JPH0494725A - Composite semipermeable membrane - Google Patents
Composite semipermeable membraneInfo
- Publication number
- JPH0494725A JPH0494725A JP21221090A JP21221090A JPH0494725A JP H0494725 A JPH0494725 A JP H0494725A JP 21221090 A JP21221090 A JP 21221090A JP 21221090 A JP21221090 A JP 21221090A JP H0494725 A JPH0494725 A JP H0494725A
- Authority
- JP
- Japan
- Prior art keywords
- semipermeable membrane
- polyethylene oxide
- membrane
- composite semipermeable
- water
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims description 44
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 31
- 239000010409 thin film Substances 0.000 claims abstract description 19
- 229920003176 water-insoluble polymer Polymers 0.000 claims abstract description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 19
- 150000003839 salts Chemical class 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003431 cross linking reagent Substances 0.000 abstract description 11
- 239000010408 film Substances 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 7
- 230000000903 blocking effect Effects 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 1
- -1 amino compound Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920005687 PMMA-PEG Polymers 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-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
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-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
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006035 cross-linked graft co-polymer Polymers 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
童栗上皇程朋分野
本発明は複合半透膜に関し、詳しくは、多孔性基材上に
半透性超薄膜を有し、更にその上に、側鎖としてポリエ
チレンオキサイドセグメントを有し、幹部分が実質的に
水不溶性の重合体からなるグラフト共重合体の膜が積層
されてなる塩阻止性能にすくれる複合半透膜に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a composite semipermeable membrane, and more specifically, it has a semipermeable ultra-thin membrane on a porous base material, and further has polyethylene oxide as a side chain thereon. The present invention relates to a composite semipermeable membrane having excellent salt blocking performance, which is obtained by stacking membranes of a graft copolymer having segments and a trunk portion of which is made of a substantially water-insoluble polymer.
。
従米企肢庸
近年、逆浸透膜として多孔性基村上に半透性を有する超
薄膜を形成させた複合半透膜が、後述するように、種々
知られている。. In recent years, various composite semipermeable membranes have been known as reverse osmosis membranes, in which an ultra-thin semipermeable membrane is formed on a porous substrate, as described below.
これらの超薄膜を備えた複合半透膜は、従来より逆浸透
膜として広く用いられている酢酸セルロース膜に比較し
て、一般に、塩阻止性能や透水性能等の逆浸透性能にす
ぐれてはいるが、しかし、実用的な脱塩に適用するには
、尚、塩阻止率の点で満足できるものではない。特に、
半導体の製造において、ＬＳＩの洗浄に用いられる超純
水には、近年のＬＳＩ集積密度の一層の高度化に伴って
、高度に脱塩された純水が要求されるに至っており、か
くして、超純水の製造に用いられる逆浸透膜には、従来
に比べて、−層、高い塩阻止率を有するものが求められ
ている。Composite semipermeable membranes with these ultra-thin membranes generally have superior reverse osmosis performance, such as salt blocking performance and water permeability, compared to cellulose acetate membranes, which have traditionally been widely used as reverse osmosis membranes. However, when applied to practical desalting, the salt rejection rate is still not satisfactory. especially,
In the manufacturing of semiconductors, highly desalinated pure water is required as ultrapure water used for cleaning LSIs, as the integration density of LSIs has become more sophisticated in recent years. Reverse osmosis membranes used for producing pure water are required to have a lower salt rejection rate than conventional ones.
が ゛ しようとする
本発明は、上記した要望に応えるためになされたもので
あって、塩阻止性能にす（れる複合半透膜を提供するこ
とを目的とする。The present invention has been made in response to the above-mentioned needs, and an object of the present invention is to provide a composite semipermeable membrane with excellent salt blocking performance.
ｉ題を”ンするための１
本発明による複合半透膜は、多孔性基材上に半透性超薄
膜を有し、更にその上に、側鎖としてボリエチレンオキ
サイドセグメントを有し、幹部分が実質的に水不溶性の
重合体からなるグラフト共重合体からなる膜が積層され
ていることを特徴とする。A composite semipermeable membrane according to the present invention has a semipermeable ultra-thin membrane on a porous substrate, further has polyethylene oxide segments as side chains thereon, and has a polyethylene oxide segment as a side chain. It is characterized in that membranes made of a graft copolymer made of a substantially water-insoluble polymer are laminated.
本発明において、半透性超薄膜は、分子内に１級及び／
又は２級アミノ基を少なくとも２個有する多価アミノ化
合物が上記アミノ基と反応し得る多官能性架橋剤で架橋
されてなる膜である。このような超薄膜は、多孔性基村
上に、分子内に１級及び／又は２級アミノ基を少なくと
も２個有する水溶性多価アミノ化合物を主成分とする水
溶液を塗布した後、この多価アミノ化合物にそのアミノ
基と反応し得る多官能性架橋剤を接触させて、界面重合
させ、架橋させることによって形成させることができ、
通常、５０〜１００００人、好ましくは１００〜５００
０人の厚みを有する。In the present invention, the semipermeable ultra-thin film contains primary and/or
Alternatively, it is a membrane in which a polyvalent amino compound having at least two secondary amino groups is crosslinked with a polyfunctional crosslinking agent capable of reacting with the above amino groups. Such an ultra-thin film is produced by coating a porous substrate with an aqueous solution mainly composed of a water-soluble polyvalent amino compound having at least two primary and/or secondary amino groups in the molecule, and then It can be formed by bringing an amino compound into contact with a polyfunctional crosslinking agent that can react with the amino group to cause interfacial polymerization and crosslinking.
Usually 50 to 10,000 people, preferably 100 to 500 people
It has a thickness of 0 people.
ここに、分子内に１級及び／又は２級アミノ基を少なく
とも２個有する水溶性多価アミノ化合物は、分子量が５
０〜５０００００の範囲の単量体化合物から高分子量重
合体を含み、具体的には、例えば、ポリエチレンイミン
、アミン変性ポリエピクロロヒドリン、エポキシ化合物
とアミノ化合物との重合による水溶性オリゴマー等の重
合体、フェニレンジアミン、ジアミノピリジン、ジアミ
ノジフェニルエーテル、ジアミノジフェニルスルホン、
ピペラジン、２，５−ジメチルピペラジン、ボモビペラ
ジン、エチレンジアミン等を挙げることができる。Here, the water-soluble polyvalent amino compound having at least two primary and/or secondary amino groups in the molecule has a molecular weight of 5.
It includes monomer compounds ranging from 0 to 500,000 to high molecular weight polymers, specifically, for example, polyethyleneimine, amine-modified polyepichlorohydrin, water-soluble oligomers obtained by polymerizing epoxy compounds and amino compounds, etc. Polymer, phenylenediamine, diaminopyridine, diaminodiphenyl ether, diaminodiphenylsulfone,
Examples include piperazine, 2,5-dimethylpiperazine, bomobiperazine, and ethylenediamine.
また、多官能性架橋剤としては、分子内にイソシアネー
ト基、酸ハライド基、Ｎ−ハロホルミル基等の前記水溶
性アミノ化合物の有するアミノ基と反応し得る官能基を
少なくとも２個有する化合物が好適に用いられ、具体的
には、塩化イソフタロイル、塩化テレフタロイル、トリ
メソイルクロライド、トリレンジイソシアネート、４，
４゛−ジフェニルエーテルジイソシアネート、４，４゛
−ジフェニルメタンジイソシアネート等を挙げることが
できる。Further, as the polyfunctional crosslinking agent, a compound having at least two functional groups capable of reacting with the amino group of the water-soluble amino compound, such as an isocyanate group, an acid halide group, or an N-haloformyl group, is preferably used as the polyfunctional crosslinking agent. Specifically, isophthaloyl chloride, terephthaloyl chloride, trimesoyl chloride, tolylene diisocyanate, 4,
Examples include 4'-diphenyl ether diisocyanate and 4,4'-diphenylmethane diisocyanate.
上記のような多価アミノ化合物と多官能性架橋剤を用い
る半透性超薄膜は、通常、上記水溶性多価アミノ化合物
の水溶液を多孔性基材上に塗布した後、多官能性架橋剤
と接触させ、界面重合を起コサセ、次いで、加熱硬化さ
せることによって、乾燥膜として得ることができる。上
記多孔性基材としては、特に、限定されるものではない
が、例えば、ポリスルホン膜、ポリエーテルスルホン膜
、ポリアクリロニトリル膜、セルロースエステル膜、ポ
リ塩化ビニル膜等を好適に用いることができる。A semipermeable ultra-thin film using a polyvalent amino compound and a polyfunctional crosslinking agent as described above is usually produced by coating an aqueous solution of the water-soluble polyvalent amino compound on a porous substrate, and then applying the polyfunctional crosslinking agent. It can be obtained as a dry film by bringing the film into contact with the film to cause interfacial polymerization, and then heating and curing the film. The porous base material is not particularly limited, but for example, polysulfone membranes, polyethersulfone membranes, polyacrylonitrile membranes, cellulose ester membranes, polyvinyl chloride membranes, etc. can be suitably used.
このように、多孔性基材上に半透性超薄膜を形成させて
なる複合半透膜は、既に種々のものが知られており、例
えば、ポリスルホン多孔性基村上でポリエチレンイミン
をトリレンジイソシアネートで架橋させた超薄膜を有す
る複合半透膜（特開昭４９−１３３２８２号公報）、ポ
リエチレンイミンに代えて、アミン変性ポリエピクロロ
ヒドリンを上記と同様の多官能性架橋剤で架橋して超薄
膜を形成してなる複合半透膜（特公昭５５−３８１６４
号公報）、エポキシ化合物とアミノ化合物との重合によ
り得られる水溶性オリゴマーを上記と同様の架橋剤で架
橋して超薄膜を形成した複合半透膜（特開昭５３−１４
４８４４号公報）、ポリエチレンイミン等の水溶性重合
体とアミノ基を分子内に２個以上有する多価アミノ化合
物単量体とを上記と同様の多官能性架橋剤で共架橋して
超薄膜を形成した複合半透膜（特開昭５６−１３９１０
５号公報）、分子内に少なくとも２個の第１級アミノ置
換基を有する芳香族単量体を多官能アシルハライド置換
の芳香族単量体で架橋して超薄膜を形成した複合半透膜
（特開昭５５−１４７１０６号公報）、ポリビニルアル
コールと第２級アミノ基を分子内に２個以上有するアミ
ノ化合物を多官能性架橋剤で架橋して超薄膜を形成した
複合半透膜（特公昭６１−２７０８３号公報）等を挙げ
ることができる。As described above, various types of composite semipermeable membranes formed by forming semipermeable ultra-thin membranes on porous substrates are already known. A composite semipermeable membrane having an ultra-thin film cross-linked with (Japanese Unexamined Patent Publication No. 133282/1982), amine-modified polyepichlorohydrin is cross-linked with the same polyfunctional cross-linking agent as above in place of polyethyleneimine. Composite semipermeable membrane formed by forming an ultra-thin film (Special Publication No. 55-38164
(Japanese Unexamined Patent Publication No. 53-14), a composite semipermeable membrane in which an ultra-thin film was formed by crosslinking a water-soluble oligomer obtained by polymerizing an epoxy compound and an amino compound with the same crosslinking agent as above (Japanese Unexamined Patent Publication No. 53-14
4844), a water-soluble polymer such as polyethyleneimine and a polyvalent amino compound monomer having two or more amino groups in the molecule are co-crosslinked using the same polyfunctional crosslinking agent as above to form an ultra-thin film. The composite semipermeable membrane formed (Japanese Patent Application Laid-Open No. 56-13910
5), a composite semipermeable membrane in which an ultra-thin film is formed by crosslinking an aromatic monomer having at least two primary amino substituents in the molecule with a polyfunctional acyl halide-substituted aromatic monomer. (Japanese Unexamined Patent Publication No. 55-147106), a composite semipermeable membrane (specially Publication No. 61-27083).
本発明による複合半透膜は、このような従来の複合半透
膜の有する半透性超薄膜の上に、更に、側鎖としてポリ
エチレンオキサイドセグメントを有し、幹部分が実質的
に水不溶性の重合体からなるグラフト共重合体からなる
膜が積層されている。The composite semipermeable membrane according to the present invention further has a polyethylene oxide segment as a side chain on top of the ultra-thin semipermeable membrane possessed by such a conventional composite semipermeable membrane, and the main portion is substantially water-insoluble. Membranes made of graft copolymers made of polymers are laminated.
かかるグラフＩ・共重合体において、幹部分を形成する
実質的に水不溶性の重合体は、好ましくは、ビニル系単
量体及びアクリル系単量体から選ばれる少な（とも１種
のラジカル重合性単量体の単独重合体又は共重合体から
なる。In such a Graph I copolymer, the substantially water-insoluble polymer forming the backbone portion is preferably a small amount selected from vinyl monomers and acrylic monomers (both of which include one type of radically polymerizable monomer). Consists of a homopolymer or copolymer of monomers.
上記ビニル系単量体としては、例えば、スチレン、α−
メチルスチレン等のスチレン系単量体、酢酸ビニル、プ
ロピオン酸ビニル等のビニルエステル、塩化ビニル、ビ
ニルピリジン等を挙げることができる。また、」二足ア
クリル系単量体としては、例えば、アクリル酸、メタク
リル酸、アクリル酸メチル、アクリル酸ブチル、メタク
リル酸メチル、メタクリル酸ブチル、２−エチルへキシ
ルアクリレート、ヒドロキシエチルメタクリレート、ヒ
ドロキシプロピルメタクリレート、グリシジルアクリレ
ート、グリシジルメタクリレート、アクリロニトリル、
メタクリレートリル等を挙げることができる。これらは
、単量体によっては単独で、又は他の単量体と組み合わ
せて用いられる。Examples of the vinyl monomer include styrene, α-
Examples include styrenic monomers such as methylstyrene, vinyl esters such as vinyl acetate and vinyl propionate, vinyl chloride, and vinylpyridine. In addition, examples of bipedal acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, hydroxypropyl Methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylonitrile,
Methacrylate trile and the like can be mentioned. Depending on the monomer, these may be used alone or in combination with other monomers.
本発明においては、グラフ１〜共重合体において幹部分
の重合体としては、特に、ポリメタクリル酸メチルやポ
リアクリル酸ブチル等のポリメタクリル酸アルキルやポ
リアクリル酸アルキル等が好ましい。In the present invention, as the polymer for the trunk portion in the copolymers from Graph 1, polyalkyl methacrylates and alkyl polyacrylates such as polymethyl methacrylate and polybutyl acrylate are particularly preferred.
本発明においては、グラフト共重合体における側鎖のポ
リエチレンオキサイドセグメントの分子量は、２００〜
５００００の範囲が適当である。In the present invention, the molecular weight of the side chain polyethylene oxide segment in the graft copolymer is 200 to
A range of 50,000 is appropriate.
この分子量が２００よりも小さいときは、塩の膜内透過
を抑制する効果に乏しく、他方、５００００を越えると
きは、ポリエチレンオキサイドセグメンｌ−の親水性が
低く、複合半透膜が透水性に劣る。When this molecular weight is less than 200, the effect of suppressing salt permeation through the membrane is poor, while when it exceeds 50,000, the hydrophilicity of the polyethylene oxide segment l- is low, and the composite semipermeable membrane has poor water permeability. .
更に、グラフト共重合体におけるポリエチレンオキサイ
ドの含有率は、５〜９０重量％の範囲にあることが好ま
しい。５重量％よりも少ないときは、得られる複合半透
膜が透水性に乏しく、他方、９０重量％を越えるときは
、得られる複合半透膜が耐水強度に劣る。Furthermore, the content of polyethylene oxide in the graft copolymer is preferably in the range of 5 to 90% by weight. If it is less than 5% by weight, the resulting composite semipermeable membrane will have poor water permeability, while if it exceeds 90% by weight, the resulting composite semipermeable membrane will have poor water resistance.
尚、側鎖のポリエチレンオキサイドの末端は、メトキシ
基、エトキシ基、ブトキシ基等のアルコキシ基又は水酸
基のほか、カルボキシル基、アミノ基、エポキシ基、ス
ルホニル基、リン酸基等であってもよい。The end of the polyethylene oxide side chain may be an alkoxy group such as a methoxy group, an ethoxy group, a butoxy group, or a hydroxyl group, as well as a carboxyl group, an amino group, an epoxy group, a sulfonyl group, a phosphoric acid group, or the like.
本発明において、上記のようなグラフト共重合体は、例
えば、以下に述べるような方法によって得ることができ
る。In the present invention, the above graft copolymer can be obtained, for example, by the method described below.
第１には、ポリエチレンオキザイドマクロモノマーを前
述したようなラジカル重合性単量体と共重合させる方法
を挙げることができる。第２には、先ず、前述したラジ
カル重合性単量体を２−イソシアネートエチルメタクリ
レートと共重合させて、イソシアネート基を有する幹部
分を形成し、次いで、このイソシアネート基にポリエチ
レングリコールモルアルキルエーテルを反応させる方法
を挙げることができる。The first method is to copolymerize a polyethylene oxide macromonomer with a radically polymerizable monomer as described above. Second, first, the above-mentioned radically polymerizable monomer is copolymerized with 2-isocyanate ethyl methacrylate to form a trunk portion having an isocyanate group, and then this isocyanate group is reacted with polyethylene glycol molar alkyl ether. Here are some ways to do it.
第３には、先ず、前述したラジカル重合性単量体を２−
ヒドロキシエチルメタクリレートのような水酸基を有す
る単量体と共重合させて、水酸基を有する幹部分を形成
し、次いで、これに例えばカリウムのようなアルカリ金
属を反応させて、水酸基をアルコキサイド様のアニオン
に変換し、この後、これにエチレンオキサイドを作用さ
せて、リビングアニオン重合させる方法を挙げることが
できる。これらの方法のなかでは、簡便であり、また、
収率も高いことから、第１の方法が最も好ましい。Thirdly, first, the above-mentioned radically polymerizable monomer is
Copolymerization with a hydroxyl-containing monomer such as hydroxyethyl methacrylate forms a hydroxyl-containing backbone, which is then reacted with an alkali metal such as potassium to convert the hydroxyl group into an alkoxide-like anion. A method may be mentioned in which living anionic polymerization is carried out by converting the polymer and then reacting it with ethylene oxide. Among these methods, it is simple and
The first method is most preferred since it also has a high yield.
本発明による複合半透膜において、このようなグラフト
共重合体からなる膜の厚さは、通常、１０人乃至１０μ
ｍの範囲がよい。グラフト共重合体の膜厚が１０人より
も薄いときは、塩の阻止性能が向上に効果がなく、他方
、１０μｍを越えるときは、膜の透水性能が著しく低下
するので好ましくない。In the composite semipermeable membrane according to the present invention, the thickness of the membrane made of such a graft copolymer is usually 10 to 10 μm.
The range of m is good. When the membrane thickness of the graft copolymer is less than 10 μm, it is not effective in improving the salt blocking performance, while when it exceeds 10 μm, the water permeability of the membrane is undesirably reduced.
グラフト共重合体を前記多孔性基材上の半透性超薄膜上
に被覆するには、グラフト共重合体を溶融塗布する方法
、多孔性基材及びその上の半透性超薄膜に有害な影響を
与えない適宜の有機溶剤にグラフト共重合体を溶解させ
、これを塗布した後、乾燥させる方法等によることもで
きるが、特に、グラフト共重合体を適当な有機溶剤に溶
解させ、その溶液を水面上に展開し、得られた薄膜を半
透性超薄膜上に積層する方法によるのが好ましい。In order to coat the graft copolymer onto the semipermeable ultra-thin film on the porous substrate, there is a method of melt-coating the graft copolymer, which is harmful to the porous substrate and the semi-permeable ultra-thin film thereon. It is also possible to dissolve the graft copolymer in an appropriate organic solvent that does not cause any adverse effects, apply it, and then dry it. It is preferable to use a method in which a film is spread on a water surface and the obtained thin film is laminated on a semi-permeable ultra-thin film.
この方法によれば、均−性及び連続性にすぐれたグラフ
ト共重合体薄膜を半透性超薄膜上に積層し、被覆するこ
とができる。According to this method, a thin graft copolymer film with excellent uniformity and continuity can be laminated and coated on a semipermeable ultra-thin film.
本発明において、かかるグラフト共重合体薄膜は、架橋
されていてもよい。例えば、適宜の方法によって、予め
適当な官能基を有せしめたグラフト共重合体と、その架
橋剤と反応し得る架橋剤との混合物の溶液を前記半透性
超薄膜上に塗布し、加熱等によって架橋反応を起こさせ
れば、架橋したグラフト共重合体からなる薄膜を半透性
超薄膜上に形成することができる。In the present invention, such a graft copolymer thin film may be crosslinked. For example, a solution of a mixture of a graft copolymer that has been provided with an appropriate functional group and a crosslinking agent capable of reacting with the graft copolymer is coated on the semipermeable ultra-thin film by an appropriate method, and heated, etc. By causing a crosslinking reaction, a thin film made of a crosslinked graft copolymer can be formed on a semipermeable ultra-thin film.
光里傅伏果
以上のように、本発明による複合半透膜は、半透性超薄
膜の上に、水不溶性の重合体からなる幹部分と、その側
鎖としてのポリエチレンオキサイドセグメントとからな
るグラフト共重合体からなる被膜を有する。従って、水
溶性であるポリエチレンオキサイドは、その幹部分によ
って、水中でも安定な被膜を形成している。As described above, the composite semipermeable membrane according to the present invention comprises a semipermeable ultra-thin membrane with a graft consisting of a trunk portion made of a water-insoluble polymer and polyethylene oxide segments as its side chains. It has a coating made of copolymer. Therefore, polyethylene oxide, which is water-soluble, forms a film that is stable even in water due to its trunk portion.
更に、ポリエチレンオキサイドセグメントは、カチオン
バインダーとして作用し、ナトリウムイオン、カリウム
イオン、カルシウムイオン等のカチオンの膜内透過を妨
げる。また、膜内においては、電気的中性が保たれるこ
とから、同時に、塩素イオン等のアニオンの透過も妨げ
られる。Furthermore, the polyethylene oxide segment acts as a cation binder and prevents cations such as sodium ions, potassium ions, and calcium ions from permeating through the membrane. Moreover, since electrical neutrality is maintained within the membrane, at the same time, the permeation of anions such as chloride ions is also prevented.
このようにして、本発明の複合半透膜は、ポリエチレン
オキサイドセグメンｌ〜を側鎖に有するグラフト共重合
体が水中で安定で強度を有し、しかも、塩の透過を妨げ
るので、高い塩層去性能を有する。In this way, the composite semipermeable membrane of the present invention has a high salt layer because the graft copolymer having polyethylene oxide segments l~ in its side chains is stable and strong in water, and also prevents salt permeation. It has the ability to remove
尖旌開
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.
参考例１
ブレイクシール法による操作にて高真空にした反応槽に
カリウムｔ−ブトキシド２５ｍｍｏｌと精製テトラヒド
ロフラン２００ｍ１とを入れた後、精製エチレンオキサ
イド５０ｇ−を仕込み、４０°Ｃの湯浴上で１２時間攪
拌して、ポリエチレンオキサイドリビングポリマーを得
た。Reference Example 1 After putting 25 mmol of potassium t-butoxide and 200 ml of purified tetrahydrofuran into a reaction tank that had been made into a high vacuum by operating the break-seal method, 50 g of purified ethylene oxide was charged, and the mixture was heated on a water bath at 40°C for 12 hours. The mixture was stirred to obtain a polyethylene oxide living polymer.
次いで、反応槽にメタクリル酸クロライド０．１ｍｏｌ
を加えて、上記ポリエチレンオキサイドリビングポリマ
ーと反応させて、末端メタクリロイル基を有するポリエ
チレンオキサイドマクロモノマーを得た。Next, 0.1 mol of methacrylic acid chloride was added to the reaction tank.
was added thereto and reacted with the polyethylene oxide living polymer to obtain a polyethylene oxide macromonomer having a terminal methacryloyl group.
このマクロモノマーの精製物をＧＰＣにて分析したとこ
ろ、数平均分子量（ポリスチレン換算）は３２６０であ
り、分子量分布は１．０８であった。When this purified macromonomer was analyzed by GPC, the number average molecular weight (in terms of polystyrene) was 3260, and the molecular weight distribution was 1.08.
また、プロトンＮＭＲ分析によると、Ｌ−ブトキシ基／
エチレンオキサイド／メタクリロイル基のモル比は１／
４５１０．９８であって、はぼ設計のとおりのマクロモ
ノマーてあった。Furthermore, according to proton NMR analysis, L-butoxy group/
The molar ratio of ethylene oxide/methacryloyl group is 1/
4510.98, and the macromonomer was as designed.
参考例２
カリウムも一ブトキシドの仕込み量Ｑ、１２ ｍｍｏｌ
とした以外は、参考例１と同様にして、ポリエチレンオ
キサイドリビングポリマーを得た。Reference example 2 Potassium monobutoxide amount Q, 12 mmol
A polyethylene oxide living polymer was obtained in the same manner as in Reference Example 1 except for the following.
このポリエチレンオキサイドリビングポリマーの精製物
をＧＰＣにて分析したところ、数千均分多量（ポリスチ
レン換算）は７０００であり、分子量分布は１．０８で
あった。また、プロトンＮＭＲ分析によると、ｔ−ブト
キシ基／エチレンオキサイド／メタクリロイル基のモル
比は１／９４１０．９６であって、はぼ設計のとおりの
マクロモノマーであった。When this purified polyethylene oxide living polymer was analyzed by GPC, it was found to have a weight of several thousand (in terms of polystyrene) of 7,000 and a molecular weight distribution of 1.08. Further, according to proton NMR analysis, the molar ratio of t-butoxy group/ethylene oxide/methacryloyl group was 1/9410.96, and it was a macromonomer as designed by Habo.
参考例３
冷却還流管を備えた２００ｍ１容量反応槽に参考例１に
て得たポリエチレンオキサイドマクロモノマー４０重量
部、メタクリル酸メチル６０重量部、トルエン１００重
量部及び２，２゛−アゾビスイソブチロニトリル０．６
重量部を仕込んだ。反応槽内を十分に窒素置換した後、
反応槽に窒素を流通させつつ、反応槽を６０°Ｃに加温
し、８時間攪拌して、粘稠な溶液を得た。Reference Example 3 40 parts by weight of the polyethylene oxide macromonomer obtained in Reference Example 1, 60 parts by weight of methyl methacrylate, 100 parts by weight of toluene, and 2,2′-azobisisobutylene were placed in a 200 ml reaction tank equipped with a cooling reflux tube. Lonitrile 0.6
I prepared the weight section. After sufficiently replacing the inside of the reaction tank with nitrogen,
While flowing nitrogen through the reaction tank, the reaction tank was heated to 60°C and stirred for 8 hours to obtain a viscous solution.
次いで、この溶液を多量のメタノール中に注ぎ、重合体
を沈殿させた。この沈殿を濾過し、乾燥させて、目的と
するポリメタクリル酸メチル−ポリエチレンオキサイド
グラフト共重合体を得た。This solution was then poured into a large amount of methanol to precipitate the polymer. This precipitate was filtered and dried to obtain the desired polymethyl methacrylate-polyethylene oxide graft copolymer.
このグラフト共重合体をＧＰＣ分析したところ、重量平
均分子量（ポリスチレン換算）は７．７×１０４であっ
た。また、プロｌ−ンＮＭＲ分析によると、グラフト共
重合体におけるポリエチレンオキサイド含有率は３９重
量％であった。GPC analysis of this graft copolymer revealed that the weight average molecular weight (in terms of polystyrene) was 7.7 x 104. Further, according to Proline NMR analysis, the polyethylene oxide content in the graft copolymer was 39% by weight.
参考例４
メタクリル酸メチルをアクリル酸ブチルに代えた以外は
、参考例３と同様にして、ポリアクリル酸ブチル−ポリ
エチレンオキサイドグラフト共重合体を得た。Reference Example 4 A polybutyl acrylate-polyethylene oxide graft copolymer was obtained in the same manner as Reference Example 3 except that butyl acrylate was used instead of methyl methacrylate.
このグラフト共重合体をＧＰＣ分析したところ、重量平
均分子量（ポリスチレン換算）は２４×１０４であった
。また、プロトンＮＭＲ分析によると、グラフト共重合
体におけるポリエチレンオキサイド含有率は３８重量％
であった。GPC analysis of this graft copolymer revealed that the weight average molecular weight (in terms of polystyrene) was 24 x 104. Furthermore, according to proton NMR analysis, the polyethylene oxide content in the graft copolymer was 38% by weight.
Met.
参考例５
冷却還流管を備えた２００ｍ１容量反応槽に参考例２に
て得たポリエチレンオキサイドマクロモノマー５０重量
部、アクリル酸ブチル５０重量部、トルエン１００重量
部及び２，２゛〜アゾビスイソフチロニ１−ツル０．５
重量部を仕込み、参考例３と同様にして、ポリアクリル
酸ブチル−ポリエチレンオキサイドグラフト共重合体を
得た。Reference Example 5 50 parts by weight of the polyethylene oxide macromonomer obtained in Reference Example 2, 50 parts by weight of butyl acrylate, 100 parts by weight of toluene, and 2,2゛ to azobisisobutylene were placed in a 200 ml reaction tank equipped with a cooling reflux tube. Roni 1-Tsuru 0.5
A polybutyl acrylate-polyethylene oxide graft copolymer was obtained in the same manner as in Reference Example 3.
このグラフト共重合体をＧＰＣ分析したところ、重量平
均分子量（ポリスチレン換算）は４８×１０４であった
。また、プロトンＮＭＲ分析によると、グラフト共重合
体におけるポリエチレンオキサイド含有率は４１重量％
であった。GPC analysis of this graft copolymer revealed that the weight average molecular weight (in terms of polystyrene) was 48 x 104. Furthermore, according to proton NMR analysis, the polyethylene oxide content in the graft copolymer was 41% by weight.
Met.
比較例１
特開昭５５−１４７１０６号公報の実施例１に従い、複
合半透膜を得た。これを比較例１とする。Comparative Example 1 A composite semipermeable membrane was obtained according to Example 1 of JP-A-55-147106. This is referred to as Comparative Example 1.
比較例２
特公昭６１−２７０８３号公報の実施例１に従い、複合
半透膜を得た。これを比較例２とする。Comparative Example 2 A composite semipermeable membrane was obtained according to Example 1 of Japanese Patent Publication No. 61-27083. This is referred to as Comparative Example 2.
実施例１
参考例３にて得たポリメタクリル酸メチル−ポリエチレ
ンオキサイドグラフト共重合体をシクロヘキサノンに溶
解して、１０重量％溶液とし、これをシリンジにて水面
に連続展開して、展開膜を調製した。Example 1 The polymethyl methacrylate-polyethylene oxide graft copolymer obtained in Reference Example 3 was dissolved in cyclohexanone to make a 10% by weight solution, and this was continuously spread on the water surface using a syringe to prepare a spread membrane. did.
この膜の空気側が表面になるように、比較例１の複合半
透膜上に積層して、本発明による複合半透膜を得た。展
開膜の厚さは１３００人であった。This membrane was laminated on the composite semipermeable membrane of Comparative Example 1 so that the air side was the surface, to obtain a composite semipermeable membrane according to the present invention. The thickness of the developed membrane was 1300.
実施例２
参考例４にて得たポリアクリル酸ブチル−ポリエチレン
オキサイドグラフト共重合体を用いて、実施例１と同様
にして、本発明による複合半透膜を得た。展開膜の厚さ
は６００人であった。Example 2 A composite semipermeable membrane according to the present invention was obtained in the same manner as in Example 1 using the polybutyl acrylate-polyethylene oxide graft copolymer obtained in Reference Example 4. The thickness of the developed membrane was 600 mm.
実施例３
参考例５にて得たポリアクリル酸ブチル−ポリエチレン
オキサイドグラフト共重合体を用いて、実施例１と同様
にして、本発明による複合半透膜を得た。展開膜の厚さ
は７００人であった。Example 3 Using the polybutyl acrylate-polyethylene oxide graft copolymer obtained in Reference Example 5, a composite semipermeable membrane according to the present invention was obtained in the same manner as in Example 1. The thickness of the developed membrane was 700 mm.
実施例４
実施例１において、比較例１の複合半透膜に代えて、比
較例２の複合半透膜を用いた以外は、実施例１と同様に
して、本発明による複合半透膜を得た。展開膜の厚さは
１３００人であった。Example 4 A composite semipermeable membrane according to the present invention was produced in the same manner as in Example 1, except that the composite semipermeable membrane of Comparative Example 2 was used in place of the composite semipermeable membrane of Comparative Example 1. Obtained. The thickness of the developed membrane was 1300.
実施例５
実施例２において、比較例１の複合半透膜に代えて、比
較例２の複合半透膜を用いた以外は、実施例１と同様に
して、本発明による複合半透膜を得た。展開膜の厚さは
６００人であった。Example 5 A composite semipermeable membrane according to the present invention was produced in the same manner as in Example 1, except that the composite semipermeable membrane of Comparative Example 2 was used in place of the composite semipermeable membrane of Comparative Example 1. Obtained. The thickness of the developed membrane was 600 mm.
実施例６
実施例３において、比較例１の複合半透膜に代えて、比
較例２の複合半透膜を用いた以外は、実施例１と同様に
して、本発明による複合半透膜を得た。展開膜の厚さは
７００人であった。Example 6 In Example 3, a composite semipermeable membrane according to the present invention was produced in the same manner as in Example 1, except that the composite semipermeable membrane of Comparative Example 2 was used in place of the composite semipermeable membrane of Comparative Example 1. Obtained. The thickness of the developed membrane was 700 mm.
以上のようにして得たそれぞれの複合半透膜について、
処理水として、塩化ナトリウム水溶液の１５００ｐｐｍ
水溶液をｐＨ６〜７、温度２５°Ｃ１圧力１５ｋｇ／ｃ
＋ｆｌの条件下に複合半透膜に接触させ、その塩阻止率
を測定して、逆浸透試験を行なった。Regarding each composite semipermeable membrane obtained as above,
As treated water, 1500 ppm of sodium chloride aqueous solution
Aqueous solution pH 6-7, temperature 25°C, pressure 15kg/c
A reverse osmosis test was conducted by contacting the membrane with a composite semipermeable membrane under +fl conditions and measuring its salt rejection rate.
結果を第１表に示す。ここに、透塩率は、次式で定義さ
れる。The results are shown in Table 1. Here, the salt permeability is defined by the following formula.
第
表
第１表に示す結果から明らかなように、実施例１〜３に
よる複合半透膜は、比較例１による複合半透膜に比べて
、また、実施例４〜６による複合半透膜は、比較例２に
よる複合半透膜に比べて、それぞれ塩阻止率が向上して
いる。As is clear from the results shown in Table 1, the composite semipermeable membranes according to Examples 1 to 3 were superior to the composite semipermeable membranes according to Comparative Example 1, and the composite semipermeable membranes according to Examples 4 to 6 Compared to the composite semipermeable membrane according to Comparative Example 2, the salt rejection rates are improved.
Claims (1)
に、側鎖としてポリエチレンオキサイドセグメントを有
し、幹部分が実質的に水不溶性の重合体からなるグラフ
ト共重合体からなる膜が積層されていることを特徴とす
る複合半透膜。(1) A graft copolymer that has a semipermeable ultra-thin film on a porous base material, further has a polyethylene oxide segment as a side chain, and the trunk portion is made of a substantially water-insoluble polymer. A composite semipermeable membrane characterized by laminated membranes consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21221090A JP2866981B2 (en) | 1990-08-10 | 1990-08-10 | Composite semipermeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21221090A JP2866981B2 (en) | 1990-08-10 | 1990-08-10 | Composite semipermeable membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0494725A true JPH0494725A (en) | 1992-03-26 |
| JP2866981B2 JP2866981B2 (en) | 1999-03-08 |
Family
ID=16618755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21221090A Expired - Fee Related JP2866981B2 (en) | 1990-08-10 | 1990-08-10 | Composite semipermeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2866981B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6280853B1 (en) * | 1999-06-10 | 2001-08-28 | The Dow Chemical Company | Composite membrane with polyalkylene oxide modified polyamide surface |
| JP2009535201A (en) * | 2006-04-28 | 2009-10-01 | ダウ グローバル テクノロジーズ インコーポレイティド | Reverse osmosis membrane with branched polyalkylene oxide modified anti-adhesive surface |
| CN104258747A (en) * | 2014-03-04 | 2015-01-07 | 上海大学 | Method for preparing nylon-66 grafted crylic acid by electronic beam pre-irradiation |
| WO2018057869A1 (en) * | 2016-09-26 | 2018-03-29 | Becton, Dickinson And Company | Breathable films with microbial barrier properties |
-
1990
- 1990-08-10 JP JP21221090A patent/JP2866981B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6280853B1 (en) * | 1999-06-10 | 2001-08-28 | The Dow Chemical Company | Composite membrane with polyalkylene oxide modified polyamide surface |
| JP2009535201A (en) * | 2006-04-28 | 2009-10-01 | ダウ グローバル テクノロジーズ インコーポレイティド | Reverse osmosis membrane with branched polyalkylene oxide modified anti-adhesive surface |
| US7918349B2 (en) | 2006-04-28 | 2011-04-05 | Dow Global Technologies Llc | Composite polyamide membrane with branched poly(alkylene oxide) modified surface |
| CN104258747A (en) * | 2014-03-04 | 2015-01-07 | 上海大学 | Method for preparing nylon-66 grafted crylic acid by electronic beam pre-irradiation |
| WO2018057869A1 (en) * | 2016-09-26 | 2018-03-29 | Becton, Dickinson And Company | Breathable films with microbial barrier properties |
| US11111362B2 (en) | 2016-09-26 | 2021-09-07 | Becton, Dickinson And Company | Breathable films with microbial barrier properties |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2866981B2 (en) | 1999-03-08 |
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