JPH0523818B2 - - Google Patents
Info
- Publication number
- JPH0523818B2 JPH0523818B2 JP5226684A JP5226684A JPH0523818B2 JP H0523818 B2 JPH0523818 B2 JP H0523818B2 JP 5226684 A JP5226684 A JP 5226684A JP 5226684 A JP5226684 A JP 5226684A JP H0523818 B2 JPH0523818 B2 JP H0523818B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- membrane
- copolymer
- vinyl
- water surface
- 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.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- -1 vinyl halide Chemical class 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 229920000620 organic polymer Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 8
- 239000004988 Nematic liquid crystal Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- GIJIKFKGLZGENN-UHFFFAOYSA-N (4-ethoxyphenyl) 4-butoxycarbonyloxybenzoate Chemical compound C1=CC(OC(=O)OCCCC)=CC=C1C(=O)OC1=CC=C(OCC)C=C1 GIJIKFKGLZGENN-UHFFFAOYSA-N 0.000 description 1
- KAEZRSFWWCTVNP-UHFFFAOYSA-N (4-methoxyphenyl)-(4-methoxyphenyl)imino-oxidoazanium Chemical compound C1=CC(OC)=CC=C1N=[N+]([O-])C1=CC=C(OC)C=C1 KAEZRSFWWCTVNP-UHFFFAOYSA-N 0.000 description 1
- LWRNQOBXRHWPGE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4a,5,5,6,6,7,7,8,8a-heptadecafluoro-8-(trifluoromethyl)naphthalene Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C2(F)C(C(F)(F)F)(F)C(F)(F)C(F)(F)C(F)(F)C21F LWRNQOBXRHWPGE-UHFFFAOYSA-N 0.000 description 1
- UEOZRAZSBQVQKG-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorooxolane Chemical compound FC1(F)OC(F)(F)C(F)(F)C1(F)F UEOZRAZSBQVQKG-UHFFFAOYSA-N 0.000 description 1
- RVCKCEDKBVEEHL-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobenzyl alcohol Chemical compound OCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl RVCKCEDKBVEEHL-UHFFFAOYSA-N 0.000 description 1
- CJFUEPJVIFJOOU-UHFFFAOYSA-N 2-perfluorobutyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1CCCO1 CJFUEPJVIFJOOU-UHFFFAOYSA-N 0.000 description 1
- ZRVIYEJYXIDATJ-UHFFFAOYSA-N 4-Heptyloxybenzoic acid Chemical compound CCCCCCCOC1=CC=C(C(O)=O)C=C1 ZRVIYEJYXIDATJ-UHFFFAOYSA-N 0.000 description 1
- CPEPWESLFZVUEP-UHFFFAOYSA-N 4-hexylbenzoic acid Chemical compound CCCCCCC1=CC=C(C(O)=O)C=C1 CPEPWESLFZVUEP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- IVRFYNSETZKRSJ-UHFFFAOYSA-N ClC=C.N#CC=CC=CC1=CC=CC=C1 Chemical compound ClC=C.N#CC=CC=CC1=CC=CC=C1 IVRFYNSETZKRSJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- SQNNHEYXAJPPKH-UHFFFAOYSA-N chloroethene;prop-2-enoic acid Chemical compound ClC=C.OC(=O)C=C SQNNHEYXAJPPKH-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NPDFIDKRMIDZNU-UHFFFAOYSA-N n-(4-butyl-2-methoxyphenyl)-1-phenylmethanimine Chemical compound COC1=CC(CCCC)=CC=C1N=CC1=CC=CC=C1 NPDFIDKRMIDZNU-UHFFFAOYSA-N 0.000 description 1
- 229950011087 perflunafene Drugs 0.000 description 1
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920005671 poly(vinyl chloride-propylene) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、物質選択機能を制御しうる有機高分
子膜の調製方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preparing an organic polymer film that can control substance selection function.
近年、工学、医学、農学等広範囲の分野で、透
過性あるいは選択透過性を利用した膜技術が開発
され、防湿膜、脱塩膜、人工腎臓用透析膜、イオ
ン交換膜等現実に実施されつつある。さらに、最
近においては、省エネルギー化技術の一つとし
て、酸素富化膜、資源分離膜、電荷分離膜等、特
異的でしかも高機能を有する膜の開発の重要性が
高まつている。 In recent years, membrane technologies that utilize permeability or permselectivity have been developed in a wide range of fields such as engineering, medicine, and agriculture, and are being put into practice, such as moisture-proof membranes, desalination membranes, dialysis membranes for artificial kidneys, and ion exchange membranes. be. Furthermore, recently, as an energy-saving technology, the development of specific and highly functional membranes such as oxygen enrichment membranes, resource separation membranes, and charge separation membranes has become increasingly important.
例えば、酸素富化膜についてみるとその素材と
して、高分子多孔膜(特開昭55−8803号)、フツ
素を含むシリコーン系ゴム−多孔性ポリテトラフ
ルオロエチレン(特開昭56−5121号)、架橋ポリ
オルガノシロキサン−直鎖ポリオルガノシロキサ
ン共重合体(特開昭56−26508号)、セルロースモ
ノカルボン酸エステル(特開昭56−26526号)、ス
チレンシロキサンポリマーα、ω−2官能ポリシ
ロキサン架橋型ポリマー(特開昭56−28604号等)
等々、種々の提案がなされている。しかしなが
ら、いずれの素材も、ガス透過係数、分離係数、
あるいは製造可能な膜厚等のバランスが不充分で
ある。 For example, regarding oxygen enrichment membranes, their materials include porous polymer membranes (Japanese Patent Laid-Open No. 55-8803), silicone rubber containing fluorine - porous polytetrafluoroethylene (Japanese Patent Laid-Open No. 56-5121). , crosslinked polyorganosiloxane-linear polyorganosiloxane copolymer (JP-A-56-26508), cellulose monocarboxylic acid ester (JP-A-56-26526), styrene siloxane polymer α, ω-bifunctional polysiloxane Cross-linked polymer (JP-A No. 56-28604, etc.)
Various proposals have been made. However, for both materials, gas permeability coefficient, separation coefficient,
Or, the balance of the film thickness etc. that can be manufactured is insufficient.
一方、有機高分子膜を調製する方法も多数提案
されている。例えば、水面上へのキヤストによる
製膜方法あるいはプラズマ気相重合により多孔質
支持体上に製膜する方法等があげられる(特開昭
50−41958号等)。しかしながら、実用に供し得る
だけの面積をもつ薄い有機高分子膜を製造するた
めの信頼性及び再現性ある方法は今日もなお当業
界において強く要望されている。 On the other hand, many methods for preparing organic polymer films have also been proposed. For example, a method of forming a film by casting onto a water surface or a method of forming a film on a porous support by plasma vapor phase polymerization (Japanese Patent Application Laid-open No.
50-41958 etc.). However, there is still a strong need in the art today for reliable and reproducible methods for producing thin organic polymer membranes with a practical area.
本発明者等は、有機高分子膜素材及びその製膜
方法について、従来の問題点を解決すべく鋭意研
究を積重ね、本発明を完成するに至つたものであ
る。すなわち、本発明の物質選択機能を制御しう
る有機高分子膜の調製方法は、ハロゲン化ビニル
重合体及び/又はハロゲン化ビニルと共重合しう
るモノマーとハロゲン化ビニルとの共重合体を、
該(共)重合体の良溶媒と貧溶媒との混合溶媒に
溶解せしめて重合体溶液を得、該重合体溶液を水
面上に展開して製膜することを特徴とするもので
ある。 The present inventors have conducted extensive research to solve the conventional problems regarding organic polymer film materials and methods for forming the same, and have completed the present invention. That is, the method for preparing an organic polymer membrane capable of controlling the substance selection function of the present invention comprises using a halogenated vinyl polymer and/or a copolymer of a monomer copolymerizable with vinyl halide and vinyl halide,
The method is characterized in that a polymer solution is obtained by dissolving the (co)polymer in a mixed solvent of a good solvent and a poor solvent, and the polymer solution is spread on a water surface to form a film.
本発明に用いられるハロゲン化ビニル重合体及
び/又はハロゲン化ビニルと共重合しうるモノマ
ーとハロゲン化ビニルとの共重合体としては、例
えば、ポリ塩化ビニル、ポリ臭化ビニル、ポリフ
ツ化ビニル、塩化ビニール−酢酸ビニル共重合
体、塩化ビニル−エチレン共重合体、塩化ビニル
−プロピレン共重合体、塩化ビニル−スチレン共
重合体、塩化ビニル−イソブチレン共重合体、塩
化ビニル−塩化ビニリデン共重合体、塩化ビニル
−スチレン−無水マレイン酸三元共重合体、塩化
ビニル−スチレン−アクリロニトリル共重合体、
塩化ビニル−ブタジエン共重合体、塩化ビニル−
イソプレン共重合体、塩化ビニル−塩素化プロピ
レン共重合体、塩化ビニル−塩素化ビニリデン−
酢酸ビニル三元共重合体、塩化ビニル−アクリル
酸エステル共重合体、塩化ビニル−マレイン酸エ
ステル共重合体、塩化ビニル−アクリロニトリル
共重合体等が挙げられる。本発明にいうハロゲン
化ビニル重合体には、ポリテトラフルオロエチレ
ン、ポリテトラフルオロクロルエチレン、ポリ弗
化ビニリデン、ポリ塩化ビニリデン等も含まれ
る。これらのポリマーは、膜の使用目的、使用場
面に応じ、広く選択しうる。例えば、酸素富化膜
として使用する場合には、適当な溶媒を有するポ
リマーが好都合である。 Examples of the vinyl halide polymer and/or the copolymer of vinyl halide and a monomer copolymerizable with vinyl halide used in the present invention include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, and vinyl chloride. Vinyl-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, chloride Vinyl-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer,
Vinyl chloride-butadiene copolymer, vinyl chloride-
Isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-chlorinated vinylidene-
Examples include vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, and the like. The halogenated vinyl polymer referred to in the present invention also includes polytetrafluoroethylene, polytetrafluorochloroethylene, polyvinylidene fluoride, polyvinylidene chloride, and the like. These polymers can be selected from a wide range depending on the intended use of the membrane and the usage situation. For example, for use as an oxygen enrichment membrane, polymers with suitable solvents are advantageous.
本発明においては、(共)重合体に、ネマチツ
ク液晶物質、物質選択向上剤等を併用することも
できる。例えば、ネマチツク液晶物質としては、
例えばメトキシベンジリデン−p−n−ブチルア
ニリン、エトキシベンジリデン−p−n−ブチリ
アニリン、n−プロピロキシベンジリデン−p−
n−ブチルアニリン、n−ブトキシベンジリデン
−p−n−ブチルアニリン、メトキシベンジリデ
ン−p−n−アミルアニリン、エトキシベンジリ
デン−p−n−アミルアニリン、n−プロピロキ
シベンジリデン−p−n−アミルアニリン、n−
ブトキシベンジリデン−p−n−アミルアニリ
ン、n−アミロキシベンジリデン−p−n−アミ
ルアニリン、メトキシベンジリデン−p−n−ヘ
キシルアニリン、p−アニシリデン−p−アミノ
フエニルアセテート、p−アニシリデン−p−ア
ミノベンゾニトリル、p−アゾキシアニソール、
p−エトキシ−p′−ヘキサノニロキシアゾベンゼ
ン、p−n−ヘキシルベンゾイツクアシツド−
p′−n−ヘキシルオキシフエニルエステル、ブチ
ル4−(4′−エトキシフエノキシカルボニル)−フ
エニルカーボネート(BEPCPC)、N−4−ペン
チロキシカルボニロキシベンジリデン−4′−アニ
シジン(PCBA)、4−n−ヘプチロキシベンゾ
イツクアシツド(HBA)、N,N′−ビス−p−
メトキシベンジリデン−3,3′−ジクロロベンジ
アジン(MBDB)等が挙げられる。 In the present invention, a nematic liquid crystal substance, a substance selection improver, etc. can also be used in combination with the (co)polymer. For example, as a nematic liquid crystal material,
For example, methoxybenzylidene-p-n-butylaniline, ethoxybenzylidene-p-n-butyaniline, n-propyloxybenzylidene-p-
n-butylaniline, n-butoxybenzylidene-pn-butylaniline, methoxybenzylidene-pn-amylaniline, ethoxybenzylidene-pn-amylaniline, n-propyloxybenzylidene-pn-amylaniline, n-
Butoxybenzylidene-p-n-amylaniline, n-amyloxybenzylidene-p-n-amylaniline, methoxybenzylidene-p-n-hexylaniline, p-anicylidene-p-aminophenyl acetate, p-anisylidene-p- Aminobenzonitrile, p-azoxyanisole,
p-ethoxy-p'-hexanonyloxyazobenzene, p-n-hexylbenzoic acid
p'-n-hexyloxyphenyl ester, butyl 4-(4'-ethoxyphenoxycarbonyl)-phenyl carbonate (BEPCPC), N-4-pentyloxycarbonyloxybenzylidene-4'-anisidine (PCBA) , 4-n-heptyloxybenzoic acid (HBA), N,N'-bis-p-
Examples include methoxybenzylidene-3,3'-dichlorobendiazine (MBDB).
ネマチツク液晶物質の使用量は、膜の使用目的
に応じ、ハロゲン化ビニル(共)重合体95〜5重
量部に対し、5〜95重量部の範囲から適宜選択す
ることができる。 The amount of the nematic liquid crystal substance to be used can be appropriately selected from the range of 5 to 95 parts by weight based on 95 to 5 parts by weight of the vinyl halide (co)polymer, depending on the intended use of the membrane.
本発明においては、ハロゲン化ビニル(共)重
合体とネマチツク液晶物質との混合物に物質選択
性向上剤を併用することもできる。物質選択性向
上剤は、膜の使用目的に応じ、広範囲の物質から
選択される。例えば、本発明に係る有機高分子膜
を酸素富化膜として使用する場合には、物質選択
性向上剤は、酸素取込能の大きな物質が好都合に
選択される。例えばパーフルオロトリブチルアミ
ン、パーフルオロデカリン、パーフルオロメチル
デカリン、パーフルオロテトラヒドロフラン、パ
ーフルオロブチルテトラヒドロフラン等が挙げら
れるまた、物質選択性向上剤として、クラウンエ
ーテルを用いると、金属イオンを選択的に透過す
る有機高分子膜が得られる。さらに、アゾクラウ
ンエーテルを使用するときは、例えば、K+イオ
ンの輸送を光で加速しうる有機高分子膜を得るこ
とができる。物質選択性向上剤の添加量は、有機
高分子膜に使用される有機高分子化合物の種類、
ネマチツク液晶物質の種類及び使用量等を勘案し
て、適宜定められる。さらに、物質選択性向上剤
の分散をよくするため、界面活性剤等を添加する
ことができる。 In the present invention, a material selectivity improver can also be used in combination with the mixture of the vinyl halide (co)polymer and the nematic liquid crystal material. The substance selectivity enhancer is selected from a wide range of substances depending on the intended use of the membrane. For example, when the organic polymer membrane according to the present invention is used as an oxygen-enriching membrane, a substance with a high oxygen uptake capacity is advantageously selected as the substance selectivity improver. Examples include perfluorotributylamine, perfluorodecalin, perfluoromethyldecalin, perfluorotetrahydrofuran, perfluorobutyltetrahydrofuran, etc. Also, when crown ether is used as a substance selectivity improver, metal ions are selectively permeated. An organic polymer film is obtained. Furthermore, when using azo crown ether, it is possible to obtain, for example, an organic polymer film in which the transport of K + ions can be accelerated with light. The amount of substance selectivity improver added depends on the type of organic polymer compound used in the organic polymer membrane,
It is determined as appropriate, taking into consideration the type and amount of nematic liquid crystal material used. Furthermore, a surfactant or the like may be added to improve the dispersion of the substance selectivity improver.
本発明に用いられるハロゲン化ビニル(共)重
合体の良溶媒としては、シクロヘキサノン、テト
ラヒドロフラン、ブタノン等があげられる。また
貧溶媒としては、ベンゼン、トルエンテトラクロ
ロエチレン等貧溶媒であり、かつ水面に展開しや
すい溶媒が選ばれる。良溶媒と貧溶媒との使用割
合は、当該重合体溶液を水面上に展開したとき、
当該重合体溶液が水面上に展開しやすく、かつ水
面上で製膜したときに、物質選択機能を制御しう
る多孔質膜となるよう、重合体の種類、良溶媒・
貧溶媒の種類に応じて適宜定められるが、例え
ば、ポリ塩化ビニル、良溶媒としてテトラヒドロ
フラン、貧溶媒としてトルエンを選択した場合に
は、トルエンの量の多い方が良い結果を与える。 Examples of good solvents for the halogenated vinyl (co)polymer used in the present invention include cyclohexanone, tetrahydrofuran, and butanone. Further, as the poor solvent, a solvent such as benzene, toluene, tetrachloroethylene, etc., which is a poor solvent and easily develops on the water surface is selected. The ratio of good and poor solvents to be used is as follows: When the polymer solution is spread on the water surface,
The type of polymer, good solvent, and
Although it is determined as appropriate depending on the type of poor solvent, for example, when polyvinyl chloride, tetrahydrofuran is selected as a good solvent, and toluene is selected as a poor solvent, a larger amount of toluene gives better results.
ハロゲン化(共)重合体を、該重合体の良溶
媒・貧溶媒の混合溶媒に溶解せしめた重合体溶液
を常法によつて水面上に展開し、水面上から膜を
取り出し、溶媒を乾燥除去することにより物質選
択機能を制御しうる有機高分子薄膜を得ることが
できる。本発明方法によれば、良溶媒と貧溶媒の
量比を変化させることにより、物質選択機能を制
御する能力に相違のある膜を自由に製造すること
ができるので、これらを目的に応じて積層するこ
とにより、多用途に応用することができる。 A polymer solution in which a halogenated (co)polymer is dissolved in a mixed solvent of a good solvent and a poor solvent for the polymer is spread on the water surface using a conventional method, the membrane is taken out from the water surface, and the solvent is dried. By removing it, it is possible to obtain an organic polymer thin film whose substance selection function can be controlled. According to the method of the present invention, by changing the ratio of good and poor solvents, it is possible to freely produce membranes with different ability to control substance selection functions, so these can be laminated according to the purpose. By doing so, it can be applied for a variety of purposes.
したがつて本発明により製膜された有機高分子
膜は、各種の物質の選択機能を特異的に制御する
ことができ、酸素富化膜をはじめとして資源分離
膜、電荷分離膜等として広い応用範囲を有するも
のである。またネマチツク液晶物質を含有してい
るので、電場を印加することにより、液晶配向を
制御し、これによつて気体その他各種物質の膜透
過性を特異的にコントロールすることができる。 Therefore, the organic polymer membrane produced according to the present invention can specifically control the selection function of various substances, and can be widely applied as an oxygen enrichment membrane, resource separation membrane, charge separation membrane, etc. It has a range. Furthermore, since it contains a nematic liquid crystal material, the liquid crystal alignment can be controlled by applying an electric field, thereby making it possible to specifically control the membrane permeability of gases and other various substances.
以下に、本発明を実施例により具体的に説明す
る。 The present invention will be specifically explained below using examples.
実施例 1
ポリ塩化ビニル(重合度1050)粉末を、テトラ
ヒドロフランとトルエンの混合溶媒(重量比で
1/1及び1/2の2種類を準備)に溶解し、4
重量%の重合体溶液を得た。Example 1 Polyvinyl chloride powder (polymerization degree 1050) was dissolved in a mixed solvent of tetrahydrofuran and toluene (two types were prepared, 1/1 and 1/2 by weight), and 4
A wt % polymer solution was obtained.
この重合体溶液を283Kに保たれた水槽中の水
面の壁際に1滴を静かに落とし、水面上に薄膜を
形成せしめ、直ちにすくい上げ、室温で真空乾燥
して約70nmの厚みの膜(水面展開膜)(約400cm2)
を得た。 A drop of this polymer solution was gently dropped on the wall of the water surface in a water tank kept at 283K to form a thin film on the water surface, which was immediately scooped up and dried under vacuum at room temperature to form a film with a thickness of about 70 nm (developed on the water surface). membrane) (approximately 400cm 2 )
I got it.
この水面展開膜を透過型電子顕微鏡で観察し
た。 This water surface-deployed film was observed using a transmission electron microscope.
第1図は、テトラヒドロフラン/トルエン=
1/1(重量比)の混合溶媒を用いたときの水面
展開膜の電顕写真であり、第2図はテトラヒドロ
フラン/トルエン=1/2(重量比)の混合溶媒
を用いたときの電顕写真である。 Figure 1 shows that tetrahydrofuran/toluene =
This is an electron micrograph of a water surface developed film when a mixed solvent of 1/1 (weight ratio) is used, and Figure 2 is an electron micrograph of a film developed on a water surface when a mixed solvent of tetrahydrofuran/toluene = 1/2 (weight ratio) is used. It's a photo.
本発明により製膜された高分子膜は、図に示す
とおり、網目状構造を示しており、積層膜は連続
相の多孔膜となつている。 As shown in the figure, the polymer membrane produced according to the present invention has a network structure, and the laminated membrane is a porous membrane with a continuous phase.
第1図は、THF/トルエン=1/1(重量比)
の混合溶媒を用いて水面展開して得た薄膜の表面
組織を示す電子顕微鏡写真である。第2図は、
THF/トルエン=1/2(重量比)の混合溶媒を
用いて水面展開して得た薄膜の表面組織を示す電
子顕微鏡写真である。
Figure 1 shows THF/toluene = 1/1 (weight ratio)
1 is an electron micrograph showing the surface structure of a thin film obtained by spreading on a water surface using a mixed solvent of Figure 2 shows
It is an electron micrograph showing the surface structure of a thin film obtained by developing it on the water surface using a mixed solvent of THF/toluene=1/2 (weight ratio).
Claims (1)
化ビニルと共重合しうるモノマーとハロゲン化ビ
ニルとの共重合体を、該(共)重合体の良溶媒と
貧溶媒との混合溶媒に溶解せしめて重合体溶液を
得、該重合体溶液を水面上に展開して製膜するこ
とを特徴とする物質選択機能を制御しうる有機高
分子膜の調製方法。1 A copolymer of a vinyl halide polymer and/or a monomer copolymerizable with vinyl halide and a vinyl halide is dissolved in a mixed solvent of a good solvent and a poor solvent for the (co)polymer. 1. A method for preparing an organic polymer film capable of controlling a substance selection function, comprising obtaining a polymer solution and forming a film by spreading the polymer solution on a water surface.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5226684A JPS60196313A (en) | 1984-03-21 | 1984-03-21 | Preparation of organic high molecular film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5226684A JPS60196313A (en) | 1984-03-21 | 1984-03-21 | Preparation of organic high molecular film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60196313A JPS60196313A (en) | 1985-10-04 |
JPH0523818B2 true JPH0523818B2 (en) | 1993-04-05 |
Family
ID=12909964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5226684A Granted JPS60196313A (en) | 1984-03-21 | 1984-03-21 | Preparation of organic high molecular film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60196313A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY172992A (en) * | 2014-02-26 | 2019-12-17 | Univ Kebangsaan Malaysia | A membrane, a method for preparing the same and a use thereof |
-
1984
- 1984-03-21 JP JP5226684A patent/JPS60196313A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60196313A (en) | 1985-10-04 |
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