上記アルキレンオキサイドグラフトポリアミ
ドの液液分離の機能性に着目してポリアミド系の新規な
液分離材を提供することを目的とし、更にまた特に水、
アルコール、塩素化炭化水素及びアミン類含有の液体混
合物からそれら含有物を選択的に分離する液分離材を用
いた液分離方法を提供することを目的にする。The present invention focuses on the liquid-liquid separation functionality of the alkylene oxide grafted polyamide, and aims to provide a new polyamide-based liquid separation material.
An object of the present invention is to provide a liquid separation method using a liquid separation material that selectively separates alcohol, chlorinated hydrocarbons, and amines from a liquid mixture containing these substances.
本発明によれば、アルキレンオキサイドグラフトポリア
ミドからなることを特徴とする液分離材が提供される。According to the present invention, there is provided a liquid separation material characterized by being made of alkylene oxide graft polyamide.
また更に、アルキレンオキサイドグラフトポリアミドか
らなる液分離材を使用して、水、アルコール、塩素化炭
化水素及びアミン類の少なくとも1種を含有する液体混
合物から含有するその化合物を分離することを特徴とす
る液分離方法が提供される。Furthermore, the method is characterized in that a liquid separation material made of alkylene oxide grafted polyamide is used to separate the compound contained in the liquid mixture containing at least one of water, alcohol, chlorinated hydrocarbon, and amines. A liquid separation method is provided.
以下、本発明について更に詳細に説明する。The present invention will be explained in more detail below.
本発明で用いるアルキレンオキサイドグラフトポリアミ
ド(以下、単にグラフトポリアミドとする。)は、ポリ
アミドと、エチレンオキサイド、1.2−プロピレンオ
キサイド、1.2−ブチレンオキサイド等の02−4の
1,2−アルキレンオキサイドとを反応させて得ること
ができる。ポリアミドとしては、ナイロン6、ナイロン
6B、ナイロン610、ナイロン11、ナイロン612
等の代表的なナイロンを用いることができる。The alkylene oxide graft polyamide (hereinafter referred to simply as graft polyamide) used in the present invention is a combination of polyamide and 02-4 1,2-alkylene such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, etc. It can be obtained by reacting with oxide. Polyamides include nylon 6, nylon 6B, nylon 610, nylon 11, and nylon 612.
Typical nylons such as nylon can be used.
本発明のグラフトポリアミドは、ポリアミドに1.2−
アルキレンオキサイドをグラフトさせる公知のいずれの
方法を用いて得てもよい。通常、上記ナイロンの粉末或
いはペレット、またはフィルム状ナイロンと上記アルキ
レンオキサイドとを約1:0.5〜10モル比で用いて
、無触媒、窒素等の不活性ガス雰囲気下にオートクレー
ブ中で、約100°C以下に所定時間保持し、未反応物
及びアルキレンオキサイドのホモポリマーを除去して得
ることができる。The graft polyamide of the present invention has 1.2-
It may be obtained using any known method of grafting alkylene oxides. Usually, the above-mentioned nylon powder or pellets or film-like nylon and the above-mentioned alkylene oxide are used in a molar ratio of about 1:0.5 to 10, and in an autoclave without a catalyst and under an inert gas atmosphere such as nitrogen, about It can be obtained by maintaining the temperature at 100°C or lower for a predetermined time to remove unreacted substances and alkylene oxide homopolymer.
この場合、前記特開昭47−897号公報に記載の方法
で得られるグラフトポリアミドは、水溶性であり分離材
として使用するには条件的に制限され好ましくない。In this case, the graft polyamide obtained by the method described in JP-A-47-897 is water-soluble and is therefore undesirable for use as a separation material due to limitations.
本発明で用いるグラフトポリアミドの1.2−アルキレ
ンオキサイドグラフト率は、特に制限されるものでない
が、通常、グラフト率の増加と共に液体透過性が上昇す
るので、所望の分離率や分離条件により適宜選択して用
いることができる。The 1,2-alkylene oxide grafting rate of the graft polyamide used in the present invention is not particularly limited, but the liquid permeability usually increases as the grafting rate increases, so it is selected as appropriate depending on the desired separation rate and separation conditions. It can be used as
−船釣には、グラフト率が約30%以上、好ましくは約
50%以上のグラフトポリアミドを用いるのが好ましい
。- For boat fishing, it is preferable to use a grafted polyamide with a graft ratio of about 30% or more, preferably about 50% or more.
上記のようにして得られるグラフトポリアミドは、主に
ポリアミドのアミド基に1,2−アルキレンオキサイド
が反応、重合し、アルキレンオキサイドの重合物がグラ
フト結合したものである。The graft polyamide obtained as described above is mainly obtained by reacting and polymerizing 1,2-alkylene oxide with the amide group of polyamide, and grafting a polymer of alkylene oxide.
本発明の液分離材は、膜状の分離膜として、また粉末状
、粒状、シート状、繊維状等の形態として容器内に充填
して吸収分離材として用いることができる。The liquid separation material of the present invention can be used as an absorption separation material by being filled into a container in the form of a membrane-like separation membrane or in the form of a powder, granules, sheet, fiber, or the like.
分離膜として使用する場合の液分離膜は、上記グラフト
ポリアミドからなる薄膜であり、通常の粉末状或いはペ
レット状ポリアミドにグラフトさせて得たグラフトポリ
アミドを適当な溶媒、例えば蟻酸、硫酸、トリフルオル
エタノール、テトラフルオルプロパツール、ヘキサフル
オルイソプロパツール等に溶解し、その溶液から薄膜を
形成し溶媒を除去して固化して均質膜に製膜する湿式製
膜法にて得ることができる。また、この場合、均質膜の
製造に用いる基材として表面の平滑な、例えば、ガラス
板、銅板及び、金属ロールまたはヘルド等を使用して製
膜し、膜形成後基材から膜を引き剥がせば、極めて薄い
フィルム状のものが得られる。また、グラフトポリアミ
ドを溶融してインフレーション成形法やTダイ成形法で
フィルムにしてもよいし、その成形フィルムを更に延伸
したフィルムでもよい。When used as a separation membrane, the liquid separation membrane is a thin film made of the above-mentioned grafted polyamide, and the grafted polyamide obtained by grafting it onto a normal powdered or pelleted polyamide is mixed with a suitable solvent such as formic acid, sulfuric acid, or trifluoroethanol. , tetrafluoropropanol, hexafluoroisopropanol, or the like, forming a thin film from the solution, removing the solvent, and solidifying to form a homogeneous film. In this case, the film is formed using a substrate with a smooth surface, such as a glass plate, a copper plate, a metal roll, or a heald, as the base material used for manufacturing the homogeneous film, and after the film is formed, the film is peeled off from the base material. By doing so, an extremely thin film can be obtained. Further, the graft polyamide may be melted and made into a film using an inflation molding method or a T-die molding method, or a film obtained by further stretching the molded film may be used.
この薄いフィルム状の均質膜は、そのまま液分離膜とし
て使用することもでき、また、他の多孔質膜と積層また
は貼合わせて使用することもできる。また均質膜製膜の
基材として多孔質膜を使用して、多孔質膜の表面に一体
に形成された複合液分離膜を得ることもできる。This thin film-like homogeneous membrane can be used as it is as a liquid separation membrane, or can be used by laminating or bonding with other porous membranes. Furthermore, by using a porous membrane as a base material for forming a homogeneous membrane, it is also possible to obtain a composite liquid separation membrane integrally formed on the surface of the porous membrane.
更にまた本発明においては、予めポリアミドフィルムを
公知の方法にて形成しそのポリアミドフィルムに直11
,2−アルキレンオキサイドをグラフトさせて得ること
もできる。予めフィルム成形したポリアミドをグラフト
して用いる場合、未延伸フィルムに1,2−アルキレン
オキサイドをグラフトして得たグラフトポリアミドフィ
ルムは、延伸フィルムのグラフトフィルムより水、メタ
ノール等のアルコール、塩素化炭化水素及びアミン類の
透過性が高く、それら−の含有液混合物の分離にはより
適する。Furthermore, in the present invention, a polyamide film is formed in advance by a known method, and the polyamide film is directly coated with a polyamide film.
, 2-alkylene oxide can also be grafted. When using a polyamide film formed in advance by grafting, the grafted polyamide film obtained by grafting 1,2-alkylene oxide onto an unstretched film is free from water, alcohol such as methanol, and chlorinated hydrocarbons than the grafted film of the stretched film. and amines, making it more suitable for separating liquid mixtures containing them.
本発明の液分離材は、グラフトポリアミドを平膜状、ま
たは中空糸状に形成して種々の構造とすることかでき、
通常の圧力差により分離する通常濾過、精密濾過、限外
濾過、逆浸透法等の液濾過膜即ち液分離膜として使用で
きる。The liquid separation material of the present invention can be formed into various structures by forming the graft polyamide into a flat membrane shape or a hollow fiber shape,
It can be used as a liquid filtration membrane, ie, a liquid separation membrane, for ordinary filtration, precision filtration, ultrafiltration, reverse osmosis, etc., which separates by ordinary pressure difference.
本発明において、液分離膜を形成するグラフトポリアミ
ドの均質層は、その厚さは特に制限されないが、通常0
.1〜500μmの厚さで用いられる。In the present invention, the thickness of the homogeneous graft polyamide layer forming the liquid separation membrane is not particularly limited, but is usually 0.
.. It is used in a thickness of 1 to 500 μm.
本発明のグラフトポリアミドの液分離膜は、水、アルコ
ール、塩素化炭化水素及びアミン類を選択的に透過し、
特に水、メタノール、塩化メチレン、クロロフォルム、
ジクロロエタン、トリクロロエタン、テトラクロロエタ
ン、ペンタクロロエタン、ヘキサメチレンジアミン、ア
ニリン、N−メチルアニリン、N−エチルアニリン、0
−メチルアニリン、m−メチルアニリン、0−クロロア
ニリン、m−クロロアニリン、ピリジンの透過性が特に
高く、これらの含有液の分離、精製、濃縮等に好適に使
用することができる。例えば、塩化メチレン等の塩素化
炭化水素を抽出や反応に溶媒として用いた場合に、それ
らの分離除去に有効に用いることができる。The graft polyamide liquid separation membrane of the present invention selectively permeates water, alcohol, chlorinated hydrocarbons, and amines,
Especially water, methanol, methylene chloride, chloroform,
Dichloroethane, trichloroethane, tetrachloroethane, pentachloroethane, hexamethylenediamine, aniline, N-methylaniline, N-ethylaniline, 0
- It has particularly high permeability for methylaniline, m-methylaniline, 0-chloroaniline, m-chloroaniline, and pyridine, and can be suitably used for separation, purification, concentration, etc. of liquids containing these. For example, when chlorinated hydrocarbons such as methylene chloride are used as a solvent in extraction or reaction, they can be effectively used for separation and removal.
本発明の液分離は、上記のように圧力差による濾過分離
のいずれにも適用できるが、特に好ましくは、限外濾過
、浸透気化等に用いることができ、これら液分離におい
て、好ましくは0〜150°C1特に好ましくは10〜
100°Cで、約0.1〜100 kg/cm2の圧力
下、特に好ましくは約0.5〜80kg/cm”の圧力
下で行うのが好ましい。The liquid separation of the present invention can be applied to any of the filtration separations using pressure differences as described above, but it can be particularly preferably used for ultrafiltration, pervaporation, etc. In these liquid separations, preferably 0 to 150°C1, particularly preferably 10~
Preferably, the reaction is carried out at 100 DEG C. and under a pressure of about 0.1 to 100 kg/cm@2, particularly preferably about 0.5 to 80 kg/cm".
本発明のグラフトポリアミドは、上記のような膜による
液分離に有効に使用できる以外に、また水、アルコール
、塩素化炭化水素及びアニリン等のアミン類等の吸収能
にも優れ、それらの吸収分離材としても適用することが
できる。The graft polyamide of the present invention can be effectively used for liquid separation using a membrane as described above, and also has excellent absorption ability for water, alcohol, chlorinated hydrocarbons, and amines such as aniline, and can be used for absorption and separation of water, alcohol, chlorinated hydrocarbons, and amines such as aniline. It can also be used as a material.
この場合、前記の通り本発明のグラフトポリアミドを粉
末状、粒状、シート状、繊維状等の形態として吸収分離
材とするのが好ましく、その形状、大きさ等は特に制限
されない。通常、粒形で平均粒径が0.01〜5mのも
のが用いられる。液体混合物から液含有物の吸収分離を
行うには、前記のようにカラム等の容器内に上記のよう
な形態状物を充填して液体混合物を流通させつつ水等所
定の液含有物を吸収させ分離させてもよい。また、液体
混合物等に上記形態状物を投入浸漬させ、所定の液含有
物を吸収して分離除去することもできる。In this case, as described above, it is preferable to use the graft polyamide of the present invention in the form of a powder, granules, sheet, fiber, etc. as an absorption/separation material, and the shape, size, etc. thereof are not particularly limited. Generally, particles having an average particle diameter of 0.01 to 5 m are used. In order to absorb and separate a liquid-containing substance from a liquid mixture, as described above, a container such as a column is filled with the above-mentioned material, and while the liquid mixture is flowing, a predetermined liquid-containing substance such as water is absorbed. It may also be separated. Alternatively, the above-mentioned shaped article can be immersed in a liquid mixture or the like, and predetermined liquid-containing substances can be absorbed and separated and removed.
本発明のグラフトポリアミドは、特に水の吸収において
特異な現象を有し、例えば、グラフト率81.8%のグ
ラフトポリアミドを用いて水を吸収する場合、平衡吸水
率(所定温度における平衡に達した時の吸水率)は、5
°Cで約200%、20°Cで約145%、100°C
で約112%と低温において平衡吸水率が大きく、高温
になるに従G1低くなる。またこの現象は、5°Cから
100°Cへ、また100°Cから5°Cへと温度を繰
り返し変化させてもその性質は変わらず、本発明のグラ
フトポリアミド液分離材が吸水と水の放出を再現性よく
繰り返すことができ、水吸収材として用いて、吸収・再
生を繰り返して使用することができる。The graft polyamide of the present invention has a unique phenomenon particularly in the absorption of water. For example, when a graft polyamide with a graft ratio of 81.8% is used to absorb water, the equilibrium water absorption water absorption rate) is 5
Approximately 200% at °C, approximately 145% at 20°C, 100°C
The equilibrium water absorption rate is approximately 112% at low temperatures, and G1 decreases as the temperature increases. In addition, this phenomenon does not change even if the temperature is repeatedly changed from 5°C to 100°C and from 100°C to 5°C. Release can be repeated with good reproducibility, and it can be used as a water absorbing material to repeatedly absorb and regenerate.
以下に、本発明の実施例について詳しく説明する。但し
、本発明は以下の実施例に限定されるものでない。Examples of the present invention will be described in detail below. However, the present invention is not limited to the following examples.
なお、本発明において、全重合率(%)、グラフト重合
率(%)、ホモ重合率(%)、重量増加率(%)、グラ
フト率(%)及びグラフト効率(%)は下記の各式によ
り算出された値である。In addition, in the present invention, the total polymerization rate (%), graft polymerization rate (%), homopolymerization rate (%), weight increase rate (%), grafting rate (%), and grafting efficiency (%) are expressed by the following formulas. This is the value calculated by
但し、下記各式において、反応仕込みポリアミド量をW
i 、アルキレンオキサイド量をQ、反応後の未反応
アルキレンオキサイドを除去した後の固形物重量をW2
、前記固形物を熱水洗浄しアルキレンオキサイドのホモ
ポリマーを除去した熱水不溶分重量をWf・とした。However, in each formula below, the amount of polyamide charged in the reaction is W
i, the amount of alkylene oxide is Q, the solid weight after removing unreacted alkylene oxide after reaction is W2
The solid material was washed with hot water to remove the homopolymer of alkylene oxide, and the weight of the hot water insoluble matter was defined as Wf.
実施例1
(液分離材の製造)
ナイロン6製の厚さ50μmの未延伸フィルムAO(宇
部興産■製、商品名:UBE1022B)20gとエチ
レンオキサイド(日本触媒化学工業■製)4(ldとを
ステンレス鋼製オートクレーブに仕込み、無触媒、窒素
ガス雰囲気下、80°Cで所定の時間反応させた。反応
後、未反応のエチレンオキサイドを蒸発除去し、沸騰水
中で1時間ずつ沸騰水を取り替えながら計4時間洗浄し
た。Example 1 (Manufacture of liquid separation material) 20 g of unstretched film AO made of nylon 6 with a thickness of 50 μm (manufactured by Ube Industries ■, trade name: UBE1022B) and ethylene oxide (manufactured by Nippon Shokubai Chemical Industry ■) 4 (ld) were combined. The mixture was placed in a stainless steel autoclave and reacted without a catalyst at 80°C under a nitrogen gas atmosphere for a predetermined time. After the reaction, unreacted ethylene oxide was removed by evaporation, and the mixture was placed in boiling water for 1 hour while replacing the boiling water. It was washed for a total of 4 hours.
その後50゛Cで72時間真空乾燥してグラフトポリア
ミドフィルムを得た。Thereafter, it was vacuum dried at 50°C for 72 hours to obtain a grafted polyamide film.
その結果、第1表に示すようなグラフト率のグラフトポ
リアミドフィルムA I−A sを得た。As a result, a grafted polyamide film AIAs having a graft ratio as shown in Table 1 was obtained.
また上記未延伸フィルムA0の代わりにナイロン6製の
厚さ25μmの二輪延伸フィルムB0(興人■製、商品
名:ボニール)を用いて全く同様にグラフト反応させた
。その結果、第1表に示すようなグラフト率のグラフト
ポリアミドフィルムB、−B、を得た。In addition, in place of the above-mentioned unstretched film A0, a two-wheeled stretched film B0 made of nylon 6 and having a thickness of 25 μm (manufactured by Kojin ■, trade name: Bonyl) was used, and the graft reaction was carried out in exactly the same manner. As a result, grafted polyamide films B and -B with graft ratios shown in Table 1 were obtained.
(以下、余白)
実施例2
実施例1で得られたグラフト率116.7%、厚さ約6
2〜67μmのグラフトポリアミドフィルムA4及びグ
ラフト率98.6%、厚さ約29〜34μmのグラフト
ポリアミドフィルムB4を、RO−3型逆浸透/限外濾
過試験器(バイオエンジニアリング■製)に取付け、各
溶剤150〆を加え、透過面積31.2 cat、圧力
20kg/cii!、室温にて3時間処理した透出量を
測定した。(Hereinafter, blank space) Example 2 Grafting rate obtained in Example 1: 116.7%, thickness: approximately 6
A graft polyamide film A4 of 2 to 67 μm and a graft polyamide film B4 of 98.6% grafting rate and a thickness of about 29 to 34 μm were attached to an RO-3 type reverse osmosis/ultrafiltration tester (manufactured by Bio Engineering ■). Add 150 ml of each solvent, permeation area 31.2 cat, pressure 20 kg/cii! The amount of permeation after treatment at room temperature for 3 hours was measured.
その結果を第2表に示した。The results are shown in Table 2.
(以下、余白)
第
表
比較例
グラフトしていないポリアミド未延伸フィルムA0を用
い実施例2と同様に透出量を測定した。(Hereinafter, blank space) Table Comparative Example The amount of permeation was measured in the same manner as in Example 2 using an unstretched polyamide film A0 that was not grafted.
その結果、いずれも透出量はOdであった。As a result, the permeation amount was Od in all cases.
実施例3
平均粒径0.2 amのナイロン6粉末(宇部興産■製
、商品名:UBE1022B)を用いて、実施例1と同
様にして、6時間反応させて、グラフト率81.8%の
粉末グラフトポリアミドを得た。得られた粉末グラフト
ポリアミドを厚さ2厘のスベ7サーに充填し、アルミ板
で挾んで熱プレス成形した。アルミ板及びスペーサーに
はシリコーンKS700 (信越化学工業■製)をコー
ティングし、温度230°C2圧力100 kg/ci
で3分間(余熱時間1分間含む。)熱プレスした。Example 3 Using nylon 6 powder (manufactured by Ube Industries, trade name: UBE1022B) with an average particle size of 0.2 am, a reaction was carried out for 6 hours in the same manner as in Example 1, resulting in a grafting rate of 81.8%. A powder graft polyamide was obtained. The obtained powder graft polyamide was filled into a 2-inch-thick slider, sandwiched between aluminum plates, and hot press-molded. The aluminum plate and spacer were coated with silicone KS700 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the temperature was 230°C and the pressure was 100 kg/ci.
It was hot pressed for 3 minutes (including 1 minute of preheating time).
熱プレス後、室温で厚さ20mmのステンレス鋼製板に
挟んで冷却し、その後50°Cで1日真空乾燥した。得
られた成形片から25X25X2mmに試験片を切断し
て、吸水性の試験に供した。After hot pressing, it was cooled by sandwiching it between 20 mm thick stainless steel plates at room temperature, and then vacuum dried at 50° C. for 1 day. A test piece of 25 x 25 x 2 mm was cut from the obtained molded piece and subjected to a water absorption test.
試験片を各2枚ずつ5°Cl2O°C1100°Cの電
子恒温水槽ECW−6WEN型(田尻機械工業■製)ま
たはオイルバス中の水中に浸漬した。水はイオン交換水
を用いた。重量変化を追跡して吸水率を算出した。その
結果、平衡吸水率は前記の通り、5°Cで200%、2
0°C?145%、100°Cで112%であった。Two test pieces each were immersed in water in an electronic thermostatic water bath ECW-6WEN model (manufactured by Tajiri Kikai Kogyo ■) or an oil bath at 5°C12O°C1100°C. Ion-exchanged water was used as water. The water absorption rate was calculated by tracking the weight change. As a result, the equilibrium water absorption rate was 200% at 5°C, 2
0°C? 145%, and 112% at 100°C.
また、試験片を5°Cの水とlOO“Cの熱水とに交互
に繰り返し浸漬する吸水サイクルテストを行い、吸水率
と時間との関係を第1図に示した。第1図に示したその
吸水率変化からグラフトポリアミドが見掛は上、水を吸
収したり、放出したりすることが分かる。In addition, a water absorption cycle test was conducted in which the specimen was repeatedly immersed in water at 5°C and hot water at lOO"C, and the relationship between water absorption rate and time is shown in Figure 1. It can be seen from the change in water absorption that the graft polyamide apparently absorbs and releases water.
[発明の効果]
本発明の液分離材は、ナイロン等のポリアミドに12−
アルキレンオキサイドをグラフトしたグラフトポリアミ
ドを用いるもので、水、アルコール、塩素化炭化水素及
びアミン類の吸収、透過性に優れ、これらを含有する液
体混合物からこれらの含有物または他の成分を透過また
は吸収して分離することができ、特に塩素化炭化水素は
、各種溶媒として多量に使用されていることから、工業
的に極めて有用である。[Effects of the Invention] The liquid separation material of the present invention has 12-
This product uses grafted polyamide grafted with alkylene oxide, and has excellent absorption and permeability for water, alcohol, chlorinated hydrocarbons, and amines, and can permeate or absorb these substances or other components from liquid mixtures containing them. In particular, chlorinated hydrocarbons are extremely useful industrially because they are used in large quantities as various solvents.
第1図は本発明のグラフトポリアミド液分離材の温度を
変化させた吸水サイクルテストにおける吸水率と時間と
の関係を示した図である。FIG. 1 is a diagram showing the relationship between water absorption rate and time in a water absorption cycle test in which the temperature of the grafted polyamide liquid separation material of the present invention was varied.
Claims (2)
ることを特徴とする液分離材。(1) A liquid separation material characterized by being made of alkylene oxide grafted polyamide.
る液分離材を使用して、水、アルコール、塩素化炭化水
素及びアミン類の少なくとも1種を含有する液体混合物
から含有するその化合物を分離することを特徴とする液
分離方法。(2) A liquid separation material made of alkylene oxide grafted polyamide is used to separate the compound contained in the liquid mixture containing at least one of water, alcohol, chlorinated hydrocarbon, and amines. Liquid separation method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2082306A JP2841670B2 (en) | 1990-03-29 | 1990-03-29 | Liquid separation material, liquid absorption separation material and liquid separation method using them |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2082306A JP2841670B2 (en) | 1990-03-29 | 1990-03-29 | Liquid separation material, liquid absorption separation material and liquid separation method using them |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03284333A true JPH03284333A (en) | 1991-12-16 |
JP2841670B2 JP2841670B2 (en) | 1998-12-24 |
Family
ID=13770872
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2082306A Expired - Lifetime JP2841670B2 (en) | 1990-03-29 | 1990-03-29 | Liquid separation material, liquid absorption separation material and liquid separation method using them |
Country Status (1)
Country | Link |
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JP (1) | JP2841670B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009535201A (en) * | 2006-04-28 | 2009-10-01 | ダウ グローバル テクノロジーズ インコーポレイティド | Reverse osmosis membrane with branched polyalkylene oxide modified anti-adhesive surface |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61283305A (en) * | 1985-06-05 | 1986-12-13 | Ube Ind Ltd | Porous hollow yarn membrane |
-
1990
- 1990-03-29 JP JP2082306A patent/JP2841670B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61283305A (en) * | 1985-06-05 | 1986-12-13 | Ube Ind Ltd | Porous hollow yarn membrane |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009535201A (en) * | 2006-04-28 | 2009-10-01 | ダウ グローバル テクノロジーズ インコーポレイティド | Reverse osmosis membrane with branched polyalkylene oxide modified anti-adhesive surface |
US7918349B2 (en) | 2006-04-28 | 2011-04-05 | Dow Global Technologies Llc | Composite polyamide membrane with branched poly(alkylene oxide) modified surface |
Also Published As
Publication number | Publication date |
---|---|
JP2841670B2 (en) | 1998-12-24 |
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