JPH052364B2 - - Google Patents
Info
- Publication number
- JPH052364B2 JPH052364B2 JP59111722A JP11172284A JPH052364B2 JP H052364 B2 JPH052364 B2 JP H052364B2 JP 59111722 A JP59111722 A JP 59111722A JP 11172284 A JP11172284 A JP 11172284A JP H052364 B2 JPH052364 B2 JP H052364B2
- Authority
- JP
- Japan
- Prior art keywords
- polysulfone copolymer
- membrane
- sulfonated polysulfone
- sulfonated
- semipermeable membrane
- 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
- 239000012528 membrane Substances 0.000 claims description 84
- 229920002492 poly(sulfone) Polymers 0.000 claims description 77
- 239000002904 solvent Substances 0.000 claims description 18
- -1 alkylene glycol monoalkyl ether Chemical class 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 239000000243 solution Substances 0.000 description 34
- 239000011521 glass Substances 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 238000000108 ultra-filtration Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000003495 polar organic solvent Substances 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明はポリスルホン複合半透膜及びその製造
方法に関し、詳しくは、スルホン化された水不溶
性ポリスルホン共重合体の均質膜からなる半透膜
及びその製造方法に関する。
式Ａ
と、式Ｂ
とを繰返し単位として有する線状ポリスルホン共
重合体は、既にカナダ特許第847963号明細書に記
載されており、また、この共重合体のスルホン化
物も既に特開昭55−57222号公報に記載されてい
る。即ち、この公報には、上記ポリスルホン共重
合体を濃硫酸に溶解させてスルホン化することに
よつて、式Ａの繰返し単位は実質的にすべてスル
ホン化されているが、式Ｂの繰返し単位は実質的
にすべてが非スルホン化状態で残存している親水
性のスルホン化ポリスルホンが生成することが記
載されている。更に、このスルホン化ポリスルホ
ン共重合体が限外濾過膜として潜在的に有用であ
ることも言及されている。
また、繰返し単位が式Ｃ
からなるポリスルホンのスルホン化物は、米国特
許第3709841号明細書に記載されており、特開昭
50−99973号公報及び特開昭５−146379号公報に
は、このようなスルホン化ポリスルホンの溶液を
異方性限外濾過膜の表面の緻密層上に塗布し、溶
剤を蒸発させることにより、半透性を有する薄膜
が限外濾過膜上をに積層されてなる逆浸透用の複
合半透膜を製造する方法が記載されている。同様
に、Office of Water Research and
Tehnology Department of the Interior、
Report No.2001−20には、前記式Ｃの繰返し単
位からなる異方性限外濾過膜を予め乳酸水溶液に
て目詰めし、この限外濾過膜上に同じく前記式Ｃ
の繰返し単位からなるポリスルホンのスルホン化
物の溶液を塗布し、溶剤を蒸発させて、複合半透
膜を得る方法が記載されている。
しかしながら、本発明者らは、前記式Ａ及び式
Ｂよりなる線状ポリスルホン共重合体をスルホン
化してなるスルホン化ポリスルホン共重合体は、
上記した複合半透膜に比べて、一層すぐれた物性
及び性能を有し、特に、好ましい場合には、塩水
の処理において、99％以上の高い塩化ナトリウム
除去率を有すると共に、耐塩素性、耐PH性、耐熱
性及び耐圧密化性にすぐれた逆浸透膜を得ること
ができることを見出して、本発明に至つたもので
ある。
従つて、本発明は、スルホン化ポリスルホン共
重合体からなる半透膜を提供することを目的と
し、更に、かかる半透膜を用いる水性液の処理方
法を提供することを目的とする。
本発明によるスルホン化ポリスルホン半透膜
は、繰返し単位Ａ
及び繰返し単位Ｂ
よりなる線状ポリスルホン共重合体をスルホン化
してなり、Ｎ−メチル−２−ピロリドン100mlに
重合体0.5ｇを溶解した溶液について、30℃の温
度において測定した対数粘度が0.5cm3／ｇ以上で
あり、且つ、イオン交換容量が２ミリ当量／ｇ以
下である水不溶性のスルホン化ポリスルホン共重
合体からなることを特徴とする。
また、かかる半透膜は、本発明に従つて、上記
のようなスルホン化ポリスルホン共重合体を、少
量の非プロトン性極性有機溶剤を含んでいてもよ
いアルキレングリコールモノアルキルエーテルに
溶解して製膜溶液とし、これを適宜の基材上に塗
布し、溶剤を蒸発させることによつて製造され
る。
本発明において用いるスルホン化ポリスルホン
共重合体は、前記したポリスルホン共重合体を濃
硫酸に溶解させ、常温にて数時間撹拌することに
よつて、容易に得ることができる。スルホン化の
程度は、前記したように、式Ａの繰返し単位は実
質的にすべてスルホン化されるが、式Ｂの繰返し
単位は実質的にすべてが非スルホン化状態で残存
するので、式Ａと式Ｂとの繰返し単位の比率を変
えた共重合体を用いることによつて、容易に制御
することができる。また、スルホン化条件を制御
することによつて、式Ａの繰返し単位のスルホン
化自体をも制御することができる。
本発明においては、かかるスルホン化ポリスル
ホン共重合体は、乾燥樹脂１ｇについて、イオン
交換容量が２ミリ当量／ｇ以下であり、且つ、Ｎ
−メチル−２−ピロリドン100mlにこの共重合体
0.5ｇを溶解した溶液について、30℃において測
定した対数粘度（以下、スルホン化ポリスルホン
の対数粘度の測定方法は同じである。）が0.5cm3／
ｇ以上、好ましくは0.7cm3／ｇ以上であることが
必要である。イオン交換容量が２ミリ当量／ｇを
越えるときは、スルホン化ポリスルホンが水溶性
を有するに至り、水性媒体を含む液体を処理する
ことが多い半透膜として不適当であり、また、対
数粘度が0.5cm3／ｇよりも小さいときは、ピンホ
ール等の欠陥のない均一な薄膜に製造することが
困難であるからである。
本発明において用いるスルホン化ポリスルホン
共重合体が有するスルホン酸基は、式−SO3Mで
表わされ、ここに、Ｍは水素、アルカリ金属又は
テトラアルキルアンモニウムを示す。例えば、ポ
リスルホン共重合体をスルホン化した後、このス
ルホン化ポリスルホン共重合体を水洗し、乾燥す
れば、遊離のスルホン酸基を有するスルホン化ポ
リスルホン共重合体を得ることができる。また、
このスルホン化ポリスルホン共重合体を水酸化ア
ルカリ金属又はアルカリ金属アルコラートの水溶
液やメタノール、エタノール溶液等にて処理すれ
ば、スルボン酸基をアルカリ金属塩とすることが
できる。水酸化アルカリ金属としては、例えば、
水酸化ナトリウム、水酸化カリウム、水酸化リチ
ウム等が、また、アルカリ金属アルコラートとし
ては、例えば、ナトリウムメチラート、カリウム
メチラート、カリウムエチラート等が用いられ
る。また、テトラアルキルアンモニウム、例え
ば、水酸化テトラメチルアンモニウム、水酸化テ
トラエチルアンモニウム、水酸化テトラプロピル
アンモニウム、水酸化テトラブチルアンモニウム
等の上記と同様の溶液で処理すれば、対応するテ
トラアルキルアンモニウム塩とすることができ
る。
本発明による半透膜は、種々の方法にて製造す
ることができるが、通常、前記スルホン化ポリス
ルホンを有機溶剤に溶解して製膜溶液とし、これ
を適宜の支持基材上に塗布し、溶剤を蒸発させる
ことによつて製造することができる。
製膜溶液を調製するための有機溶剤としては、
ジメチルスルホキシド、Ｎ−メチル−２−ピロリ
ドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−
ジメチルアセトアミド等の非プロトン性極性有機
溶剤や、エチレングリコールモノメチルエーテ
ル、エチレングリコールモノエチルエーテル、プ
ロピレングリコールモノメチルエーテル、プロピ
レングリコールモノエチルエーテル等のアルキレ
ン基の炭素数が２又は３であり、アルキル基の炭
素数が１〜４であるアルキレングリコールモノア
ルキルエーテルを挙げることができる。尚、用い
るスルホン化ポリスルホン共重合体によつては、
上記アルキレングリコールモノエーテルに溶解し
ないか、又は膨潤のみする場合もあるが、このよ
うなスルホン化ポリスルホン共重合体も、アルキ
レングリコールモノエーテルに少量の上記非プロ
トン性極性有機溶剤を添加してなる混合溶剤には
よく溶解する。
製膜溶液の溶剤として、アルキレングリコール
モノアルキルエーテル又はこれと少量の前記非プ
ロトン性極性有機溶剤との混合溶剤を用いること
は、後述する溶剤の蒸発除去において、常温乃至
僅かの加熱によつて溶剤を除去することができ、
且つ、欠陥のない均一な薄膜を得ることができる
ので有利である。
製膜溶液におけるスルホン化ポリスルホン共重
合体濃度は、得られる半透膜の膜厚にも関係する
が、通常、0.01〜15重量％の範囲が好ましく、特
に、0.1〜10重量％の範囲が好ましい。
製膜溶液を塗布するための基材は特に制限され
ないが、例えば、ガラス、ステンレス鋼、アルミ
ニウム、ポリエチレン樹脂、ポリプロピレン樹脂
等からなる平滑な面を有するものが好ましく用い
られる。溶剤を蒸発させるために、必要に応じて
加熱してもよい。加熱温度は用いた溶剤に応じて
適宜に選べない。尚、製膜溶液を基材上に塗布後
の溶剤の蒸発を促進するために、製膜溶液を予め
加熱しておいてもよい。
次いで、支持基材上に塗布した製膜溶液から溶
剤を蒸発除去させることによつて、本発明による
半透膜を得ることができる。溶剤を蒸発除去した
後、支持基材を水中に浸漬すれば、膜を容易に支
持基材から剥離することができる。
得られる半透膜の膜厚は、製膜溶液におけるス
ルホン化ポリスルホン共重合体濃度や、支持基材
への製膜溶液の塗布厚みにもよるが、膜の透水速
度を高くするには薄いほうがよく、強度の高める
ためには厚いほうがよい。従つて、特に、制限さ
れるものではないが、通常、膜厚は0.05〜5μｍの
範囲である。
このようにして得られる本発明による半透膜は
異方性をもたず、厚み方向に均質な膜であつて、
且つ、耐塩素性、耐PH性、耐熱性等にすぐれ、逆
浸透膜として使用するのに好適であり、更に、本
発明による半透膜は、長期間にわたる連続使用に
よつても圧密化することなく、当初の高い透水速
度を維持する。
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。尚、実施例において、得られた半透膜の
溶質除去率及び透水速度の測定は、濃度5000ppm
の塩化ナトリウム水溶液を原液として、温度25
℃、圧力50Kg／cm2で透過実験を行ない、それぞれ
次式により求めた。
除去率＝（１−膜透過液中の溶質濃度／膜供給液中の溶
質濃度）×100（％）
透水速度＝透過水量（m2）／有効膜面積（m2）×透過時
間（日）
実施例 １
(1) ポリスルホン共重合体の製造
特公昭46−21458号に記載されている方法に
従つて、式A1
の繰返し単位57モル％と、式Ｂの繰返し単位43
モル％とからなる線状ポリスルホン共重合体を
製造した。
即ち、４，4′−ジヒドロキシジフエニルスル
ホン15.0ｇ（0.06モル）及びヒドロキノン8.8ｇ
（0.08モル）を撹拌器、窒素ガス導入管、水抜
き管及び温度計を備えたフラスコに入れ、これ
にスルホラン200mlとキシレン100mlを加えた。
マントルヒーターによる加熱下に撹拌しなが
ら、155℃で１時間還流を行ない、この際、水
5.6mlを抜き出した。
次いで、温度を110℃まで下げ、４，4′−ジ
クロルジフエニルスルホン40.2ｇ（0.14モル）
と炭酸カリウム27.6ｇ（0.20モル）を加えて重
合反応を開始した。162℃で１時間還流した後、
2.5時間の間に水を抜きながら、200℃まで昇温
し、更に、200〜215℃で４時間還流を続けた。
この反応の間に抜き出された水量は2.0mlであ
つた。
反応液の一部をガラス板に塗布し、水中に浸
漬したとき、フイルムを形成し得ることを確認
した後、100℃まで温度を下げ、ジクロルメタ
ン20mlを加えた。このようにして得た反応混合
物を純水中に投じて、ポリスルホン共重合体を
凝固させ、純水、次にアセトンで洗浄した後、
80℃で6.5時間乾燥した。
このようにして得られたポリスルホン共重合
体（収率100％）は、淡黄色粒状物であつて、
この共重合体をＮ−メチル−２−ピロニドン
100mlに溶解した溶液として30℃で測定した対
数粘度（以下、ポリスルホン共重合体の対数粘
度の測定条件は同じである。）は0.84cm3／ｇで
あつた。
(2) スルホン化ポリスルホン共重合体の製造
上記のようにして得たポリスルホン共重合体
10ｇを97％濃硫酸80mlに加えて溶解させ、常温
にて４時間撹拌反応させて、黒褐色の粘稠な反
応液を得た。これを氷浴中に投入して、スルホ
ン化ポリスルホン共重合体を凝固させた。水に
て洗浄後、0.5N水酸化ナトリウム水溶液800ml
中に一晩放置した。次いで、洗浄液が中性にな
るまでこの重合体を洗浄した後、60℃で５時間
真空乾燥した。
このようにして得られた淡黄色粒状のスルホ
ン化ポリスルホン共重合体は、対数粘度が0.84
cm3／ｇ、イオン交換容量は1.23ミリ当量／ｇで
あつた。
(3) 半透膜の製造
上記のようにして得たスルホン化ポリスルホ
ン共重合体８ｇをＮ，Ｎ−ジメチルホルムアミ
ド110ｇに溶解し、孔径10μｍの濾紙を用いて
異物を除いて、均一な製膜溶液を調製した。60
℃に加熱したガラス板上にこの製膜溶液を55μ
ｍのギヤツプにて流延塗布し、熱風乾燥器にて
ガラス板上の塗布膜に熱風を送風して溶剤を蒸
発させ、除去した。ガラス板を水中に浸漬し
て、膜をガラス板より剥離し、支持膜としての
ポリスルホン限外濾過膜にすくい上げた。半透
膜の膜厚は0.3μｍであつた。
この半透膜の表面に濃度50ppmのオレンジ
水溶液を塗布し、ポリスルホン限外濾過膜が着
色されないことから、半透膜にピンホール等の
欠陥のないことが確認された。
(4) 膜特性の評価
上記のように水中でガラス板から剥離したス
ルホン化ポリスルホン半透膜をポリスルホン限
外濾過膜にすくいあげ、前記の条件にて透過実
験を行なつた。結果を第１表に示す。
実施例 ２
実施例１と同様にして、繰返し単位A1と繰返
し単位Ｂとの組成比率が種々異なる線状ポリスル
ホン共重合体を調製し、スルホン化し、半透膜を
得た。このようにして得た半透膜の膜性能を第１
表に示す。
実施例 ３
実施例１で得た部分スルホン化ポリスルホン
0.1ｇをエチレングリコールモノメチルエーテル
10ｇに溶解し、10μｍの濾紙を用いて異物を除い
て、製膜溶液を調製した。これを25℃の温度で
55μｍのギヤツプにてガラス板上に流延塗布し、
30分間放置し、更に、60℃で30分間加熱して溶剤
を除去した。次いで、ガラス板を水中に浸漬し
て、膜をガラス板より剥離した。この膜の膜厚は
0.2μｍであつた。
この膜の性能は、除去率99.3％、透水速度0.9
m3／m2・日であつた。
実施例 ４
The present invention relates to a polysulfone composite semipermeable membrane and a method for producing the same, and more particularly to a semipermeable membrane comprising a homogeneous membrane of a sulfonated water-insoluble polysulfone copolymer and a method for producing the same. Formula A and formula B A linear polysulfone copolymer having as a repeating unit has already been described in Canadian Patent No. 847963, and a sulfonated product of this copolymer has also been described in JP-A-55-57222. ing. That is, in this publication, substantially all of the repeating units of formula A are sulfonated by dissolving the polysulfone copolymer in concentrated sulfuric acid and sulfonation, but the repeating units of formula B are sulfonated. It is described that hydrophilic sulfonated polysulfones are produced which remain essentially all in the non-sulfonated state. Additionally, it is mentioned that this sulfonated polysulfone copolymer is potentially useful as an ultrafiltration membrane. Also, the repeating unit is the formula C A sulfonated product of polysulfone consisting of is described in U.S. Pat.
50-99973 and JP-A-5-146379 disclose that by applying a solution of such sulfonated polysulfone onto a dense layer on the surface of an anisotropic ultrafiltration membrane and evaporating the solvent, A method for producing a composite semipermeable membrane for reverse osmosis in which a semipermeable thin membrane is laminated on an ultrafiltration membrane is described. Similarly, the Office of Water Research and
Technology Department of the Interior;
In Report No. 2001-20, an anisotropic ultrafiltration membrane consisting of repeating units of the above formula C was packed in advance with an aqueous lactic acid solution, and a repeating unit of the above formula C was packed in advance with a lactic acid aqueous solution.
A method is described in which a composite semipermeable membrane is obtained by applying a solution of a sulfonated polysulfone consisting of repeating units of and evaporating the solvent. However, the present inventors have discovered that a sulfonated polysulfone copolymer obtained by sulfonating a linear polysulfone copolymer consisting of formulas A and B is
It has better physical properties and performance than the above-mentioned composite semipermeable membranes, and in particular, in preferable cases, it has a high sodium chloride removal rate of 99% or more in salt water treatment, as well as chlorine resistance and The present invention was achieved by discovering that it is possible to obtain a reverse osmosis membrane with excellent PH properties, heat resistance, and compaction resistance. Therefore, the present invention aims to provide a semipermeable membrane made of a sulfonated polysulfone copolymer, and further aims to provide a method for treating an aqueous liquid using such a semipermeable membrane. The sulfonated polysulfone semipermeable membrane according to the present invention has repeating units A and repeating unit B A linear polysulfone copolymer made of It is characterized by being made of a water-insoluble sulfonated polysulfone copolymer having an ion exchange capacity of 2 milliequivalents/g or less. Further, according to the present invention, such a semipermeable membrane is prepared by dissolving a sulfonated polysulfone copolymer as described above in an alkylene glycol monoalkyl ether which may contain a small amount of an aprotic polar organic solvent. It is produced by forming a membrane solution, applying it onto a suitable substrate, and evaporating the solvent. The sulfonated polysulfone copolymer used in the present invention can be easily obtained by dissolving the polysulfone copolymer described above in concentrated sulfuric acid and stirring at room temperature for several hours. Regarding the degree of sulfonation, as described above, substantially all of the repeating units of formula A are sulfonated, but substantially all of the repeating units of formula B remain in a non-sulfonated state. This can be easily controlled by using copolymers with varying ratios of repeating units with Formula B. Moreover, by controlling the sulfonation conditions, the sulfonation itself of the repeating unit of formula A can also be controlled. In the present invention, such a sulfonated polysulfone copolymer has an ion exchange capacity of 2 meq/g or less per 1 g of dry resin, and N
-Add this copolymer to 100ml of methyl-2-pyrrolidone.
The logarithmic viscosity (hereinafter, the method for measuring the logarithmic viscosity of sulfonated polysulfone is the same) measured at 30°C for a solution containing 0.5 g of sulfonated polysulfone is 0.5 cm 3 /
g or more, preferably 0.7 cm 3 /g or more. When the ion exchange capacity exceeds 2 milliequivalents/g, the sulfonated polysulfone becomes water-soluble and is unsuitable as a semipermeable membrane that often treats liquids containing aqueous media, and the logarithmic viscosity is This is because when it is smaller than 0.5 cm 3 /g, it is difficult to produce a uniform thin film without defects such as pinholes. The sulfonic acid group possessed by the sulfonated polysulfone copolymer used in the present invention is represented by the formula -SO3M , where M represents hydrogen, an alkali metal, or a tetraalkylammonium. For example, by sulfonating a polysulfone copolymer, washing the sulfonated polysulfone copolymer with water, and drying it, a sulfonated polysulfone copolymer having free sulfonic acid groups can be obtained. Also,
By treating this sulfonated polysulfone copolymer with an aqueous solution of an alkali metal hydroxide or alkali metal alcoholate, methanol, ethanol solution, etc., the sulfonic acid group can be converted into an alkali metal salt. As the alkali metal hydroxide, for example,
Sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are used, and as the alkali metal alcoholate, for example, sodium methylate, potassium methylate, potassium ethylate, etc. are used. In addition, if a tetraalkylammonium, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc. is treated with the same solution as above, the corresponding tetraalkylammonium salt can be obtained. be able to. The semipermeable membrane according to the present invention can be produced by various methods, but usually, the sulfonated polysulfone is dissolved in an organic solvent to prepare a membrane-forming solution, and this is coated on an appropriate support substrate. It can be produced by evaporating the solvent. Organic solvents for preparing film forming solutions include:
Dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-
Aprotic polar organic solvents such as dimethylacetamide, and alkylene groups such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether have 2 or 3 carbon atoms; Alkylene glycol monoalkyl ethers having 1 to 4 carbon atoms can be mentioned. Depending on the sulfonated polysulfone copolymer used,
Although there are cases where the sulfonated polysulfone copolymer does not dissolve in the above alkylene glycol monoether or only swells, it is possible to prepare a mixture made by adding a small amount of the above aprotic polar organic solvent to the alkylene glycol monoether. It dissolves well in solvents. When alkylene glycol monoalkyl ether or a mixed solvent of alkylene glycol monoalkyl ether and a small amount of the aprotic polar organic solvent is used as the solvent for the membrane forming solution, the solvent can be removed by evaporation at room temperature or by slight heating. can be removed,
Moreover, it is advantageous because a uniform thin film without defects can be obtained. The concentration of the sulfonated polysulfone copolymer in the membrane forming solution is also related to the thickness of the semipermeable membrane obtained, but it is usually preferably in the range of 0.01 to 15% by weight, particularly preferably in the range of 0.1 to 10% by weight. . The substrate for applying the film-forming solution is not particularly limited, but for example, those having a smooth surface made of glass, stainless steel, aluminum, polyethylene resin, polypropylene resin, etc. are preferably used. Heating may be applied if necessary to evaporate the solvent. The heating temperature cannot be selected appropriately depending on the solvent used. Incidentally, in order to promote evaporation of the solvent after coating the film-forming solution on the substrate, the film-forming solution may be heated in advance. The semipermeable membrane according to the present invention can then be obtained by evaporating the solvent from the membrane forming solution applied onto the support substrate. After the solvent is removed by evaporation, the membrane can be easily peeled off from the supporting substrate by immersing the supporting substrate in water. The thickness of the resulting semipermeable membrane depends on the concentration of the sulfonated polysulfone copolymer in the membrane-forming solution and the thickness of the coating of the membrane-forming solution on the supporting substrate, but the thinner the membrane is, the higher the water permeation rate. Generally speaking, the thicker the better for greater strength. Therefore, although not particularly limited, the film thickness is usually in the range of 0.05 to 5 μm. The semipermeable membrane of the present invention thus obtained has no anisotropy and is homogeneous in the thickness direction,
Moreover, it has excellent chlorine resistance, PH resistance, heat resistance, etc., and is suitable for use as a reverse osmosis membrane.Furthermore, the semipermeable membrane according to the present invention is compacted even when used continuously for a long period of time. The initial high water permeability rate is maintained without any problems. The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the examples, the solute removal rate and water permeation rate of the obtained semipermeable membrane were measured at a concentration of 5000 ppm.
of sodium chloride aqueous solution as a stock solution at a temperature of 25
A permeation experiment was carried out at a temperature of 50 kg/cm 2 at a temperature of 50 kg/cm 2 and the values were calculated using the following formulas. Removal rate = (1 - solute concentration in membrane permeate / solute concentration in membrane feed solution) x 100 (%) Water permeation rate = permeated water amount (m 2 ) / effective membrane area (m 2 ) x permeation time (days) Example 1 (1) Production of polysulfone copolymer According to the method described in Japanese Patent Publication No. 46-21458, formula A 1 57 mol% of repeating units of formula B and 43 mol% of repeating units of formula B
A linear polysulfone copolymer consisting of mol %. i.e. 15.0 g (0.06 mol) of 4,4'-dihydroxydiphenyl sulfone and 8.8 g of hydroquinone.
(0.08 mol) was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a water drain tube, and a thermometer, and 200 ml of sulfolane and 100 ml of xylene were added thereto.
Reflux was carried out at 155℃ for 1 hour while stirring and heating with a mantle heater.
5.6 ml was extracted. Then, the temperature was lowered to 110°C, and 40.2 g (0.14 mol) of 4,4'-dichlorodiphenyl sulfone was added.
and 27.6 g (0.20 mol) of potassium carbonate were added to start the polymerization reaction. After refluxing at 162°C for 1 hour,
The temperature was raised to 200°C while water was removed over a period of 2.5 hours, and reflux was continued at 200 to 215°C for 4 hours.
The amount of water drawn off during this reaction was 2.0 ml. After confirming that a film could be formed when a portion of the reaction solution was applied to a glass plate and immersed in water, the temperature was lowered to 100°C and 20 ml of dichloromethane was added. The reaction mixture thus obtained was poured into pure water to coagulate the polysulfone copolymer, and after washing with pure water and then with acetone,
It was dried at 80°C for 6.5 hours. The polysulfone copolymer thus obtained (yield 100%) was pale yellow granular,
This copolymer was converted into N-methyl-2-pyronidone.
The logarithmic viscosity measured as a solution dissolved in 100 ml at 30°C (hereinafter, the measurement conditions for the logarithmic viscosity of the polysulfone copolymer are the same) was 0.84 cm 3 /g. (2) Production of sulfonated polysulfone copolymer Polysulfone copolymer obtained as above
10 g was added and dissolved in 80 ml of 97% concentrated sulfuric acid, and stirred and reacted at room temperature for 4 hours to obtain a dark brown viscous reaction liquid. This was placed in an ice bath to solidify the sulfonated polysulfone copolymer. After washing with water, 800ml of 0.5N sodium hydroxide aqueous solution
I left it inside overnight. Next, the polymer was washed until the washing solution became neutral, and then vacuum-dried at 60°C for 5 hours. The light yellow granular sulfonated polysulfone copolymer thus obtained has a logarithmic viscosity of 0.84.
cm 3 /g, and the ion exchange capacity was 1.23 meq/g. (3) Production of semipermeable membrane 8 g of the sulfonated polysulfone copolymer obtained as above was dissolved in 110 g of N,N-dimethylformamide, foreign matter was removed using a filter paper with a pore size of 10 μm, and a uniform membrane was formed. A solution was prepared. 60
Pour 55μ of this film-forming solution onto a glass plate heated to ℃.
The solution was cast and coated with a gap of m, and the solvent was evaporated and removed by blowing hot air onto the coating film on the glass plate using a hot air dryer. The glass plate was immersed in water, and the membrane was peeled off from the glass plate and scooped onto a polysulfone ultrafiltration membrane as a support membrane. The thickness of the semipermeable membrane was 0.3 μm. An orange aqueous solution with a concentration of 50 ppm was applied to the surface of this semipermeable membrane, and since the polysulfone ultrafiltration membrane was not colored, it was confirmed that the semipermeable membrane had no defects such as pinholes. (4) Evaluation of membrane properties The sulfonated polysulfone semipermeable membrane peeled from the glass plate in water as described above was scooped onto a polysulfone ultrafiltration membrane, and a permeation experiment was conducted under the conditions described above. The results are shown in Table 1. Example 2 In the same manner as in Example 1, linear polysulfone copolymers having various composition ratios of repeating unit A 1 and repeating unit B were prepared and sulfonated to obtain semipermeable membranes. The membrane performance of the semipermeable membrane obtained in this way was evaluated as
Shown in the table. Example 3 Partially sulfonated polysulfone obtained in Example 1
0.1g ethylene glycol monomethyl ether
A membrane forming solution was prepared by dissolving the mixture in 10 g and removing foreign matter using a 10 μm filter paper. This at a temperature of 25℃
Cast coating onto a glass plate with a gap of 55μm,
The mixture was left to stand for 30 minutes, and then heated at 60°C for 30 minutes to remove the solvent. Next, the glass plate was immersed in water to peel off the film from the glass plate. The thickness of this film is
It was 0.2 μm. The performance of this membrane is 99.3% removal rate and 0.9 water permeation rate.
The temperature was m 3 /m 2 ·day. Example 4
【表】
＊ スルホン化ポリスルホンの対数粘度
実施例２で得た17モル％の繰返し単位A1と83
モル％の繰返し単位Ｂからなるポリスルホン共重
合体のスルホン化物0.1ｇをエチレングリコール
モノメチルエーテル10ｇとＮ，Ｎ−ジメチルホル
ムアミド0.1ｇとの溶剤に溶解し、10μｍの濾紙を
用いて異物を除いて、製膜溶液を調製した。これ
を25℃の温度で55μｍのギヤツプにてガラス板上
に流延塗布し、30分間放置し、更に、80℃で１時
間加熱して溶剤を除去した。次いで、ガラス板を
水中に浸漬して、膜をガラス板より剥離した。こ
の膜の膜厚は0.2μｍであつた。
この膜の性能は、除去率99.8％、透水速度0.15
m3／m2・日であつた。
実施例 ５
実施例１において、ポリスルホン共重合体をス
ルホン化し、反応液を氷浴中に投入して、スルホ
ン化ポリスルホン共重合体を凝固させ、水にて洗
浄後、0.5N水酸化ナトリウム水溶液で処理する
ことなく、そのまま60℃で６時間乾燥した。
このスルホン化ポリスルホン共重合体0.1ｇを
エチレングリコールモノメチルエーテル10ｇに溶
解し、孔径10μｍの濾紙を用いて異物を除いて、
製膜溶液を調製した。
25℃の温度において、この製膜溶液をガラス板
上に55μｍのギヤツプにて流延塗布し、雰囲気温
度に約30分間放置して溶剤を蒸発除去した。ガラ
ス板を水中に浸漬して、膜をガラス板から剥離し
た。この膜の膜厚は0.4μｍ、性能は除去率98.5
％、透水速度1.1m3／m2・日であつた。
比較例
式Ｃの繰返し単位を有するポリスルホン（ICI
社製Ｐ−1700）をNoshayらの方法（J.Applied
Polymer Sci.、20、1885（1976））に従つてスル
ホン化した。
即ち、上記ポリスルホン60ｇを１，２−ジクロ
ルエタン300mlに溶解して、ポリスルホン溶液を
調製した。別に、活栓付き200ml三角フラスコに
リン酸トリエチル11.5ml（0.07モル）と１，２−
ジクロロエタン83mlを入れ、氷浴による冷却下、
撹拌しながら、これに三酸化イオウ６ml（0.16モ
ル）を加えて、三酸化イオウ溶液を調製した。
撹拌機、二つの滴下ろうと及び塩化カルシウム
管を備えたフラスコに１，２−ジクロルエタン
120mlを入れ、撹拌しながら、一方の滴下ろうと
から上記ポリスルホン溶液を、他方の滴下ろうと
から上記三酸化イオウ溶液を１時間を要して上記
フラスコ内に滴下し、更に、室温にて２時間撹拌
を続けた。この後、イソプロピルアルコール、次
に純水で洗浄した後、90℃で13時間乾燥した。
このようにして得られたスルホン化ポリスルホ
ン共重合体（収率75％）は、対数粘度0.91cm3／
ｇ、イオン交換容量1.0ミリ当量／ｇであつた。
このスルホン化ポリスルホンを用いて、実施例
１と同様にして、厚み0.3μｍの半透膜を調製し
た。この膜の性能は、除去率98.2％、透水速度
0.6m3／m2・日であつた。
実施例 ６
実施例１において、ヒドロキノンの代わりにレ
ゾルシノールを用いた以外は、実施例１と同様に
して、式A2
なる繰返し単位43モル％と、式Ｂの繰返し単位57
モル％からなるポリスルホン共重合体を調製し、
実施例１と同様にしてこれをスルホン化して、対
数粘度1.0cm3／ｇ、イオン交換容量1.03ミリ当
量／ｇのスルホン化ポリスルホン共重合体を得
た。
このスルホン化ポリスルホン共重合体を用い
て、実施例１と同様にして厚み0.2μｍの半透膜を
調製した。膜性能は、除去率99.3％、透水速度
0.8m3／m2・日であつた。
実施例 ７
実施例１において、ヒドロキノンの代わりにカ
テコールを用いた以外は、実施例１と同様にし
て、式A3
なる繰返し単位57モル％と、式Ｂの繰返し単位43
モル％からなるポリスルホン共重合体を調製し、
実施例１と同様にしてこれをスルホン化して、対
数粘度0.9cm3／ｇ、イオン交換容量1.32ミリ当
量／ｇのスルホン化ポリスルホン共重合体を得
た。
このスルホン化ポリスルホン共重合体を用い
て、実施例１と同様にして厚み0.3μｍの半透膜を
調製した。膜性能は、除去率98.4％、透水速度
1.4m3／m2・日であつた。
実施例 ８[Table] * Logarithmic viscosity of sulfonated polysulfone 17 mol% repeating unit A 1 and 83 obtained in Example 2
Dissolve 0.1 g of a sulfonated polysulfone copolymer consisting of mol% of repeating units B in a solvent of 10 g of ethylene glycol monomethyl ether and 0.1 g of N,N-dimethylformamide, and remove foreign substances using a 10 μm filter paper. A film forming solution was prepared. This was cast onto a glass plate at a temperature of 25° C. with a gap of 55 μm, left for 30 minutes, and further heated at 80° C. for 1 hour to remove the solvent. Next, the glass plate was immersed in water to peel off the film from the glass plate. The thickness of this film was 0.2 μm. The performance of this membrane is 99.8% removal rate and 0.15 water permeation rate.
The temperature was m 3 /m 2 ·day. Example 5 In Example 1, the polysulfone copolymer was sulfonated, the reaction solution was put into an ice bath, the sulfonated polysulfone copolymer was solidified, and after washing with water, it was washed with 0.5N aqueous sodium hydroxide solution. It was dried as it was at 60°C for 6 hours without any treatment. 0.1 g of this sulfonated polysulfone copolymer was dissolved in 10 g of ethylene glycol monomethyl ether, and foreign matter was removed using a filter paper with a pore size of 10 μm.
A film forming solution was prepared. This film-forming solution was cast onto a glass plate with a gap of 55 μm at a temperature of 25° C., and left at ambient temperature for about 30 minutes to evaporate the solvent. The membrane was peeled off from the glass plate by immersing it in water. The film thickness of this film is 0.4 μm, and the removal rate is 98.5.
%, and the water permeability rate was 1.1 m 3 /m 2 ·day. Comparative Example: Polysulfone (ICI) having a repeating unit of formula C
P-1700) manufactured by Noshay et al. (J.Applied).
Polymer Sci., 20 , 1885 (1976)). That is, 60 g of the above polysulfone was dissolved in 300 ml of 1,2-dichloroethane to prepare a polysulfone solution. Separately, in a 200 ml Erlenmeyer flask with a stopcock, add 11.5 ml (0.07 mol) of triethyl phosphate and 1,2-
Add 83 ml of dichloroethane and cool in an ice bath.
While stirring, 6 ml (0.16 mol) of sulfur trioxide was added thereto to prepare a sulfur trioxide solution. 1,2-dichloroethane in a flask equipped with a stirrer, two addition funnels, and a calcium chloride tube.
Add 120 ml of the flask, and while stirring, drop the polysulfone solution from one dropping funnel and the sulfur trioxide solution from the other dropping funnel into the flask over 1 hour, and stir at room temperature for 2 hours. continued. Thereafter, it was washed with isopropyl alcohol and then with pure water, and then dried at 90°C for 13 hours. The sulfonated polysulfone copolymer thus obtained (yield 75%) has a logarithmic viscosity of 0.91 cm 3 /
g, and the ion exchange capacity was 1.0 meq/g. Using this sulfonated polysulfone, a semipermeable membrane with a thickness of 0.3 μm was prepared in the same manner as in Example 1. The performance of this membrane is 98.2% removal rate and water permeation rate.
The temperature was 0.6m 3 /m 2 ·day. Example 6 In the same manner as in Example 1, except that resorcinol was used instead of hydroquinone, formula A 2 43 mol% of repeating units of formula B and 57 mol% of repeating units of formula B
Prepare a polysulfone copolymer consisting of mol%
This was sulfonated in the same manner as in Example 1 to obtain a sulfonated polysulfone copolymer having a logarithmic viscosity of 1.0 cm 3 /g and an ion exchange capacity of 1.03 meq/g. Using this sulfonated polysulfone copolymer, a semipermeable membrane having a thickness of 0.2 μm was prepared in the same manner as in Example 1. Membrane performance: removal rate 99.3%, water permeation rate
It was 0.8m 3 /m 2 ·day. Example 7 Formula A 3 was prepared in the same manner as in Example 1 except that catechol was used instead of hydroquinone . 57 mol% of repeating units of formula B and 43 mol% of repeating units of formula B
Prepare a polysulfone copolymer consisting of mol%
This was sulfonated in the same manner as in Example 1 to obtain a sulfonated polysulfone copolymer having a logarithmic viscosity of 0.9 cm 3 /g and an ion exchange capacity of 1.32 meq/g. Using this sulfonated polysulfone copolymer, a semipermeable membrane with a thickness of 0.3 μm was prepared in the same manner as in Example 1. Membrane performance: removal rate 98.4%, water permeation rate
It was 1.4m 3 /m 2 ·day. Example 8
【表】
（耐圧密化性）
実施例１において得た半透膜について、実施例
１と同じ条件にて塩化ナトリウム水溶液の透過実
験を連続して行ない、膜性能の経時変化を測定し
た。結果を第２表に示すように、膜性能は経時的
に変化せず、膜は圧密化は起こらなかつた。
（耐熱性の評価）
実施例１において得た半透膜を95℃の熱水中に
30分間浸漬し、除去率及び透水速度を測定した。
更に、このように熱水を30分間浸漬する操[Table] (Consolidation Resistance) Regarding the semipermeable membrane obtained in Example 1, permeation experiments of an aqueous sodium chloride solution were conducted continuously under the same conditions as in Example 1, and changes in membrane performance over time were measured. As the results are shown in Table 2, the membrane performance did not change over time and the membrane did not undergo compaction. (Evaluation of heat resistance) The semipermeable membrane obtained in Example 1 was placed in hot water at 95°C.
After soaking for 30 minutes, the removal rate and water permeation rate were measured.
Furthermore, the operation of soaking in hot water for 30 minutes like this
【表】
作を繰り返して、同様に除去率及び透水速度を測
定した。結果を第３表に示す。本発明による半透
膜は、熱水中への繰り返しての浸漬によつても、
その膜性能が実質的に変化せず、従つて、高温の
液体混合物の処理に好適に用いることができる。
（耐酸性）
実施例１において得た半透膜を蒸留水に２時間
浸漬し、次いで、25℃の0.5N塩酸水溶液に２時
間浸漬した後、実施例１と同じ条件下で塩化ナト
リウム水溶液についての膜性能を測定した。除去
率は98.6％、透水速度は1.2m3／m2・日であつて、
実質的に変化がなかつた。従つて、本発明の半透
膜は耐酸性にすぐれていることが理解される。
（耐アルカリ性）
実施例１において得た半透膜を蒸留水に２時間
浸漬し、次いで、25℃の0.5N水酸化ナトリウム
水溶液に２時間浸漬した後、実施例１と同じ条件
下で塩化ナトリウム水溶液についての膜性能を測
定した。除去率は98.4％、透水速度は1.3m3／
m2・日であつて、実質的に変化がなかつた。従つ
て、本発明の半透膜は耐アルカリにすぐれている
ことが理解される。
（耐乾燥性）
実施例１において得た半透膜を蒸留水に２時間
浸漬し、次いで、25℃で２時間乾燥した後、実施
例１と同じ条件下で塩化ナトリウム水溶液につい
ての膜性能を測定した。除去率は98.5％、透水速
度は1.2m3／m2・日であつて、実質的に変化がな
かつた。従つて、本発明の半透膜は乾燥後も、こ
れを再湿潤化すれば、当初と同等の膜性能を有す
ることが理解される。[Table] The removal rate and water permeation rate were measured in the same manner by repeating the cultivation. The results are shown in Table 3. The semipermeable membrane according to the present invention can also be immersed in hot water repeatedly.
The membrane performance is not substantially changed and therefore it can be suitably used to treat high temperature liquid mixtures. (Acid resistance) The semipermeable membrane obtained in Example 1 was immersed in distilled water for 2 hours, then in a 0.5N hydrochloric acid aqueous solution at 25°C for 2 hours, and then immersed in a sodium chloride aqueous solution under the same conditions as in Example 1. The membrane performance was measured. The removal rate was 98.6% and the water permeability rate was 1.2m 3 /m 2 ·day.
There was virtually no change. Therefore, it is understood that the semipermeable membrane of the present invention has excellent acid resistance. (Alkali resistance) The semipermeable membrane obtained in Example 1 was immersed in distilled water for 2 hours, then in a 0.5N sodium hydroxide aqueous solution at 25°C for 2 hours, and then immersed in sodium chloride under the same conditions as Example 1. Membrane performance was measured for aqueous solutions. Removal rate is 98.4%, water permeability rate is 1.3m 3 /
m 2 days, and there was virtually no change. Therefore, it is understood that the semipermeable membrane of the present invention has excellent alkali resistance. (Drying resistance) The semipermeable membrane obtained in Example 1 was immersed in distilled water for 2 hours, then dried at 25°C for 2 hours, and then the membrane performance for sodium chloride aqueous solution was evaluated under the same conditions as Example 1. It was measured. The removal rate was 98.5%, and the water permeation rate was 1.2 m 3 /m 2 ·day, with virtually no change. Therefore, it is understood that even after the semipermeable membrane of the present invention has been dried, if it is rewetted, it will have the same membrane performance as the original membrane performance.
Claims (1)
してなり、Ｎ−メチル−２−ピロリドン100mlに
重合体0.5ｇを溶解した溶液について、30℃の温
度において測定した対数粘度が0.5cm3／ｇ以上で
あり、且つ、イオン交換容量が２ミリ当量／ｇ以
下である水不溶性のスルホン化ポリスルホン共重
合体からなる異方性をもたない実質的に均質な半
透膜。 ２ スルホン化ポリスルホン共重合体が10モル％
以上の繰返し単位Ａと、90モル％以下の繰返し単
位Ｂとからなることを特徴とする特許請求の範囲
第１項記載のスルホン化ポリスルホン共重合体か
らなる半透膜。 ３ スルホン化ポリスルホン共重合体の有するス
ルホン酸基が式−SO3M（但し、Ｍは水素、アル
カリ金属又はテトラアルキルアンモニウムを示
す。）で表わされることを特徴とする特許請求の
範囲第１項又は第２項記載のスルホン化ポリスル
ホン共重合体からなる半透膜。 ４ 繰返し単位Ａ 及び繰返し単位Ｂ よりなる線状ポリスルホン共重合体をスルホン化
してなり、Ｎ−メチル−２−ピロリドン100mlに
重合体0.5ｇを溶解した溶液について、30℃の温
度において測定した対数粘度が0.5cm3／ｇ以上で
あり、且つ、イオン交換容量が２ミリ当量／ｇ以
下である水不溶性のスルホン化ポリスルホン共重
合体を含んでいてもよいアルキレングリコールモ
ノアルキルエーテルに溶解して製膜溶液とし、こ
れを適宜の基材上に塗布し、溶剤を蒸発させるこ
とを特徴とするスルホン化ポリスルホン共重合体
からなる異方性をもたない実質的に均質な半透膜
の製造方法。 ５ スルホン化ポリエステル共重合体が10モル％
以上の繰返し単位Ａと、90モル％以下の繰返し単
位Ｂとからなることを特徴とする特許請求の範囲
第４項記載のスルホン化ポリスルホン共重合体か
らなる半透膜の製造方法。 ６ スルホン化ポリスルホン共重合体の有するス
ルホン酸基が式−SO3M（但し、Ｍは水素、アル
カリ金属又はテトラアルキルアンモニウムを示
す。）で表わされることを特徴とする特許請求の
範囲第４項又は第５項記載のスルホン化ポリスル
ホン共重合体からなる半透膜の製造方法。[Claims] 1. Repeating unit A and repeating unit B A linear polysulfone copolymer made of A substantially homogeneous semipermeable membrane having no anisotropy and comprising a water-insoluble sulfonated polysulfone copolymer having an ion exchange capacity of 2 meq/g or less. 2 10 mol% of sulfonated polysulfone copolymer
A semipermeable membrane made of a sulfonated polysulfone copolymer according to claim 1, characterized in that it consists of the above repeating units A and 90 mol% or less of repeating units B. 3. Claim 1, wherein the sulfonic acid group of the sulfonated polysulfone copolymer is represented by the formula -SO 3 M (where M represents hydrogen, an alkali metal, or tetraalkylammonium) Or a semipermeable membrane made of the sulfonated polysulfone copolymer according to item 2. 4 Repeating unit A and repeating unit B A linear polysulfone copolymer made of and an alkylene glycol monoalkyl ether which may contain a water-insoluble sulfonated polysulfone copolymer with an ion exchange capacity of 2 milliequivalents/g or less to prepare a membrane-forming solution, and this is mixed with an appropriate group. 1. A method for producing a substantially homogeneous semipermeable membrane having no anisotropy comprising a sulfonated polysulfone copolymer, the method comprising coating the membrane on a material and evaporating a solvent. 5 10 mol% of sulfonated polyester copolymer
5. The method for producing a semipermeable membrane made of a sulfonated polysulfone copolymer according to claim 4, characterized in that it is composed of the above repeating units A and 90 mol% or less of repeating units B. 6 Claim 4, characterized in that the sulfonic acid group possessed by the sulfonated polysulfone copolymer is represented by the formula -SO 3 M (where M represents hydrogen, an alkali metal, or tetraalkylammonium) Or a method for producing a semipermeable membrane made of the sulfonated polysulfone copolymer according to item 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11172284A JPS60255109A (en) | 1984-05-30 | 1984-05-30 | Sulfonated polysulfone semipermeable membrane and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11172284A JPS60255109A (en) | 1984-05-30 | 1984-05-30 | Sulfonated polysulfone semipermeable membrane and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60255109A JPS60255109A (en) | 1985-12-16 |
| JPH052364B2 true JPH052364B2 (en) | 1993-01-12 |
Family
ID=14568501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11172284A Granted JPS60255109A (en) | 1984-05-30 | 1984-05-30 | Sulfonated polysulfone semipermeable membrane and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60255109A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS614506A (en) * | 1984-06-15 | 1986-01-10 | Nitto Electric Ind Co Ltd | Polysulfone composite semipermeable membrane and its manufacture |
| US6026968A (en) * | 1996-05-13 | 2000-02-22 | Nitto Denko Corporation | Reverse osmosis composite membrane |
| JP3724064B2 (en) * | 1996-06-28 | 2005-12-07 | 住友化学株式会社 | Polymer electrolyte for fuel cell and fuel cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5548222A (en) * | 1978-09-05 | 1980-04-05 | Ici Ltd | Sulfonated polyarylether sulfone copolymer |
-
1984
- 1984-05-30 JP JP11172284A patent/JPS60255109A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5548222A (en) * | 1978-09-05 | 1980-04-05 | Ici Ltd | Sulfonated polyarylether sulfone copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60255109A (en) | 1985-12-16 |
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