JPS6283006A - Manufacturing process for separating functional material - Google Patents
Manufacturing process for separating functional materialInfo
- Publication number
- JPS6283006A JPS6283006A JP22282785A JP22282785A JPS6283006A JP S6283006 A JPS6283006 A JP S6283006A JP 22282785 A JP22282785 A JP 22282785A JP 22282785 A JP22282785 A JP 22282785A JP S6283006 A JPS6283006 A JP S6283006A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- porous
- cation exchange
- membrane
- group
- 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 25
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000005341 cation exchange Methods 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 12
- 238000010559 graft polymerization reaction Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 229920005597 polymer membrane Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 230000005865 ionizing radiation Effects 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000005855 radiation Effects 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は各種液性混合溶液中の陽イオンを選択的に効率
よく吸着し、かつ混合物質を濾過分離する分離機能材料
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a separation functional material that selectively and efficiently adsorbs cations in various liquid mixed solutions and filters and separates mixed substances.
（従来の技術）
従来より、液性混合物の分離精製法は数多く実用化され
、産業の発展に寄与してきた。たとえば、ミクロフィル
ター膜は水性液中から微粒子や細菌を分離精製し、限外
濾過膜はコロイドや発熱性物質などを分離することがで
きる。しかし、−上記いずれの膜も濾過分離性能を有す
るのみで、イオン吸着性能と濾過分離性能の複合機能を
合わせ持つものではない。また、上記複合機能を付与す
るための試みも数多くなされているが、濾過性能をそこ
なうことなく化学的、物理的に安定なイオン吸着性能を
付与することは困難であり、極めて不満足であった。(Prior Art) Many separation and purification methods for liquid mixtures have been put to practical use and have contributed to the development of industry. For example, microfilter membranes can separate and purify fine particles and bacteria from aqueous liquids, and ultrafiltration membranes can separate colloids and pyrogenic substances. However, - all of the above membranes only have filtration and separation performance, and do not have a combined function of ion adsorption performance and filtration and separation performance. In addition, many attempts have been made to impart the above-mentioned composite functions, but it has been difficult to impart chemically and physically stable ion adsorption performance without impairing filtration performance, and these have been extremely unsatisfactory.
他方、イオン交換樹脂の多孔膜化も試みられているが、
含水性のイオン交換樹脂を皮膜加工する方法では、イオ
ン交換物質の流出、および、寸法安定性、耐熱性、耐薬
品性、特に耐久性や物理的性質の低下などの問題点が生
じ、不充分な点が多い。On the other hand, attempts have been made to make porous membranes from ion exchange resins;
The method of coating hydrous ion-exchange resins causes problems such as leakage of the ion-exchange material and decreases in dimensional stability, heat resistance, chemical resistance, especially durability, and physical properties, making it unsatisfactory. There are many points.
（発明が解決しようとする問題点）
現代の工業技術の発展に伴なって、分離、精製材料の高
機能化が望まれており、より高度な複合機能材料の開発
が急がれている。(Problems to be Solved by the Invention) With the development of modern industrial technology, there is a desire for higher functionality in separation and purification materials, and there is an urgent need to develop more advanced composite functional materials.
本発明の目的は、上述の欠点を解消した優れた複合機能
を有する材料の製造方法を提供することにある。An object of the present invention is to provide a method for producing a material with excellent multifunctionality that eliminates the above-mentioned drawbacks.
（問題を解決するための手段）
本発明は、多孔性基材に、カチオン交換基を含有するモ
ノマーまたはカチオン交換基に交換しうる官能基を有す
るモノマーをグラフト重合、特に放射線でグラフト重合
することを特徴とする分離機能材料の製造方法である。(Means for Solving the Problems) The present invention involves graft polymerization, particularly radiation graft polymerization, of a monomer containing a cation exchange group or a monomer having a functional group exchangeable to a cation exchange group onto a porous substrate. This is a method for producing a separation functional material characterized by the following.
以下、本発明の構成を詳しく説明する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明を実施するにあたって使用される多孔性基材は、
放射線照射によりモノマーをグラフト重合できるもので
あればよく、たとえば多孔性高分子膜および無機物を含
有する多孔性高分子膜が用いられる。膜の材料としては
、ポリオレフィン類、ハロゲン化ポリオレフィン類、ポ
リエステル類、ポリエーテル類、セルロースおよびこれ
らの共重合体があげられるが、特にオレフィン系重合体
およびハロゲン化オレフィン系重合体が好ましい。The porous substrate used in carrying out the present invention is
Any material may be used as long as the monomer can be graft-polymerized by radiation irradiation, such as porous polymer membranes and porous polymer membranes containing inorganic substances. Examples of the membrane material include polyolefins, halogenated polyolefins, polyesters, polyethers, cellulose, and copolymers thereof, with olefin polymers and halogenated olefin polymers being particularly preferred.
多孔性基材の形状は、平膜状、チューブ状、中空糸状の
いずれも適用可能である。多孔性基材の空孔構造として
は、延伸法やエツチング法などにより得られた直孔貫通
型の空孔構造よりも、たとえば特公昭５９−３７２９２
号公報、特公昭４０−９５７号公報および特公昭４７−
１７４６０号公報に示されたミクロ相分離法や混合抽出
法などにより形成される３次元網目構造を有するものが
好ましい。特に、特開昭５５−１３１０２８号公報Ｇこ
示された構造体の製造技術が確立することに伴なって、
本発明の意義が明確化し、従来技術では得られない優れ
た性能を有する材料の製造方法を達成することができた
。The shape of the porous base material may be a flat membrane, a tube, or a hollow fiber. The pore structure of the porous base material is better than a straight pore structure obtained by a stretching method or an etching method.
Publication No. 40-957 and Special Publication No. 47-
Those having a three-dimensional network structure formed by the microphase separation method, mixed extraction method, etc. disclosed in Japanese Patent No. 17460 are preferred. In particular, with the establishment of the manufacturing technology for the structure shown in Japanese Patent Application Laid-Open No. 55-131028,
The significance of the present invention has been clarified, and a method for manufacturing a material with excellent performance that cannot be obtained with conventional techniques has been achieved.
本発明に使用されるカチオン交換基を含有するモノマー
またはカチオン交換基に変換しうる官能基を有するモノ
マーとしては、スルホン酸基、カルボン酸基、フェノー
ル性水酸基またはこれらのアルカリ金属塩を有する、炭
化水素系または含ハロゲン炭化水素系上ツマ−があげら
れる。具体的には、ビニルスルホン酸、スチレンスルホ
ン酸、アクリル酸、メタクリル酸、バラビニルフェノー
ル、フルオロビニルスルホン酸、フルオロビニルカルボ
ン酸およびスチレンなどの単独または２種以上を混合し
たものが用いられる。The monomer containing a cation exchange group or the monomer having a functional group convertible into a cation exchange group used in the present invention includes carbonized monomers having a sulfonic acid group, a carboxylic acid group, a phenolic hydroxyl group, or an alkali metal salt thereof. Examples include hydrogen-based or halogen-containing hydrocarbon-based materials. Specifically, vinylsulfonic acid, styrenesulfonic acid, acrylic acid, methacrylic acid, paravinylphenol, fluorovinylsulfonic acid, fluorovinylcarboxylic acid, and styrene may be used alone or in combination of two or more thereof.
多孔性基材にモノマーをグラフト重合させるには放射綿
を用いる。用いられる電離性放射線は、α線、β線、γ
線、加速電子線、Ｘ線などであるが、実用的には電子線
またはγ線が好ましい。グラフト重合させる方法として
は、多孔性基材とモノマーの共存下に放射線を照射し、
グラフト重合させる同時照射法と、多孔性基材のみにあ
らかじめ放射線を照射し、そののち多孔性基材にモノマ
ーを接触反応させてグラフト重合させる前照射法がある
が、同時照射法では多孔性基材へのモノマーのグラフト
重合が進行すると同時に、グラフト重合に関与しないモ
ノマーのみが単独重合し、多孔性基材の空孔を閉塞する
という問題が生じるので、前照射法が好ましい。前照射
法では、多孔性基材にモノマーを接触させる以前に基材
にあらかじめ放射線を照射し、モノマーと接触させるま
での間マイナス１０“Ｃ以下に保ち、５０℃以下、好ま
しくは１５℃〜５０℃の低温でモノマーと接触させてグ
ラフト重合を行う。放射線を照射したのちに多孔性基材
を低温保存しない場合は、生成ラジカルが急速に減衰し
、室温（２５℃）で３０分経過するとその数は半分にな
る。さらに、それと同時に生成ラジカルが微量の吸着酸
素と反応し、目的物質の耐熱耐薬品性を損なうという欠
陥を生しる。また、グラフト重合温度が６０℃以上にな
ると、グラフト重合にあずからないモノマーの単独熱重
合物が生成し、多孔性基材の空孔を閉塞するとか、反応
後の後処理工程では抽出されない単独熱重合物が親水化
の後に流出してきて２次公害の原因となる、といった問
題が生じる。Radiant cotton is used to graft-polymerize the monomer onto the porous substrate. The ionizing radiation used is alpha rays, beta rays, and γ rays.
rays, accelerated electron beams, X-rays, etc., but electron beams or γ-rays are practically preferred. The method of graft polymerization is to irradiate the porous base material and monomer with radiation,
There is a simultaneous irradiation method in which the porous base material undergoes graft polymerization, and a pre-irradiation method in which only the porous base material is irradiated with radiation in advance, and then the monomer is brought into contact with the porous base material for graft polymerization. The pre-irradiation method is preferable because the problem arises that while the graft polymerization of monomers onto the material progresses, only the monomers that do not participate in the graft polymerization are homopolymerized, thereby clogging the pores of the porous base material. In the pre-irradiation method, the base material is irradiated with radiation before contacting the monomer with the porous base material, and the temperature is maintained at -10"C or less until it comes into contact with the monomer, and the temperature is kept at 50 °C or less, preferably 15 °C to 50 °C. Graft polymerization is carried out by contacting the monomer at a low temperature of 30°C.If the porous substrate is not stored at a low temperature after irradiation, the generated radicals will rapidly decay and will disappear after 30 minutes at room temperature (25°C). The number will be halved.Furthermore, at the same time, the generated radicals will react with a trace amount of adsorbed oxygen, resulting in a defect that impairs the heat and chemical resistance of the target substance.Furthermore, if the graft polymerization temperature exceeds 60°C, the graft Homopolymerized monomers of monomers that do not participate in polymerization may be generated and block the pores of the porous substrate, or homopolymerized monomers that are not extracted in the post-treatment process after the reaction may flow out after hydrophilization and cause secondary Problems such as causing pollution arise.
以下、実施例により本発明の構成および効果を具体的に
述べるが、いずれも本発明を限定するものではない。Hereinafter, the structure and effects of the present invention will be specifically described with reference to Examples, but these are not intended to limit the present invention.
（実施例）
実施例１
特開昭５５−１３１０２８号公報に記載された方法で得
た３次元網目構造からなるポリエチレン多孔膜を、電子
加速器（加速電圧１．５ＭｅＶ、電子線電流１ｍＡ）を
用いて窒素雰囲気下１ＯＯＫＧｙで照射し、あらかじめ
溶存酸素を０．１ ｐｐｍ以下にした５０％アクリル酸
水溶液（０，２５ｗｔ％のモール塩を含有）に浸漬して
２５°Ｃで１時間反応させた。これにより、グラフト率
６３％の膜を得た。この膜の陽イオン交換容量は４゜７
ミリ当量／グラム重合体であった。(Example) Example 1 A porous polyethylene film having a three-dimensional network structure obtained by the method described in JP-A-55-131028 was processed using an electron accelerator (acceleration voltage 1.5 MeV, electron beam current 1 mA). The sample was irradiated with 1 OOKGy under a nitrogen atmosphere, immersed in a 50% aqueous acrylic acid solution (containing 0.25 wt% Mohr's salt) in which dissolved oxygen had been reduced to 0.1 ppm or less, and reacted at 25°C for 1 hour. As a result, a membrane with a graft ratio of 63% was obtained. The cation exchange capacity of this membrane is 4°7
milliequivalents/gram polymer.
この膜を用い、膜面積１００ｃｎｌ、濾過圧力１ｋｇ／
Ｃａで原水（０，２ｕ以上の微粒子１０４″／ＣＣ％
Ｎａ’？ｌ’Ａ度５０ｐｐｍ）の濾過テストを行った。Using this membrane, membrane area 100cnl, filtration pressure 1kg/
Raw water with Ca (fine particles of 0.2 u or more 104″/CC%
Na'? A filtration test was conducted.
その結果、通水８時間において透水’ｆｔ９００１／ｒ
ｒｒ ｉ＋ｒ−ａｔｍ、微粒子およびナトリウムイオン
除去率は１００％であった。As a result, the water permeability was 9001/r after 8 hours of water flow.
rr i+r-atm, the removal rate of fine particles and sodium ions was 100%.
一方、比較のため、反応温度を７０℃としたほかは上記
と同じ方法で反応させたところ、反応開始１０分後から
反応液の粘度が上昇し、反応終了後には多孔膜の空孔が
閉塞し、膜が透明化した。On the other hand, for comparison, when the reaction was carried out in the same manner as above except that the reaction temperature was changed to 70°C, the viscosity of the reaction liquid increased 10 minutes after the start of the reaction, and the pores of the porous membrane were blocked after the reaction was completed. The film became transparent.
この膜を前記と同様な方法で濾過テストしたところ、透
水量は前記実施例の１％以下であった。When this membrane was subjected to a filtration test in the same manner as described above, the amount of water permeation was 1% or less of that in the above example.
実施例２
実施例１と同様な膜を、実施例１と同様に１０Ｍｒａｄ
電子線照射し、溶存酸素０．ｌｐｐｍ以下のスチレンモ
ノマーに浸漬し、２５℃で１時間反応させた。これによ
り、グラフト率６７％の膜を得た。Example 2 The same membrane as in Example 1 was prepared at 10 Mrad in the same manner as in Example 1.
Electron beam irradiation, dissolved oxygen 0. It was immersed in styrene monomer of 1 ppm or less and reacted at 25° C. for 1 hour. As a result, a membrane with a grafting rate of 67% was obtained.
これを無水硫酸のジオキサンとジクロロエタンの飽和溶
液中で５°Ｃ１８時間反応させ、スルホン化した。得ら
れた膜の陽イオン交換容量は３．５ミリ当量／グラム重
合体であった。この膜を実施例１と同様な方法で濾過テ
ストしたところ、通水８時間で平均透水速度は８００１
／ｍ −ｈｒ−ａｔｍ 、 ６粒子およびナトリウムイ
オン除去率は１００％であった。This was reacted in a saturated solution of anhydrous sulfuric acid in dioxane and dichloroethane at 5°C for 18 hours to sulfonate it. The resulting membrane had a cation exchange capacity of 3.5 meq/g polymer. When this membrane was subjected to a filtration test in the same manner as in Example 1, the average water permeation rate was 8001 after 8 hours of water flow.
/m-hr-atm, 6 particles and the sodium ion removal rate was 100%.
一方、比較のため、膜として延伸法により得られた多孔
膜（平均孔径０．１ミクロン）を用いたほかは上記と同
じ方法で反応させたところ、グラフト率５５％の膜を得
た。この膜を上記と同様な方法でスルホン化したところ
、３．０ミリグラム当量／グラム重合体の陽イオン交換
容量を得た。この膜を実施例１と同様な方法で濾過テス
トしたところ、通水８時間における透水量は５０１／ｍ
−ｈｒ・ａｔｍであり、ナトリウムイオン除去率は１０
０％、微粒子除去率は８０％であった。この膜を走査型
電子顕微鏡で観察した結果、直孔貫通空孔の一部閉塞が
確認され、また、反応時の膨潤による孔径拡大と孔径分
布のひろがりが確認された。On the other hand, for comparison, the reaction was carried out in the same manner as above except that a porous membrane (average pore diameter: 0.1 micron) obtained by a stretching method was used as the membrane, and a membrane with a graft ratio of 55% was obtained. This membrane was sulfonated in a manner similar to that described above, resulting in a cation exchange capacity of 3.0 milliequivalents/gram polymer. When this membrane was subjected to a filtration test in the same manner as in Example 1, the water permeation rate after 8 hours of water flow was 501/m2.
-hr・atm, and the sodium ion removal rate is 10
The particle removal rate was 80%. As a result of observing this membrane with a scanning electron microscope, it was confirmed that some of the straight pores were blocked, and that the pore size had expanded and the pore size distribution had expanded due to swelling during the reaction.
（発明の効果）
本発明により、多孔性高分子膜に濾過性能を損なうこと
なくイオン選択吸着性能を付与することが可能となり、
化学的および物理的に極めてすぐれた複合機能材料を提
供することができる。(Effects of the Invention) According to the present invention, it is possible to impart ion selective adsorption performance to a porous polymer membrane without impairing filtration performance,
Composite functional materials with excellent chemical and physical properties can be provided.
Claims (6)
ーまたはカチオン交換基に変換しうる官能基を有するモ
ノマーをグラフト重合することを特徴とする分離機能材
料の製造方法(1) A method for producing a separation functional material, which comprises graft-polymerizing a monomer containing a cation exchange group or a monomer having a functional group that can be converted into a cation exchange group onto a porous substrate.
多孔性高分子膜であることを特徴とする特許請求の範囲
第１項記載の製造方法(2) The manufacturing method according to claim 1, wherein the porous base material is a porous polymer membrane having communicating pores with a three-dimensional network structure.
オレフィン系重合体からなることを特徴とする特許請求
の範囲第２項記載の製造方法(3) The manufacturing method according to claim 2, wherein the porous polymer membrane is made of an olefin-based or halogenated olefin-based polymer.
ノール性水酸基またはこれらのアルカリ金属塩を有する
、炭化水素系または含ハロゲン炭化水素系モノマーであ
ることを特徴とする特許請求の範囲第１項記載の製造方
法(4) Claim 1, characterized in that the monomer is a hydrocarbon-based or halogen-containing hydrocarbon-based monomer having a sulfonic acid group, a carboxylic acid group, a phenolic hydroxyl group, or an alkali metal salt thereof. Manufacturing method described
工程と、それにつづくモノマーを基材に接触反応させる
工程とからなることを特徴とする特許請求の範囲第１項
記載の製造方法(5) The production method according to claim 1, wherein the graft polymerization comprises a step of irradiating the base material with ionizing radiation, and a subsequent step of causing the monomer to contact and react with the base material.
を特徴とする特許請求の範囲第５項記載の製造方法(6) The production method according to claim 5, characterized in that the catalytic reaction is carried out in a range of 15°C to 50°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60222827A JPH07114945B2 (en) | 1985-10-08 | 1985-10-08 | Method for manufacturing separation functional material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60222827A JPH07114945B2 (en) | 1985-10-08 | 1985-10-08 | Method for manufacturing separation functional material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6283006A true JPS6283006A (en) | 1987-04-16 |
| JPH07114945B2 JPH07114945B2 (en) | 1995-12-13 |
Family
ID=16788530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60222827A Expired - Fee Related JPH07114945B2 (en) | 1985-10-08 | 1985-10-08 | Method for manufacturing separation functional material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07114945B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5743940A (en) * | 1988-04-07 | 1998-04-28 | Japan Atomic Energy Research Institute | Process for producing gas adsorbent |
| US5783608A (en) * | 1994-11-22 | 1998-07-21 | Ebara Corporation | Process for producing separation functional fibers and ion-exchange fibers produced therefrom |
| WO1999009091A1 (en) * | 1997-08-18 | 1999-02-25 | Pall Corporation | Ion exchange membrane |
| WO2002033135A1 (en) * | 2000-10-18 | 2002-04-25 | Johnson Matthey Public Limited Company | Precious metal scavenging from a liquid medium with a functionalised polymer fiber |
| WO2004099297A1 (en) * | 2003-05-06 | 2004-11-18 | Organo Corporation | Graft-modified organic porous material and process for producing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5644098A (en) * | 1979-09-18 | 1981-04-23 | Ebara Infilco Co Ltd | Treating method of hydrazine content waste water |
| JPS5773027A (en) * | 1980-10-24 | 1982-05-07 | Yuasa Battery Co Ltd | Production of graft polymer |
-
1985
- 1985-10-08 JP JP60222827A patent/JPH07114945B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5644098A (en) * | 1979-09-18 | 1981-04-23 | Ebara Infilco Co Ltd | Treating method of hydrazine content waste water |
| JPS5773027A (en) * | 1980-10-24 | 1982-05-07 | Yuasa Battery Co Ltd | Production of graft polymer |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5743940A (en) * | 1988-04-07 | 1998-04-28 | Japan Atomic Energy Research Institute | Process for producing gas adsorbent |
| US5783608A (en) * | 1994-11-22 | 1998-07-21 | Ebara Corporation | Process for producing separation functional fibers and ion-exchange fibers produced therefrom |
| US6127433A (en) * | 1994-11-22 | 2000-10-03 | Ebara Corporation | Process for producing separation functional fibers and ion-exchange fibers produced therefrom |
| WO1999009091A1 (en) * | 1997-08-18 | 1999-02-25 | Pall Corporation | Ion exchange membrane |
| WO2002033135A1 (en) * | 2000-10-18 | 2002-04-25 | Johnson Matthey Public Limited Company | Precious metal scavenging from a liquid medium with a functionalised polymer fiber |
| WO2004099297A1 (en) * | 2003-05-06 | 2004-11-18 | Organo Corporation | Graft-modified organic porous material and process for producing the same |
| CN100348651C (en) * | 2003-05-06 | 2007-11-14 | 奥加诺株式会社 | Graft-modified organic porous material and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07114945B2 (en) | 1995-12-13 |
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