JPH0316624A - Composite membrane and its production - Google Patents
Composite membrane and its productionInfo
- Publication number
- JPH0316624A JPH0316624A JP1148472A JP14847289A JPH0316624A JP H0316624 A JPH0316624 A JP H0316624A JP 1148472 A JP1148472 A JP 1148472A JP 14847289 A JP14847289 A JP 14847289A JP H0316624 A JPH0316624 A JP H0316624A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- thin layer
- composite membrane
- natural polymer
- partially hydrolyzed
- 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 78
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 21
- 229920005615 natural polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 150000004676 glycans Chemical class 0.000 claims abstract 2
- 229920001282 polysaccharide Polymers 0.000 claims abstract 2
- 239000005017 polysaccharide Substances 0.000 claims abstract 2
- 238000005373 pervaporation Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000001913 cellulose Substances 0.000 abstract description 3
- 229920002678 cellulose Polymers 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 15
- 239000010408 film Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229920001661 Chitosan Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000012510 hollow fiber Substances 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- -1 ion salt Chemical class 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical class O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002230 Pectic acid Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は複合膜及びその製造方法に関する。さらに詳し
くは、部分的に加水分解されたポリアクリロニトリル系
基材模に親水性天然高分子からなる薄膜が形成された複
合膜及び複合膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a composite membrane and a method for manufacturing the same. More specifically, the present invention relates to a composite membrane in which a thin film made of a hydrophilic natural polymer is formed on a partially hydrolyzed polyacrylonitrile base material, and a method for producing the composite membrane.
［従来の技術〕
従来から種々の分離プロセスに複合膜を用いることが検
討されており、このような嘆は分離方法に対応して浸透
気化膜、蒸気透過膜、逆浸透膜、限外枦過嘆、除湿膜等
と呼ばれている。[Prior art] The use of composite membranes in various separation processes has been considered, and these methods include pervaporation membranes, vapor permeation membranes, reverse osmosis membranes, and ultrafiltration membranes, depending on the separation method. It is also called a dehumidifying membrane.
とくに、分離模で区割された二つの室の供給液側（一次
側）に分離されるべき液体混合物を供給１丸的に透過さ
せる浸透気化法は、水一有機液体混合物から水を除去す
るのにエネルギー効率の高い分離技術として注目されて
おり、種々の複合模が研究されている。In particular, the pervaporation method, in which the liquid mixture to be separated is completely passed through the feed liquid side (primary side) of two chambers separated by a separation chamber, removes water from a water-organic liquid mixture. However, it is attracting attention as a highly energy-efficient separation technology, and various composite models are being studied.
これらの複合膜において、膜の透過性能を向上させるた
めには膜の厚みを極力薄くすることが重要であるが、あ
まり膜が薄くなると透過性能が上昇する反面、機械的強
度が小さくなるため、実用的には強度を補うための支持
体が必要となる。In order to improve the permeation performance of these composite membranes, it is important to make the membrane as thin as possible, but if the membrane becomes too thin, the permeation performance will increase, but the mechanical strength will decrease. Practically speaking, a support is required to supplement the strength.
近年、基材膜上に薄膜を形戊することによって透過性能
、機械的強度ともに優れた膜を得る検討がなされており
、すでに種々のものが提案されている。例えば、特開昭
５９− １０９２０４号明細書には、微多孔性支持層に
ポリビニルアルコール等からなる活性層が形成された複
合分離膜が、特開昭６０−７８６０１号及び特開昭６０
− ９７００２号明細書には、微多孔性支持層にアセチ
レン系ボリマーからなる活性智が形成された複合分離膜
が開示されている。又、特開昭６２− ２５５４４１号
明細書には、２枚の限外枦過膜の間に高分子イオン塩の
層を設けた複合膜が、しかしながら、上記明細書に開示
されている複合膜には、分雌係数及び透過速度で代表さ
れる膜の透過性能、ならびに機械的強度全てを満足する
離法の実用化という点で極めて重要なことであり、嘆分
離技術の分野では上記のような性能を併せもった実用に
耐える複合膜が要望されている。In recent years, studies have been made to obtain membranes with excellent permeability and mechanical strength by forming thin membranes on base membranes, and various membranes have already been proposed. For example, JP-A-59-109204 discloses a composite separation membrane in which an active layer made of polyvinyl alcohol or the like is formed on a microporous support layer, as described in JP-A-60-78601 and JP-A-60.
-97002 discloses a composite separation membrane in which an active layer made of an acetylene polymer is formed on a microporous support layer. Furthermore, JP-A No. 62-255441 discloses a composite membrane in which a layer of polymer ion salt is provided between two ultrafiltration membranes, but the composite membrane disclosed in the above specification is This is extremely important in terms of the practical application of separation methods that satisfy all of the membrane permeation performance represented by the separation coefficient and permeation rate, as well as mechanical strength. There is a need for a composite membrane that has both excellent performance and is durable for practical use.
従って、本発明の目的は、透過性能及び分離性能が優れ
、かつ機械的強度にも優れた工業的に満足しうる複合分
Ｍｌとその製造方法を提供することにある。Therefore, an object of the present invention is to provide an industrially satisfactory composite component Ml that has excellent permeation performance, separation performance, and mechanical strength, and a method for producing the same.
［！ＩＩ題を解決するための手段］
本発明者らは鋭意検討し、部分的に加水分解されたポリ
アクリロニトリル系基材膜に、親水性天然高分子からな
る薄層を形成させた複合膜が上記性能を満足する複合膜
であることを見い出し、本発明に至った。すなわち本発
明により、部分的に加水分解されたポリアクリロニトリ
ル系基材膜に輯水性天然高分子からなる薄層が形成され
た複合膜及びその製造方法が提供される。[! Means for Solving Problem II] The present inventors have made extensive studies and have developed a composite membrane in which a thin layer made of a hydrophilic natural polymer is formed on a partially hydrolyzed polyacrylonitrile base membrane. We have discovered that this is a composite membrane that satisfies the performance, and have arrived at the present invention. That is, the present invention provides a composite membrane in which a thin layer of a water-soluble natural polymer is formed on a partially hydrolyzed polyacrylonitrile base membrane, and a method for producing the same.
本発明に用いられるポリアクリａニトリル系基材膜は、
アクリロニトリルを主構成単位とするボリマーからなる
膜であり、このようなポリマーのような大きな孔を有す
る多孔膜の場合は、基ＩｔＭ４上に親水性天然高分子か
らなる薄層を形成したときにピンホールが発生しやすく
、又実質的に無孔の緻密膜では充分な透過流速を得るこ
とが困難であるので、微多孔質であることが好ましく、
とくルピロリドン、酢酸ビニル、ビニルビリジン、塩化
ビニリデン、ビニルスルホン酸、スチレンスルホン酸、
アリルスルホン酸、（メタ）アクリル酸等との少なくと
も１種以上の単位とを構成威分とするコボリマー、ボリ
アクリロニトリルホモポリマー又はそのコポリマーと他
のボリマーとのブレンド物等をあげることができる。The polyacrylic nitrile base film used in the present invention is
It is a membrane made of a polymer whose main constituent unit is acrylonitrile, and in the case of a porous membrane with large pores such as this polymer, when a thin layer made of a hydrophilic natural polymer is formed on the ItM4 group, pin Since holes are likely to occur and it is difficult to obtain a sufficient permeation flow rate with a substantially non-porous dense membrane, it is preferably microporous.
Tokurupyrrolidone, vinyl acetate, vinylpyridine, vinylidene chloride, vinylsulfonic acid, styrenesulfonic acid,
Examples include a copolymer having at least one unit with allylsulfonic acid, (meth)acrylic acid, etc., a polyacrylonitrile homopolymer, or a blend of the copolymer with another polymer.
アクリロニトリルを主構成単位とするコボリマーの場合
、加水分解によって生ずる親和性の増加という観点から
アクリロニトリル単位は５０モル％以上含まれることが
好ましい。In the case of a copolymer having acrylonitrile as the main constitutional unit, it is preferable that the acrylonitrile unit is contained in an amount of 50 mol % or more from the viewpoint of increasing affinity caused by hydrolysis.
ポリアクリロニトリル系基材膜の形態は、平膜、管状膜
、中空糸膜等いずれの形態でも使用可能である。基材峡
の構造は孔径がミクロンオーダーのボリアクリロニトリ
ル系基材膜を部分加水分解するにはアルカリ水溶液また
はアルカリのアルコール性水溶液中に静置するか、これ
らの液中を適度な速度で通過させるなどの固液接触方法
で達成できる。使用しうるアルカリとしては、アルカリ
金属の水酸化物、アミン類またはこれらの混合物等があ
げられるが、水酸化ナトリウムまたは水酸化カリウムが
実用的であり好適である。The polyacrylonitrile base membrane may be in any form such as a flat membrane, a tubular membrane, or a hollow fiber membrane. In order to partially hydrolyze a polyacrylonitrile base film with a pore size on the order of microns, the structure of the base material gorge must be left standing in an alkaline aqueous solution or alkaline alcoholic aqueous solution, or passed through these solutions at a moderate speed. This can be achieved using solid-liquid contact methods such as Examples of the alkali that can be used include alkali metal hydroxides, amines, and mixtures thereof, and sodium hydroxide or potassium hydroxide is preferred as it is practical.
ポリアクリロニトリル系ボリマーの加水分解の程度は、
アルカリの濃度、アルカリ溶液の温度及び接触時間等の
処理条件によって制御することができ、該処理条件は、
加水分解されるべきポリマー又はコボリマーの組威、膜
の耐熱性等により適宜選択される。一般的にはＯ．１〜
２Ｎ濃度のアルカリ溶液中５０〜８０℃、５〜６０分と
いう処理条件が選ばれる。The degree of hydrolysis of polyacrylonitrile polymers is
It can be controlled by processing conditions such as concentration of alkali, temperature of alkaline solution and contact time, and the processing conditions are:
It is appropriately selected depending on the composition of the polymer or copolymer to be hydrolyzed, the heat resistance of the membrane, etc. Generally O. 1~
Processing conditions of 50-80° C. and 5-60 minutes in a 2N alkaline solution are chosen.
アクリロニトリル系ボリマーが加水分解されていること
は赤外吸収スペクトルにより、カルボキシル基に由来す
る吸収の出現または増加を確認す部分的に加水分解され
たポリアクリロニトリル系基材膜は、カルボキシル基が
使用したアルカリの種類に対応した種々の金属塩、アミ
ン塩等の形態となっているが、酸処理により酸型に変換
することもできる。部分的に加水分解されたポリアクリ
ロニトリル系基材膜はそのままで分離膜として使用でき
るが、該基材膜上に親水性天然高分子からなる薄層を形
成させて複合膜とすることにより、分離係敗、透過速度
、及び機械的性能等の機能性明の効果が発現しにくいの
で、本発明においては膜の形態を保持できる範囲内で適
宜用途に応じて加水分解されるべきである。上述のよう
に、太発明において、ポリアクリロニトリル系基材膜を
部分的に加水分解するとは、膜形態が保持される程度に
加水分鱗することを意味している。従って、本発明にお
いては、アルカリ水溶液を種々の条件で膜表面に接触さ
せることによって膜表面部分を加水分解すればよい。Hydrolysis of the acrylonitrile polymer is confirmed by the appearance or increase of absorption derived from carboxyl groups using an infrared absorption spectrum.Partially hydrolyzed polyacrylonitrile base film shows that carboxyl groups are used. It is in the form of various metal salts, amine salts, etc. depending on the type of alkali, but it can also be converted to the acid form by acid treatment. A partially hydrolyzed polyacrylonitrile base membrane can be used as a separation membrane as it is, but it can be used as a separation membrane by forming a thin layer of a hydrophilic natural polymer on the base membrane to create a composite membrane. In the present invention, it should be hydrolyzed as appropriate depending on the application within a range that can maintain the membrane form, since it is difficult to achieve functional effects such as anchorage, permeation rate, and mechanical performance. As mentioned above, in the present invention, partially hydrolyzing the polyacrylonitrile base film means hydrolyzing it to such an extent that the film form is maintained. Therefore, in the present invention, the membrane surface portion may be hydrolyzed by bringing an alkaline aqueous solution into contact with the membrane surface under various conditions.
しボリイオンコンプレックス化されるため高性能で耐久
性のある複合膜を得るうえで好都合である。Since it is made into a polyion complex, it is convenient for obtaining a high-performance and durable composite membrane.
本発明に用いられる親水性天然高分子の例としては、キ
トサン、キトサン塩、キトサン誘導体（塩）、アルギン
酸、アルギン酸塩、アルギン酸誘導体（塩）、ペクチン
酸（塩）、カルボキシメトキシキチン、プルラン、カラ
ギーナン、コンドロイチン硫酸、ヒアロン酸、カルボキ
シメトキシセルロース、硫酸セルロース等の水溶性セル
ロース誘導体等の多糖類をあげることができる。Examples of hydrophilic natural polymers used in the present invention include chitosan, chitosan salt, chitosan derivative (salt), alginic acid, alginate, alginic acid derivative (salt), pectic acid (salt), carboxymethoxychitin, pullulan, carrageenan. , chondroitin sulfate, hyalonic acid, carboxymethoxycellulose, cellulose sulfate, and other water-soluble cellulose derivatives.
本発明においては、支持層である部分的に加水分解・さ
れたポリアクリロニトリル系基材膜に親水性天然高分子
からなるｔｉｉ＋を形成させることが重要であり、かか
る点に最大の特徴を有している。In the present invention, it is important to form tii+ made of a hydrophilic natural polymer on the partially hydrolyzed polyacrylonitrile base film that is the support layer, and this is the most distinctive feature. ing.
すなわち、部分的に加水分解されたポリアクリロニトリ
ル系基材膜は薄層を形成する親水性天然高分子との親和
性が強いため容易に薄層を形成することができる。さら
に、薄層としてキトサン等のカチオン性親水性天然高分
子を用いる場合には、リロニトリル系基材膜が中空糸膜
の場合、薄層は中空糸膜の内面又は外面のいずれにも形
成することができ、形成後、乾燥することによって本発
明の複合膜を得ることができる。That is, the partially hydrolyzed polyacrylonitrile base film has a strong affinity with the hydrophilic natural polymer forming the thin layer, so that a thin layer can be easily formed. Furthermore, when using a cationic hydrophilic natural polymer such as chitosan as the thin layer, if the rylonitrile base membrane is a hollow fiber membrane, the thin layer may be formed on either the inner or outer surface of the hollow fiber membrane. After formation, the composite membrane of the present invention can be obtained by drying.
得られた攪合膜の透過流速を大きくするためには、基材
膜上に形成される薄層の厚みはできる限り薄い方が好ま
しいが、この厚みは基材膜表面の平滑性や基材膜と薄層
を形成する天然高分子物質との親和性等により制約され
る。薄層の厚みは一般にこれらの制約条件を考慮のうえ
、ドープ液の濃度及び各種の薄層形成方法の条件を調整
することによりコントロールすることが可能である。ま
た、作成した複合膜は素材や活性層（薄層）の性質に応
じて、限外枦過、逆浸透、除湿、浸透気化、蒸気透過な
どの複合膜として使用できることば明系基材膜上に親水
性天然高分子からなる薄層を形成するＩ二は、高分子水
溶液中（ドープ液）への浸漬、バーコーター等による塗
布、スビンコート等の公知の方法を適用することができ
る。ポリアクポリアクリロニトリル系限外が過中空糸膜
（内径０．８ｓｍｑ外径１．４ＩＩｍ＋，分画分千＠
１３００Ｇ）をｇｏ”ｃのＮ／５ Ｍａｉｌ水溶液中に
１０分間浸漬することにより、該膜のニトリル基の部分
加水分解を行なった。In order to increase the permeation flow rate of the resulting stirred membrane, it is preferable that the thin layer formed on the base membrane be as thin as possible, but this thickness may vary depending on the smoothness of the base membrane surface and the base material. It is limited by the affinity between the membrane and the natural polymer substance that forms the thin layer. The thickness of the thin layer can generally be controlled by taking these constraints into account and adjusting the concentration of the dope and the conditions of the various thin layer formation methods. In addition, depending on the material and properties of the active layer (thin layer), the composite membrane created can be used as a composite membrane for ultrafiltration, reverse osmosis, dehumidification, pervaporation, vapor permeation, etc. For forming a thin layer of a hydrophilic natural polymer on the substrate, known methods such as immersion in an aqueous polymer solution (dope solution), coating with a bar coater or the like, and tin coating can be applied. Polyacrylonitrile-based hollow fiber membrane (inner diameter 0.8smq outer diameter 1.4IIm+, fraction 1,000@
1300G) was immersed in an aqueous N/5 Mail solution of go''c for 10 minutes, the nitrile groups of the membrane were partially hydrolyzed.
様にして複合膜を作製した。実施例１と同様にして９５
重量％エタノール水溶液からの脱水を行なったところ、
分離係数は４．８、透過速度は１．１ｋｇ／ｓ”・ｂｒ
であった（比較例１）。A composite membrane was prepared in the same manner. 95 in the same manner as in Example 1
When dehydration was performed from a wt% ethanol aqueous solution,
Separation coefficient is 4.8, permeation rate is 1.1 kg/s"・br
(Comparative Example 1).
実施例２および比較例２
親水性天然高分子液として０．８重量％のアルギ実施例
１および比較例ｌ
参考例で得られた部分的に加水分解されたポリアクリロ
ニトリル系基材屓を０．３重量％キトサン水溶液（０．
６重量％酢酸を含む）中に１時間浸漬した後、風乾し、
該基材膜外面上にキトサン酢酸塩からなる薄層を形成し
た。薄層の厚さは走査型電ａｌｌ察の結果から約０．Ｉ
Ｉ１ｍであった。Example 2 and Comparative Example 2 0.8% by weight of Algi as a hydrophilic natural polymer liquid Example 1 and Comparative Example 1 The partially hydrolyzed polyacrylonitrile base material obtained in the Reference Example was 0.8% by weight. 3% by weight chitosan aqueous solution (0.
(containing 6 wt% acetic acid) for 1 hour, then air-dried.
A thin layer of chitosan acetate was formed on the outer surface of the base membrane. The thickness of the thin layer is approximately 0.0 mm based on the results of scanning electron microscopy. I
It was I1m.
この複合膜を用い、９５重量％エタノール水溶液からの
脱水を６０”Ｃ、２次側の圧カＱ．６ｓｓＨｇの条件で
浸透気化法により行なったところ、分離係数８８、透過
速度０．２７ｋｇ／１・ｈｒが得られた（実施例！）．
参考例で得られた加水分解されていないポリアクリロニ
トリル系暎を基材膜とし、実施例ｌと同た（実施例２）
。Using this composite membrane, dehydration from a 95% by weight ethanol aqueous solution was carried out by pervaporation under the conditions of 60"C and secondary side pressure Q.6ssHg, resulting in a separation coefficient of 88 and a permeation rate of 0.27kg/1.・hr was obtained (Example!).
The same procedure as Example 1 was carried out using the unhydrolyzed polyacrylonitrile resin obtained in Reference Example as the base film (Example 2).
.
親水性天然高分子溶液として０．６重量％のアルギン酸
ナトリウム水溶液を用い、比較例１と同じ基材膜を用い
る以外は実施例ｌと同様にして複合膜を作製し、実施例
ｌと同様に浸透気化法により脱水を行なったところ、分
離係数は！．７、浸透速度は６．０ｋｇ／１・ｈｒであ
った（比較例２）。A composite membrane was prepared in the same manner as in Example 1, except that a 0.6% by weight sodium alginate aqueous solution was used as the hydrophilic natural polymer solution and the same base membrane as in Comparative Example 1 was used. When dehydration was performed by pervaporation, the separation coefficient was! ．． 7. The penetration rate was 6.0 kg/1·hr (Comparative Example 2).
実施例３
実施例ｌで得られた複合膜をＮ ；／ １００硫酸のエ
タノール水溶液（水／エタノール＝ ５０／ ５０重量
比）中に２分間浸漬し、＊ｍ中のキトサンの対アニオン
を酢酸イオンから硫酸イオンに変換した後、実施例ｌと
同様にして９５重隋％エタノール水溶液からの脱水を浸
透気化法により行なったところ、分離係数３２０、透過
速度０．２４ｋｇ／ｓ″・ｈ『であった。Example 3 The composite membrane obtained in Example 1 was immersed for 2 minutes in an aqueous ethanol solution of N;/100 sulfuric acid (water/ethanol = 50/50 weight ratio), and the counteranion of chitosan in *m was converted to acetate ion. After converting it into sulfate ion, the 95% ethanol aqueous solution was dehydrated by the pervaporation method in the same manner as in Example 1. As a result, the separation coefficient was 320 and the permeation rate was 0.24 kg/s''·h. Ta.
以上の実施例および比較例の結果から本発明の効果は明
らかである。The effects of the present invention are clear from the results of the above Examples and Comparative Examples.
［発明の効果］
本発明により、部分的に加水分解されたポリアクリロニ
トリル系基材膜上に親水性天然高分子からなる薄層が形
成された複合膜を容易に作製することができる。このよ
うな襟合膜は、基材嘆と薄層の親和性が良好であるため
欠陥の少ない薄層を形成しやすく、良好な耐久性と透過
性能を有するので、浸透気化法、蒸気透過法等による種
々の水−有機液体混合物からの脱水、空気からの除湿、
ならびに透析、限外が過、逆浸透などの方法による水系
混合物の分離に好適に使用される。[Effects of the Invention] According to the present invention, a composite membrane in which a thin layer made of a hydrophilic natural polymer is formed on a partially hydrolyzed polyacrylonitrile base membrane can be easily produced. This type of collar film has good affinity with the base material and the thin layer, so it is easy to form a thin layer with few defects, and it has good durability and permeation performance, so it can be used by pervaporation method, vapor permeation method. Dehydration from various water-organic liquid mixtures, dehumidification from air, etc.
It is also suitably used to separate aqueous mixtures by methods such as dialysis, ultrafiltration, and reverse osmosis.
Claims (1)
材膜に親水性天然高分子をコーティングして製造するこ
とを特徴とする複合膜。 ２、親水性天然高分子が天然多糖類である請求項１記載
の複合膜。 ３、浸透気化用に使用することを特徴とする請求項１又
は請求項２記載の複合膜。 ４、ポリアクリロニトリル系基材膜に親水性天然高分子
をコーティングして複合膜を製造する際、ポリアクリロ
ニトリル系基材膜をあらかじめ部分的に加水分解して親
水性を高めておくことを特徴とする複合膜の製造方法。[Claims] 1. A composite membrane produced by coating a partially hydrolyzed polyacrylonitrile base membrane with a hydrophilic natural polymer. 2. The composite membrane according to claim 1, wherein the hydrophilic natural polymer is a natural polysaccharide. 3. The composite membrane according to claim 1 or 2, which is used for pervaporation. 4. When manufacturing a composite membrane by coating a polyacrylonitrile base film with a hydrophilic natural polymer, the polyacrylonitrile base film is partially hydrolyzed in advance to increase its hydrophilicity. A method for manufacturing a composite membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1148472A JPH0316624A (en) | 1989-06-13 | 1989-06-13 | Composite membrane and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1148472A JPH0316624A (en) | 1989-06-13 | 1989-06-13 | Composite membrane and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0316624A true JPH0316624A (en) | 1991-01-24 |
Family
ID=15453513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1148472A Pending JPH0316624A (en) | 1989-06-13 | 1989-06-13 | Composite membrane and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0316624A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009533217A (en) * | 2006-04-11 | 2009-09-17 | マサチューセッツ・インスティテュート・オブ・テクノロジー | Film with fouling resistance formed by polyacrylonitrile graft copolymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242106A (en) * | 1988-03-23 | 1989-09-27 | Toray Ind Inc | Composite semipermeable membrane |
-
1989
- 1989-06-13 JP JP1148472A patent/JPH0316624A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01242106A (en) * | 1988-03-23 | 1989-09-27 | Toray Ind Inc | Composite semipermeable membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009533217A (en) * | 2006-04-11 | 2009-09-17 | マサチューセッツ・インスティテュート・オブ・テクノロジー | Film with fouling resistance formed by polyacrylonitrile graft copolymer |
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