JPS61146301A - Membrane and its preparation - Google Patents
Membrane and its preparationInfo
- Publication number
- JPS61146301A JPS61146301A JP26629384A JP26629384A JPS61146301A JP S61146301 A JPS61146301 A JP S61146301A JP 26629384 A JP26629384 A JP 26629384A JP 26629384 A JP26629384 A JP 26629384A JP S61146301 A JPS61146301 A JP S61146301A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- copolymer
- block copolymer
- microdomain
- graft copolymer
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は主としてブロック共重合体あるいはグラフト共
重合体よりなり表裏を貫通するミクロドメインから実質
的に構成されている膜及びその膜を製造する方法に係り
、例えば逆浸透膜、限外濾過膜、モザイク荷電膜等の分
離膜に使用し得る膜及びその製造方法に係る。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the production of a membrane that is mainly made of a block copolymer or a graft copolymer and is substantially composed of microdomains penetrating the front and back surfaces, and the membrane. The present invention relates to a membrane that can be used as a separation membrane such as a reverse osmosis membrane, an ultrafiltration membrane, a mosaic charged membrane, and a method for manufacturing the same.
［従来技術］
ブロックあるいはグラフト共重合体からなる膜の従来の
製造法は大きく分けると溶液製膜法（流延法）と溶融製
膜法とになる。いづれの方法も重合体を流動状態にして
膜を形成するものである。[Prior Art] Conventional methods for producing membranes made of block or graft copolymers can be roughly divided into solution casting methods (casting methods) and melt casting methods. In either method, a membrane is formed by making the polymer fluid.
流動状態にするのに溶剤の助けをかりる場合、溶液濃度
が充分低い場合には、溶剤により共重合体分子は分子分
散してミクロドメインは消滅するものの溶剤の蒸発過程
に於いて膜面に平行な方向への温度勾配はつくれなかっ
た。熱の力をかりる場合には流動状態における温度が秩
序−無秩序転移温度以下であったためミクロドメインは
消滅しない状態での製膜であった。又、秩序−無秩序転
移Ｉｉ度以上で無秩序状態であったとしても製膜過程で
膜面に平行な方向への温度勾配は作れなかった。When a solvent is used to create a fluidized state, if the solution concentration is low enough, the copolymer molecules are dispersed by the solvent and the microdomains disappear, but in the process of evaporation of the solvent, the copolymer molecules remain parallel to the membrane surface. It was not possible to create a temperature gradient in that direction. When applying heat, the temperature in the fluid state was below the order-disorder transition temperature, so the film was formed without the microdomains disappearing. Further, even if the film was in a disordered state at an order-disorder transition of Ii degree or higher, a temperature gradient in the direction parallel to the film surface could not be created during the film forming process.
従って、従来法では膜表面に関してランダムな配向を有
するミクロドメインが形成されることになる。即ちブロ
ック共重合体をこの様な従来法によって製膜すると、場
合によっては部分的にミクロドメイン構造の界面が表面
に直交あるいは斜めになることもあるが、あくまでも偶
然でありかつ部分的であるため全体としての膜性能はミ
クロドメインがランダムな配向を有するものとしての性
能により支配されることは言うまでもない。Therefore, in the conventional method, microdomains having random orientation with respect to the membrane surface are formed. In other words, when a block copolymer is formed into a film using such a conventional method, the interface of the microdomain structure may be partially perpendicular or oblique to the surface depending on the case, but this is only a coincidence and only partially. It goes without saying that the performance of the film as a whole is controlled by the performance of the microdomains as having random orientation.
［発明の目的］
従来の製膜法では膜表面に対して垂直の方向に物性、材
質に変化のある膜はできても平行方向に物性及び材質の
変化のある膜は作ることができなかったのを、本発明は
表面に平行な方向で分子レベルの大きさで部分々々の物
性、材質が異なり、それが繰返し連続した膜を作ること
を目的として見いだされたものである。[Purpose of the invention] Conventional film-forming methods can produce films that change in physical properties and materials in the direction perpendicular to the film surface, but cannot produce films that change in physical properties and materials in the parallel direction. However, the present invention was discovered with the aim of creating a continuous film in which the physical properties and materials of each part are different at the molecular level in the direction parallel to the surface, and these are repeated repeatedly.
即ち、予じめ形成された膜を加熱領域とそれに隣接した
冷却領域を連続的に通過させるか、あるいは加熱領域か
ら冷却領域へ膜に成形しつつ移行させる。加熱領域はブ
ロック共重合体あるいはグラフト共重合体が秩序−無秩
序転移温度以上になるように加熱しておく。このように
加熱された膜は分子が無秩序状態になっていて、次いで
秩序−無秩序転移温度以下に冷却する冷却領域に移動さ
せられる。That is, a preformed membrane may be passed successively through a heating zone and an adjacent cooling zone, or it may be transferred from a heating zone to a cooling zone while being formed into a membrane. The heating region is heated so that the block copolymer or graft copolymer is heated to a temperature higher than the order-disorder transition temperature. The thus heated film, in which the molecules are in a disordered state, is then transferred to a cooling region where it is cooled below the order-disorder transition temperature.
その結果、形成されたミクロドメイン構造の界面が膜面
に垂直でしかも膜面を貫通したものとなる。これをブロ
ック共重合体あるいはグラフト共重合体で作り得るなら
ば、ブロック共重合体あるいはグラフト共重合体のいづ
れの成分からなるミクロドメインも、実質的にそれらの
界面が膜面に直交し膜の表裏を貫通しているものが得ら
れ、方の成分の性質が他方の成分に制約されることなく
発現され得るばかりでなく、他方の成分が隣接して存在
することによる効果も期待し得る。As a result, the interface of the formed microdomain structure is perpendicular to the membrane surface and penetrates through the membrane surface. If this could be made from a block copolymer or graft copolymer, the microdomains made of either the block copolymer or graft copolymer would have their interfaces substantially perpendicular to the membrane surface and A material that penetrates the front and back surfaces is obtained, and not only can the properties of one component be expressed without being constrained by the other component, but also the effects of the presence of the other component adjacent to each other can be expected.
［発明の構成］
（膜）
本発明は主としてブロック共重合体あるいはグラフト共
重合体よりなり実質的にそれらのミクロドメイン構造の
界面が膜面に直交し、かつ表裏を貫通している膜で、ブ
ロック共重合体は線状又は星形ｎ元ｍブロック共重合体
（ｎは成分ポリマー数、ｍは全ブロック数とする）で特
に限定されない。例えば、線状ブロック共重合体の例を
あげれば、Ａ−８二元ブロック共重合体、Ａ−Ｂ−Ａ、
Ｂ−Ａ−８，二元トリブロック共重合体、 Ａ−Ｂ／ｌ
二元マルチブロック共重合体（二元セグメント化マルチ
ブロック共重合体） 、Ａ−Ｂ−Ｃ三元トリブロック共
重合体、Ａ−Ｂ−Ａ−Ｃ−Ａ三元ペンタブロック共重合
体、（但し、Ａ、Ｂ、Ｃは成分ポリマーである）等があ
り、より具体的に例示すれば、ポリスチレンーボリイソ
プレンニ元ブロック共重合体、ポリイソプレン−ポリス
チレン−ポリイソプレン、あるいはポリスブレンーボリ
イソプレンーポリスチレンニ元トリブロック共重合体、
ポリイソプレン−スルホン化したポリスチレン−ポリイ
ソプレン−四級化したポリ−ｐ−ビニルベンジルメチル
アミン−ポリイソプレンの三元ベンタブロック共重合体
等が挙げられる。グラフト共重合体についても同様であ
る。[Structure of the Invention] (Membrane) The present invention is a membrane mainly composed of a block copolymer or a graft copolymer, in which the interface of the microdomain structure is substantially perpendicular to the membrane surface and penetrates the front and back sides, The block copolymer is not particularly limited and may be a linear or star-shaped n-element m block copolymer (n is the number of component polymers, m is the total number of blocks). For example, examples of linear block copolymers include A-8 diblock copolymer, A-B-A,
B-A-8, binary triblock copolymer, A-B/l
binary multiblock copolymer (binary segmented multiblock copolymer), A-B-C ternary triblock copolymer, A-B-A-C-A ternary pentablock copolymer, ( However, A, B, and C are component polymers), and more specific examples include polystyrene-polyisoprene diblock copolymer, polyisoprene-polystyrene-polyisoprene, or polysbrene-polyisoprene. -Polystyrene triblock copolymer,
Examples include a ternary bentablock copolymer of polyisoprene, sulfonated polystyrene, polyisoprene, and quaternized poly-p-vinylbenzylmethylamine-polyisoprene. The same applies to graft copolymers.
なお、ブロック共重合体あるいはグラフト共重合体の秩
序−無秩序転移温度の高いものの場合は適当に可塑剤、
成型助剤（たとえば重合性モノマーを添加し本発明の処
理後の重合）または他の重合体を混合してあっても良い
。ミクロドメインの形状は第１図に示したラメラ状でも
第２図に示したようなシリンダー状海島構造でもよい。In addition, if the block copolymer or graft copolymer has a high order-disorder transition temperature, a plasticizer,
Molding aids (for example, polymerizable monomers are added and polymerized after the treatment of the present invention) or other polymers may be mixed. The shape of the microdomain may be a lamella as shown in FIG. 1 or a cylindrical sea-island structure as shown in FIG.
ブロック共重合体あるいはグラフト共重合体の組成比、
重合度比によってミクロドメインの構造が変化する。ラ
メラ状の場合ミクロドメインの膜面方向での大きさは巾
５０〜１０００ 程度にでき、シリンダー状海島構造の
場合のシリンダーの直径は２５〜５００ 程度にできる
。また多元ブロック共重合体を使用すればモザイク荷電
膜になる。Composition ratio of block copolymer or graft copolymer,
The structure of microdomains changes depending on the polymerization degree ratio. In the case of a lamellar structure, the size of the microdomain in the membrane surface direction can be about 50 to 1000 mm in width, and in the case of a cylindrical sea-island structure, the diameter of the cylinder can be about 25 to 500 mm. Furthermore, if a multi-block copolymer is used, a mosaic charged film can be obtained.
本発明において秩序−無秩序転移温度とは秩序状態即ち
ミクロドメインの存在する状態から無秩序状態即ち、ミ
クロドメイン構造が消滅してブロックあるいはグラフト
共重合体の分子が分子状に混合した状態に転移する温度
である。この転移温度は、マクロモレキューシス１θ８
３年第１６巻１０９３頁に掲載されているＸ線小角散乱
法により測定できる。In the present invention, the order-disorder transition temperature refers to the temperature at which the ordered state, that is, the state where microdomains exist, transitions to the disordered state, that is, the state where the microdomain structure disappears and the molecules of the block or graft copolymer are mixed molecularly. It is. This transition temperature is the macromolecule 1θ8
It can be measured by the small-angle X-ray scattering method published in Vol. 16, p. 1093 of 2013.
［製造方法］
本発明の膜を製造するにはブロック共重合体あるいはグ
ラフト共重合体をそれらの秩序−無秩序転移温度以上に
加熱する加熱領域とそれと隣接した秩序−無秩序転移温
度以下に冷却する冷却領域を通過させて製造する。例え
ば、上述のブロック共重合体あるいはグラフト共重合体
を一旦従来の方法で膜状に成形する。この膜は前述の如
く溶液製膜法、溶融製膜法のいづれで作っても、一般に
不規則なミクロドメイン配列をとっていて本発明の如く
膜表面に垂直な界面をもつ構造のものが得られることは
無かった。本発明の製造方法は、このような膜を下記の
ように処理するものである。[Manufacturing method] To manufacture the membrane of the present invention, there is a heating region in which the block copolymer or graft copolymer is heated above its order-disorder transition temperature, and an adjacent cooling region in which the block copolymer or graft copolymer is cooled to below its order-disorder transition temperature. Manufacture by passing through the area. For example, the above-mentioned block copolymer or graft copolymer is once formed into a membrane by a conventional method. As mentioned above, whether this film is made by solution casting or melt casting, it generally has an irregular microdomain arrangement, and as in the present invention, a structure with interfaces perpendicular to the membrane surface can be obtained. There was nothing to be done. In the manufacturing method of the present invention, such a film is treated as follows.
即ち、予じめ形成された膜を加熱領域とそれに隣接した
冷却領域を連続的に通過させる。加熱領域はブロック共
重合体あるいはグラフト共重合体が秩序−無秩序転移温
度以上になるように加熱しておく。このように加熱され
た膜は分子が無秩序状態になっていて、次いで秩序−無
秩序転移温度以下にある冷却領域に移動させられる。That is, the preformed membrane is passed successively through a heating zone and an adjacent cooling zone. The heating region is heated so that the block copolymer or graft copolymer is heated to a temperature higher than the order-disorder transition temperature. The heated film, whose molecules are in a disordered state, is then transferred to a cooling region below the order-disorder transition temperature.
又、予め膜に成形しておくのではなく、粉状、粒状のブ
ロック共重合体あるいはグラフト共重合体を本発明所定
温度への加熱を行い膜状に成形しつつ冷却領域に移動さ
せてもよく、あるいは予備加熱溶融領域を設は膜状にし
ながら所定温度の加熱領域にもたらし更に冷却領域へと
移動させても製造出来る。Alternatively, instead of forming the block copolymer or graft copolymer in the form of a film in advance, the block copolymer or graft copolymer in the form of powder or particles may be heated to a predetermined temperature according to the present invention, and then transferred to the cooling area while being formed into a film. Alternatively, it can be produced by setting a preheated melting region in the form of a film, bringing it to a heating region at a predetermined temperature, and then moving it to a cooling region.
従来の溶融製膜法の場合は、溶融温度が秩序−無秩序転
移温度以下にしか加熱されていない為ミクロドメイン構
造が消滅しておらず、このミクロドメインがその界面を
膜面に垂直に、又、膜面を貫通しうるような充分な再配
列がおこらない。In the case of the conventional melt film forming method, the microdomain structure does not disappear because the melting temperature is heated only below the order-disorder transition temperature. , sufficient rearrangement does not occur to penetrate the membrane surface.
本発明方法で得られるラメラ状ミクロドメインを有する
膜を模型的に示せば第１図の如くなる。A schematic diagram of a film having lamellar microdomains obtained by the method of the present invention is shown in FIG.
矢印１は、膜２の製造時の膜の移動方向で矢印１に直角
方向に界面を有するラメラ状ミクロドメイン３の繰返し
によって膜が形成される。ラメラ状ミクロドメイン３は
例えばポリスチレンとポリイソプレンＡＢＡ型ブロック
共重合体を使用した場合ポリスチレンミクロドメイン４
とポリイソプレンミクロドメイン５とから成り立ってい
る。Arrow 1 indicates the direction of movement of the membrane during production of membrane 2, and the membrane is formed by repeating lamellar microdomains 3 having interfaces in a direction perpendicular to arrow 1. For example, when a polystyrene and polyisoprene ABA type block copolymer is used, the lamellar microdomains 3 can be formed using polystyrene microdomains 4.
and polyisoprene microdomains 5.
シリンダー状海島槙造ミクロドメインを有する膜を模型
的に示せば第２図のごとくで例えば、ポリイソプレン３
０重量部とポリスチレン７０ｆｆｌｆｆ１部とのブロッ
ク共重合体を使用した場合に得られ、海部６はポリスチ
レン部、高部７はポリイソプレン部から成り立っている
。６と７との界面は矢印１に垂直に形成されている。A schematic diagram of a membrane having cylindrical microdomains is shown in Figure 2. For example, polyisoprene 3
It is obtained when a block copolymer of 0 parts by weight and 70 fflff of polystyrene is used, and the sea part 6 is made up of a polystyrene part and the high part 7 is made of a polyisoprene part. The interface between 6 and 7 is formed perpendicular to arrow 1.
また、例えば陽イオン交換基を持つ高分子と陰イオン交
換Ｕを持つ高分子とイオン交換基をもたない高分子が直
鎖状に結合した分子構造を持つ三元ブロック共重合物を
使用すれば第３図の如く海部８はイオン交換基を持たな
い高分子よりなり、高部９は陽イオン、高部１０は陰イ
オンの交換基を夫々持った高分子より成り立ついわゆる
モザイク荷電膜が得られる。In addition, for example, a ternary block copolymer having a molecular structure in which a polymer with a cation exchange group, a polymer with an anion exchange U, and a polymer without an ion exchange group are bonded in a linear chain can be used. For example, as shown in Fig. 3, a so-called mosaic charged membrane is obtained in which the sea part 8 is made of a polymer having no ion exchange groups, the high part 9 is made of a polymer having cation exchange groups, and the high part 10 is made of polymers having anion exchange groups. It will be done.
冷却領域の温度は秩序−無秩序転移温度以下であること
は言うまでもないが、加熱領域との温度差は大きい程よ
い。膜の移動速度は１．０ａｍ／時間以下の低速にする
のが好ましいが特に限定はされない。It goes without saying that the temperature of the cooling region is below the order-disorder transition temperature, but the larger the temperature difference from the heating region, the better. The moving speed of the membrane is preferably as low as 1.0 am/hour or less, but is not particularly limited.
使用する装置は第４図に原理的に側面略示図として示し
たが、従来法で作った膜１１を垂下し一定速度で加熱領
域１２．１２′間及びそれに隣接した冷却領域１３．１
３′間に移動させる。The apparatus used, which is shown in principle in a schematic side view in FIG. 4, allows a conventionally produced membrane 11 to be suspended at a constant speed between the heating areas 12, 12' and the adjacent cooling area 13.1.
Move it between 3'.
［発明の効果］
以上の如く本発明の膜は全面にわたってミクロドメイン
構造の界面が実質的に膜面に直交し、かつ表裏を貫通し
ているので、一つの成分を除去して孔を開は分離膜に使
用する場合に有効孔面積が大きく、しかも略々垂直に貫
通しているので通過長が短い利点がある。更に、孔径が
両面間で略々一定になるため目ずまりを起こしがたく、
使用による性能低下が少ないのも利点である。モザイク
荷電膜の場合も同様、有効面積が大きく通過長が短い。[Effects of the Invention] As described above, in the membrane of the present invention, the interface of the microdomain structure is substantially perpendicular to the membrane surface over the entire surface and penetrates the front and back surfaces, so it is not possible to open pores by removing one component. When used in a separation membrane, it has the advantage of having a large effective pore area and a short passage length since it penetrates almost vertically. Furthermore, since the pore diameter is approximately constant between both sides, it is difficult to cause clogging.
Another advantage is that there is little performance deterioration due to use. Similarly, in the case of a mosaic charged film, the effective area is large and the passage length is short.
実施例１
ポリスチレンとポリイソプレンＡＢＡ型トリブロック共
重合体で数平均分子ｆｆ１３．５Ｘ１０’、ポリスチレ
ンの割合が５０重（６）％のものを用い、これに５０重
石％のジオクチルフタレートを加えて混練したのち、約
２０μ膜厚のフィルムを作成した。このフィルムを第４
図に示したような膜製作装置を用い、加熱領域１２．１
２′および冷却領域１３．１３−のそれぞれの間隙を２
０μとし、加熱領域を秩序−無秩序転移温度である１５
０’Ｃ以上の１８０℃とし冷却領域を１０℃としてフィ
ルムを１ｍ／ｈｒの速度で通過させた。Example 1 A polystyrene and polyisoprene ABA type triblock copolymer with a number average molecular weight of ff 13.5 x 10' and a polystyrene ratio of 50% by weight (6) was used, and 50% by weight of dioctyl phthalate was added thereto and kneaded. After that, a film having a thickness of about 20 μm was prepared. This film is the fourth
Using the film manufacturing equipment shown in the figure, heating area 12.1
2' and cooling area 13.13-.
0μ, and the heating region is 15 which is the order-disorder transition temperature.
The temperature was set to 180°C, which was 0'C or higher, and the cooling region was set to 10°C, and the film was passed through the film at a speed of 1 m/hr.
得られたフィルムはオスミウム酸染色法を用いた電子顕
微鏡観察及びＸ線小角散乱測定の結果、略々全面が第１
図のごときラメラ状構造になっており、各ミクロドメイ
ンの巾は０．０１μであって、膜面に直交し両面間を貫
通していた。As a result of electron microscopy observation using osmic acid staining and small-angle X-ray scattering measurements, almost the entire surface of the obtained film was found to be the first layer.
It had a lamellar structure as shown in the figure, and each microdomain had a width of 0.01μ, was perpendicular to the membrane surface, and penetrated between both surfaces.
実施例２
ポリスチレンとポリイソプレンＡＢＡ型トリブロック共
重合体で数平均分子ｆｆ１３．５Ｘ１０４、ポリスチレ
ンの割合が７０重量％のものを用い、これに１０重量％
のジオクチルフタレートを加えて混練したのち約２０μ
の膜厚のフィルムを作成した。このフィルムを第４図に
示したような膜製作装置を用い、加熱領域１２．１２−
および冷却領域１３．１３−のそれぞれの間隙が２０μ
とし加熱領域（１８０℃）と冷却領域（１０’Ｃ）と順
次Ｌｓ／ｈｒの速度で通過させた。かくして得られたフ
ィルムは電子顕微鏡観察及びＸ線小角散乱測定の結果略
々全面が第２図のごとき海島構造を有し、高部７は、ポ
リイソプレンよりなり略々０゜０１μの直径を有し、膜
面に直交したミクロドメインを形成し両面間を貫通して
いた。この通過後のフィルムを更にオゾン酸化させるこ
とによりポリイソプレンを分解させた多孔膜を作成した
。この多孔膜を１０ｐｓｉｇの差圧で純水の透過損を測
定したところ２４ ／ｉ＋１ｎ−７ｄ・Ｋ９ ／ ｃ
ｉとなった。電顕写真から孔径は０．０１μであった。Example 2 A polystyrene and polyisoprene ABA type triblock copolymer with a number average molecular weight of ff 13.5 x 104 and a polystyrene proportion of 70% by weight was used, and 10% by weight of polystyrene was used.
After adding and kneading dioctyl phthalate, approximately 20μ
A film with a thickness of . This film was heated in the heating area 12.12-
and cooling area 13.13- each gap is 20μ
The sample was then passed sequentially through a heating region (180° C.) and a cooling region (10° C.) at a rate of Ls/hr. As a result of electron microscopy and small-angle X-ray scattering measurements, the film thus obtained had a sea-island structure on almost the entire surface as shown in Figure 2, and the high portion 7 was made of polyisoprene and had a diameter of approximately 0°01μ. However, microdomains were formed perpendicular to the membrane surface and penetrated between both surfaces. After passing through the film, the film was further oxidized with ozone to create a porous film in which the polyisoprene was decomposed. When the permeation loss of pure water was measured through this porous membrane at a differential pressure of 10 psig, it was 24/i+1n-7d・K9/c
It became i. The pore diameter was 0.01μ from electron micrographs.
比較例１
実施例２に用いたのと同様の１０重山％のＤＯＰを加え
たポリスチレンとポリイソプレンのブロック共重合体の
膜厚的２０μのフィルムを用いた。Comparative Example 1 A 20 μm thick film of a block copolymer of polystyrene and polyisoprene to which 10% DOP was added, similar to that used in Example 2, was used.
このフィルムを１８０℃、２０分冊熱処理後室温まで徐
冷した。膜厚に変化はなかった。この徐冷フィルムを実
施例２と同一条件でオゾン処理した後、実施例２と同一
条件で純水の透過量を測定したところ１．２ ／ｎ＋
ｉｎ −ｒｄ・Ｋ９／ｃｌとなった。This film was heat treated at 180° C. for 20 volumes and then slowly cooled to room temperature. There was no change in film thickness. After this slowly cooled film was treated with ozone under the same conditions as in Example 2, the amount of pure water permeated was measured under the same conditions as in Example 2, and the result was 1.2/n+
It became in-rd・K9/cl.
比較例２
市販品ニュウクリボア−ＮＯＯ５（０，０５μφ、５μ
Ｉｔ）を用いて実施例２と同一条件で純水の透過量を測
定したところ４．９ ／ｍｔｎ −ｒｒｔ・Ｋ９／ａ
ｉであった。Comparative Example 2 Commercial product Nuclebore-NOO5 (0.05μφ, 5μ
When the amount of permeation of pure water was measured under the same conditions as in Example 2 using It), it was 4.9 /mtn -rrt・K9/a
It was i.
比較例３
実施例２に於いて加熱領域を秩序−無秩序転移温度の１
５０℃以下の１４０℃として作った膜について実施例２
と同一条件で純水の透過量を測定したところ１．６／＋
ｇｉｎ−７ｄ・幻／ｄとなった。Comparative Example 3 In Example 2, the heating region was set to 1 of the order-disorder transition temperature.
Example 2 about a film made at 140°C below 50°C
The amount of pure water permeated was measured under the same conditions as 1.6/+
It became gin-7d/phantom/d.
実施例３
ポリイソプレンーポリスチレンーボリイソブレンーボリ
Ｐ−ビニルベンジルメチルアミン−ポリイソブレン三元
ペンタブロック共重合体のポリーＰ−ビニルベンジルジ
メチルアミン部分を臭化エチレンで四級化した後、ポリ
スチレン部分を濃硫酸でスルホン化したものに５０重量
％ジオクチルフタレートを配合し、実施例１と同様にし
て２０μに製膜し、第３図のごとき構造の膜を得た。Example 3 After quaternizing the poly-P-vinylbenzyldimethylamine part of a polyisoprene-polystyrene-polyisobrene-polyP-vinylbenzylmethylamine-polyisoprene tertiary pentablock copolymer with ethylene bromide, the polystyrene part was sulfonated with concentrated sulfuric acid, and 50% by weight of dioctyl phthalate was added thereto, and a film having a thickness of 20μ was formed in the same manner as in Example 1 to obtain a film having the structure shown in FIG.
第１〜３図は本発明の３つの代表的膜の構造を示す部分
欠切見取図で、第１図および第３図はミクロドメインが
ラメラ状の場合、第２図はシリンダー状海島構造の場合
である。
第４図は本発明の膜の製造に使用する装置の側面概念図
である。
１は膜２の製造時の膜の移動方向である。４゜５．６．
７．８．９．１０は夫々の場合のミクロドメイン構造を
示す。
特許出願人 ダイセル化学工業株式会社第１図Figures 1 to 3 are partially cutaway diagrams showing the structures of three representative membranes of the present invention. Figures 1 and 3 are for cases in which the microdomains are lamellar, and Figure 2 is for the case in which the microdomains are in the form of a cylindrical sea-island structure. It is. FIG. 4 is a conceptual side view of the apparatus used for manufacturing the membrane of the present invention. 1 is the direction in which the membrane 2 moves when it is manufactured. 4゜5.6.
7.8.9.10 shows the microdomain structure in each case. Patent applicant: Daicel Chemical Industries, Ltd. Figure 1
Claims (13)
合体よりなり、実質的にそれらのミクロドメイン構造の
界面が膜面に直交し、かつ表裏を貫通していることを特
徴とする膜(1) A membrane mainly composed of a block copolymer or a graft copolymer, characterized in that the interface of the microdomain structure is substantially perpendicular to the membrane surface and penetrates the front and back surfaces.
リスチレンとポリイソプレンとのブロック共重合体ある
いはグラフト共重合体である特許請求の範囲第１項記載
の膜(2) The membrane according to claim 1, wherein the block copolymer or graft copolymer is a block copolymer or graft copolymer of polystyrene and polyisoprene.
第１、２項記載の膜(3) The membrane according to claims 1 and 2, wherein the microdomains are lamellar.
ある特許請求の範囲第１〜３項記載の膜(4) The membrane according to claims 1 to 3, wherein the width of the lamellar microdomain is 50 to 1000 mm.
許請求の範囲第１、２項記載の膜(5) The membrane according to claims 1 and 2, wherein the microdomain has a cylindrical sea-island structure.
０である特許請求の範囲第１、２、５項記載の膜(6) The diameter of the cylindrical microdomain is 25 to 50
The membrane according to claims 1, 2, and 5, which is
塑剤又は他の重合体を含む特許請求の範囲第１〜６項記
載の膜(7) The membrane according to claims 1 to 6, wherein the block copolymer or graft copolymer contains a plasticizer or other polymer.
れらの秩序−無秩序転移温度以上に加熱する加熱領域と
それと隣接した秩序−無秩序転移温度以下に冷却する冷
却領域を通過させることを特徴とする、主として、ブロ
ック共重合体あるいはグラフト共重合体よりなり実質的
にそれらのミクロドメイン構造の界面が膜面に直交し、
かつ表裏を貫通している膜の製造方法(8) passing the block copolymer or graft copolymer through a heating region that heats it above its order-disorder transition temperature and an adjacent cooling region that cools it below its order-disorder transition temperature; Mainly made of block copolymers or graft copolymers, the interface of their microdomain structure is substantially perpendicular to the membrane surface,
A method for producing a membrane that penetrates the front and back surfaces.
重合体の秩序−無秩序転移温度以上である特許請求の範
囲第８項記載の膜の製造方法(9) The method for producing a membrane according to claim 8, wherein the heating region is above the order-disorder transition temperature of the block copolymer or graft copolymer.
共重合体の秩序−無秩序転移温度より低温である特許請
求の範囲第８項記載の膜の製造方法(10) The method for producing a membrane according to claim 8, wherein the temperature of the cooling region is lower than the order-disorder transition temperature of the block copolymer or graft copolymer.
許請求の範囲第８項記載の膜の製造方法(11) The method for producing a membrane according to claim 8, wherein the membrane passing speed is 100 mm/hour or less.
ポリスチレンとポリイソプレンとのブロック共重合体あ
るいはグラフト共重合体である特許請求の範囲第８項記
載の膜の製造方法(12) The method for producing a membrane according to claim 8, wherein the block copolymer or graft copolymer is a block copolymer or graft copolymer of polystyrene and polyisoprene.
体と可塑剤または他の重合体とを含む特許請求の範囲第
８項記載の膜の製造方法(13) The method for producing a membrane according to claim 8, wherein the membrane contains a block copolymer or a graft copolymer and a plasticizer or other polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26629384A JPS61146301A (en) | 1984-12-19 | 1984-12-19 | Membrane and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26629384A JPS61146301A (en) | 1984-12-19 | 1984-12-19 | Membrane and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61146301A true JPS61146301A (en) | 1986-07-04 |
| JPH0454486B2 JPH0454486B2 (en) | 1992-08-31 |
Family
ID=17428930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26629384A Granted JPS61146301A (en) | 1984-12-19 | 1984-12-19 | Membrane and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61146301A (en) |
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|---|---|---|---|---|
| WO2000058760A1 (en) * | 1999-03-31 | 2000-10-05 | Cpfilms Inc. | Film composites |
| US7118784B1 (en) * | 2005-06-27 | 2006-10-10 | The Regents Of The University Of California | Method and apparatus for controlling nucleation in self-assembled films |
| JP2006299106A (en) * | 2005-04-21 | 2006-11-02 | Kyoto Institute Of Technology | Block copolymer membrane having cylinder structure orienting perpendicularly |
| JP2006334693A (en) * | 2005-05-31 | 2006-12-14 | Furukawa Electric Co Ltd:The | Nanostructure, porous nanostructure, functional nanostructure, and method of manufacturing same |
| WO2009104423A1 (en) * | 2008-02-22 | 2009-08-27 | 有限会社サンサーラコーポレーション | Polymer composition and molded article produced from the composition |
| WO2010119858A1 (en) * | 2009-04-13 | 2010-10-21 | 国立大学法人山口大学 | Ion-exchange membrane and method for producing same |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311988A (en) * | 1976-07-16 | 1978-02-02 | Hoechst Ag | Method for drying chlorinated polymer |
-
1984
- 1984-12-19 JP JP26629384A patent/JPS61146301A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5311988A (en) * | 1976-07-16 | 1978-02-02 | Hoechst Ag | Method for drying chlorinated polymer |
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