JP2021171720A - Method for producing selective permeable membrane and method for treating water - Google Patents
Method for producing selective permeable membrane and method for treating water Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 27
- 239000000178 monomer Substances 0.000 claims abstract description 54
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- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
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- 239000000463 material Substances 0.000 claims abstract description 15
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- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
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- 239000000126 substance Substances 0.000 description 7
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- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
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- KILNVBDSWZSGLL-KXQOOQHDSA-N 1,2-dihexadecanoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCCCCCCCCC KILNVBDSWZSGLL-KXQOOQHDSA-N 0.000 description 1
- TZCPCKNHXULUIY-RGULYWFUSA-N 1,2-distearoyl-sn-glycero-3-phosphoserine Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OC[C@H](N)C(O)=O)OC(=O)CCCCCCCCCCCCCCCCC TZCPCKNHXULUIY-RGULYWFUSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PAZGBAOHGQRCBP-DDDNOICHSA-N 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoglycerol Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCC(O)CO)OC(=O)CCCCCCC\C=C/CCCCCCCC PAZGBAOHGQRCBP-DDDNOICHSA-N 0.000 description 1
- UGEHFOSBNBEWMP-UHFFFAOYSA-N 2,3-diaminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1N UGEHFOSBNBEWMP-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- SAAWBXNYGGDHSP-UHFFFAOYSA-N 4,4-diaminobutylphosphonic acid Chemical compound NC(CCCP(O)(O)=O)N SAAWBXNYGGDHSP-UHFFFAOYSA-N 0.000 description 1
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 1
- APKFDSVGJQXUKY-KKGHZKTASA-N Amphotericin-B Natural products O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1C=CC=CC=CC=CC=CC=CC=C[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 APKFDSVGJQXUKY-KKGHZKTASA-N 0.000 description 1
- 102000010637 Aquaporins Human genes 0.000 description 1
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- OCJBHPHJJRGNDC-UHFFFAOYSA-N COS(C(C=C1)=CC(N)=C1N)(=O)=O Chemical compound COS(C(C=C1)=CC(N)=C1N)(=O)=O OCJBHPHJJRGNDC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- JZNWSCPGTDBMEW-UHFFFAOYSA-N Glycerophosphorylethanolamin Natural products NCCOP(O)(=O)OCC(O)CO JZNWSCPGTDBMEW-UHFFFAOYSA-N 0.000 description 1
- ZWZWYGMENQVNFU-UHFFFAOYSA-N Glycerophosphorylserin Natural products OC(=O)C(N)COP(O)(=O)OCC(O)CO ZWZWYGMENQVNFU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
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- 229920002873 Polyethylenimine Polymers 0.000 description 1
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- HIHOWBSBBDRPDW-PTHRTHQKSA-N [(3s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] n-[2-(dimethylamino)ethyl]carbamate Chemical compound C1C=C2C[C@@H](OC(=O)NCCN(C)C)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HIHOWBSBBDRPDW-PTHRTHQKSA-N 0.000 description 1
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- ALVIPGWBQWVQQB-UHFFFAOYSA-N ethyl 2,5-diaminobenzoate Chemical compound CCOC(=O)C1=CC(N)=CC=C1N ALVIPGWBQWVQQB-UHFFFAOYSA-N 0.000 description 1
- NUJBTXFFJUGENN-UHFFFAOYSA-N ethyl 3,4-diaminobenzoate Chemical compound CCOC(=O)C1=CC=C(N)C(N)=C1 NUJBTXFFJUGENN-UHFFFAOYSA-N 0.000 description 1
- IDLVQOMJOKNXSL-UHFFFAOYSA-N ethyl 3,5-diaminobenzoate Chemical compound CCOC(=O)C1=CC(N)=CC(N)=C1 IDLVQOMJOKNXSL-UHFFFAOYSA-N 0.000 description 1
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- IOPLHGOSNCJOOO-UHFFFAOYSA-N methyl 3,4-diaminobenzoate Chemical compound COC(=O)C1=CC=C(N)C(N)=C1 IOPLHGOSNCJOOO-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
本発明は、水処理分野で使用される選択性透過膜の製造方法に係り、緻密層を有する選択性透過膜の製造方法に関する。 The present invention relates to a method for producing a selective permeable membrane used in the field of water treatment, and relates to a method for producing a selective permeable membrane having a dense layer.
海水、かん水の淡水化や、工業用水および超純水の製造、排水回収などの分野で、選択性透過膜として、逆浸透（ＲＯ）膜やナノ濾過（ＮＦ）膜が広く用いられている。ＲＯ膜処理は、イオンや低分子有機物を高度に除去できるという利点を有するが、精密濾過（ＭＦ）膜や限外濾過（ＵＦ）膜と比べ、高い運転圧力を必要とする。ＮＦ膜はＲＯ膜よりは高い運転圧力を要しないが、イオンや低分子有機物の除去性がＲＯ膜よりも劣る。 Reverse osmosis (RO) membranes and nanofiltration (NF) membranes are widely used as selective permeable membranes in fields such as desalination of seawater and brackish water, production of industrial water and ultrapure water, and wastewater recovery. RO membrane treatment has the advantage of being able to highly remove ions and low molecular weight organic substances, but requires higher operating pressure than microfiltration (MF) membranes and ultrafiltration (UF) membranes. The NF membrane does not require a higher operating pressure than the RO membrane, but its ability to remove ions and small molecule organic substances is inferior to that of the RO membrane.
高透水性を有するＮＦ膜の開発は盛んに行われているが、既存のＮＦ膜の透過流束は１１ＬＭＨ／ｂａｒ、ＮａＣｌ阻止率５０％程度である。 Although NF membranes having high water permeability have been actively developed, the permeation flux of existing NF membranes is 11 LMH / bar and the NaCl inhibition rate is about 50%.
非特許文献１には、界面重合法によりＲＯ膜表面に緻密層を形成することが記載されている。 Non-Patent Document 1 describes that a dense layer is formed on the surface of an RO film by an interfacial polymerization method.
界面重合法で緻密層を形成させた選択性透過膜において、透水性と塩阻止性にはトレードオフの関係があり、高透水性と高い塩阻止性を有する膜を作製することは困難であった。本発明は、高透水性と高い塩阻止性を有する選択性透過膜の製造方法を提供することを課題とする。 In a selective permeable membrane in which a dense layer is formed by an interfacial polymerization method, there is a trade-off relationship between water permeability and salt blocking property, and it is difficult to prepare a membrane having high water permeability and high salt blocking property. rice field. An object of the present invention is to provide a method for producing a selective permeable membrane having high water permeability and high salt blocking property.
本発明は、次を要旨とする。 The gist of the present invention is as follows.
［１］ 多官能アミンモノマーと多官能酸クロライドモノマーを透水性基材の表面で界面重合させることによって該透水性基材の表面に緻密層を形成する工程を有する選択性透過膜の製造方法であって、界面重合の際の多官能アミンモノマーの少なくとも一部がヒドロキシ基を有する有機化合物によってエステル化されたものであり、界面重合の後にエステル結合を加水分解させることにより該緻密層に荷電基を与える加水分解工程を有することを特徴とする選択性透過膜の製造方法。 [1] A method for producing a selective permeable film, which comprises a step of forming a dense layer on the surface of a water-permeable base material by interfacially polymerizing a polyfunctional amine monomer and a polyfunctional acid chloride monomer on the surface of the water-permeable base material. At least a part of the polyfunctional amine monomer during interfacial polymerization is esterified with an organic compound having a hydroxy group, and the dense layer is charged with a charged group by hydrolyzing the ester bond after interfacial polymerization. A method for producing a selective permeable membrane, which comprises a hydrolysis step of providing an ester.
［２］ 前記エステル化されている多官能アミンモノマーがジアミノ安息香酸のエステル、ジアミノベンゼンスルホン酸のエステル、ジアミノベンゼンホスホン酸のエステル、及びジアミノブチルホスホン酸のエステルの少なくとも１種である［１］に記載の選択性透過膜の製造方法。 [2] The esterified polyfunctional amine monomer is at least one of a diaminobenzoic acid ester, a diaminobenzenesulfonic acid ester, a diaminobenzenephosphonic acid ester, and a diaminobutylphosphonic acid ester [1]. The method for producing a selective permeable membrane according to.
［３］ 前記荷電基がカルボキシ基である［１］又は［２］に記載の選択性透過膜の製造方法。 [3] The method for producing a selective permeable membrane according to [1] or [2], wherein the charged group is a carboxy group.
［４］ 前記エステル化されている多官能アミンモノマーがジアミノ安息香酸メチルである［１］に記載の選択性透過膜の製造方法。 [4] The method for producing a selective permeable membrane according to [1], wherein the esterified polyfunctional amine monomer is methyl diaminobenzoate.
［５］ 前記多官能酸クロライドモノマーが、トリメシン酸、フタル酸又はフマル酸の酸クロライドである［１］〜［４］のいずれかの選択性透過膜の製造方法。 [5] The method for producing a selective permeable membrane according to any one of [1] to [4], wherein the polyfunctional acid chloride monomer is an acid chloride of trimesic acid, phthalic acid or fumaric acid.
［６］ エステル結合を加水分解させる方法が、ｐＨ１０以上のアルカリ性溶液に接触させる方法である［１］〜［５］のいずれかに記載の選択性透過膜の製造方法。 [6] The method for producing a selective permeable membrane according to any one of [1] to [5], wherein the method for hydrolyzing the ester bond is a method for contacting with an alkaline solution having a pH of 10 or higher.
［７］ 前記加水分解工程の後に、前記選択性透過膜にカチオン性高分子を吸着させるカチオン性高分子吸着工程を有する［１］〜［６］のいずれかに記載の選択性透過膜の製造方法。 [7] Production of the selective permeable membrane according to any one of [1] to [6], which comprises a cationic polymer adsorption step of adsorbing the cationic polymer to the selective permeable membrane after the hydrolysis step. Method.
［８］ 前記加水分解工程の後に、前記選択性透過膜にリン脂質を吸着させるリン脂質吸着工程を有する［１］〜［７］のいずれかに記載の選択性透過膜の製造方法。 [8] The method for producing a selective permeable membrane according to any one of [1] to [7], which comprises a phospholipid adsorption step of adsorbing phospholipids on the selective permeable membrane after the hydrolysis step.
［９］ ［１］〜［８］のいずれかに記載の方法によって製造された選択性透過膜を用いて被処理水を膜分離処理する工程を有する水処理方法。 [9] A water treatment method comprising a step of membrane separation treatment of water to be treated using a selective permeable film produced by the method according to any one of [1] to [8].
本発明によると、高透水性と高い塩阻止性を有した選択性透過膜を製造することができる。 According to the present invention, a selective permeable membrane having high water permeability and high salt blocking property can be produced.
本発明方法により製造された選択性透過膜の作用機構は以下の通りである。 The mechanism of action of the selective permeable membrane produced by the method of the present invention is as follows.
界面重合法により選択性透過膜の膜表面に荷電基を導入するに際し、アニオン荷電をエステル基でマスクして界面重合を行い、その後、エステル基を加水分解させて、アニオン性の荷電基を生成させる。アニオン性の荷電基が導入されていることで、緻密性が同じでも塩阻止性が向上するため、高い透水性の選択性透過膜が得られる。 When introducing a charged group onto the membrane surface of a selective permeable membrane by the interfacial polymerization method, the anionic charge is masked with an ester group to perform interfacial polymerization, and then the ester group is hydrolyzed to generate an anionic charged group. Let me. Since the anionic charged group is introduced, the salt blocking property is improved even if the density is the same, so that a highly water-permeable selective permeable membrane can be obtained.
作製した膜表面にカチオン性高分子を吸着させることで、カチオン性の荷電基を導入することができる。また、チャネル物質を導入した脂質二分子膜を形成させることで、塩阻止性を向上させることができる。 By adsorbing a cationic polymer on the surface of the prepared membrane, a cationic charged group can be introduced. In addition, the salt inhibitory property can be improved by forming a lipid bilayer membrane into which a channel substance is introduced.
本発明の選択性透過膜の製造方法では、多官能アミンモノマーと多官能酸クロライドモノマーを透水性基材の表面で界面重合させることによって該透水性基材の表面に緻密層を形成する。本発明では、界面重合の際の多官能アミンモノマーの少なくとも一部がヒドロキシ基を有する有機化合物によってエステル化されたものであり、界面重合の後にエステル結合を加水分解させることにより該緻密層に荷電基を与える。 In the method for producing a selective permeable membrane of the present invention, a dense layer is formed on the surface of the water permeable base material by interfacial polymerization of a polyfunctional amine monomer and a polyfunctional acid chloride monomer on the surface of the water permeable base material. In the present invention, at least a part of the polyfunctional amine monomer during interfacial polymerization is esterified with an organic compound having a hydroxy group, and the dense layer is charged by hydrolyzing the ester bond after interfacial polymerization. Give a group.
［透水性基材］
本発明で用いる透水性基材は、ＭＦ膜、ＵＦ膜、ＲＯ膜、ＮＦ膜などのいずれでもよい。
[Water permeable base material]
The water-permeable substrate used in the present invention may be any of MF membrane, UF membrane, RO membrane, NF membrane and the like.
［緻密層の形成］
選択性透過膜の塩阻止性を向上させる手段の一つとして、膜の流入側の表面に荷電基を有する緻密層を形成することが挙げられる。膜の緻密性が同じであっても、荷電基が膜表面にあると、荷電反発によって塩阻止性は高くなる。
[Formation of dense layer]
One of the means for improving the salt blocking property of the selective permeable membrane is to form a dense layer having a charged group on the surface on the inflow side of the membrane. Even if the density of the film is the same, if the charged group is on the surface of the film, the salt blocking property is enhanced by the charge repulsion.
界面重合法によって荷電基を有する緻密層を形成するに際して、荷電基であるカルボキシ基、スルホン基、リン酸基などのアニオン性基、あるいは２〜４級アミノ基などのカチオン性基を有するモノマーを用いる場合、油相に溶解させる酸クロライドモノマーにこれらの荷電基を導入すると、油相への溶解度が低下するため、界面重合が出来なくなってしまう。多官能アミンモノマーに荷電基を導入した場合においては、水相への溶解度は問題ないが、界面重合の際の油相への移動が起こり難くなり、充分な界面重合が行われないという問題が生じる。 When forming a dense layer having a charged group by an interfacial polymerization method, a monomer having an anionic group such as a carboxy group, a sulfone group or a phosphoric acid group, or a monomer having a cationic group such as a 2 to 4th amino group is used. When used, if these charged groups are introduced into the acid chloride monomer to be dissolved in the oil phase, the solubility in the oil phase is lowered, so that interfacial polymerization cannot be performed. When a charged group is introduced into the polyfunctional amine monomer, the solubility in the aqueous phase is not a problem, but the transfer to the oil phase during interfacial polymerization is difficult to occur, and there is a problem that sufficient interfacial polymerization is not performed. Occurs.
本発明は、かかる問題を解決すべく、荷電基であるアニオン性基をヒドロキシ基を有する化合物でエステル化した多官能アミンモノマーを用いて多官能酸クロライドモノマーと界面重合させる。その結果、界面重合の際にはアニオン性基はマスクされているため、親水性が過剰になることは無く、油相への移動が制限されず、界面重合反応を進行させることが可能となる。 In order to solve this problem, the present invention interpolymerizes an anionic group, which is a charged group, with a polyfunctional acid chloride monomer using a polyfunctional amine monomer esterified with a compound having a hydroxy group. As a result, since the anionic group is masked during the interfacial polymerization, the hydrophilicity is not excessive, the movement to the oil phase is not restricted, and the interfacial polymerization reaction can proceed. ..
作製した緻密層への荷電性の付与は、エステル化されている部分を加水分解することによって行う。アルカリ性水溶液や酸性水溶液に接触させると、ヒドロキシ基を有する化合物が加水分解して乖離して、アニオン性の荷電基が膜表面に生成する。 Chargeability is imparted to the produced dense layer by hydrolyzing the esterified portion. When contacted with an alkaline aqueous solution or an acidic aqueous solution, the compound having a hydroxy group is hydrolyzed and dissociated, and an anionic charged group is generated on the film surface.
本発明における界面重合による緻密層の形成は、荷電基であるアニオン性基をヒドロキシ基を有する化合物でエステル化した多官能アミンモノマーを用いること以外は従来（非特許文献１など）の界面重合法と同様に方法により行うことができる。 The formation of a dense layer by interfacial polymerization in the present invention is a conventional interfacial polymerization method (Non-Patent Document 1 and the like) except that a polyfunctional amine monomer in which an anionic group as a charged group is esterified with a compound having a hydroxy group is used. It can be done by the same method as above.
例えば、透水性基材の流入側表面の全面に多官能アミンを溶解させた水溶液を供給し、該水溶液をドレンした後にエアーブローすること等により過剰の水溶液を除去した後に、該水溶液が付着した透水性基材の表面の全面に、多官能酸クロライドを溶解させたヘキサン溶液を供給する。該ヘキサン溶液の供給後、０．１〜３分程度この状態に保持し、その後、該ヘキサン溶液をドレンすることによりヘキサン溶液を除去し、８０〜１４０℃で１〜３０ｍｉｎ乾燥及び熱処理を行う。 For example, an aqueous solution in which a polyfunctional amine is dissolved is supplied to the entire surface of the water-permeable substrate on the inflow side, the aqueous solution is drained, and then an air blow is performed to remove the excess aqueous solution, and then the aqueous solution adheres. A hexane solution in which polyfunctional acid chloride is dissolved is supplied over the entire surface of the water-permeable substrate. After supplying the hexane solution, it is kept in this state for about 0.1 to 3 minutes, and then the hexane solution is removed by draining the hexane solution, and drying and heat treatment are performed at 80 to 140 ° C. for 1 to 30 minutes.
アニオン性荷電基をヒドロキシ基を有する化合物でエステル化させた多官能アミンモノマーとしては、ジアミノ安息香酸のエステル、ジアミノベンゼンスルホン酸のエステル、ジアミノベンゼンホスホン酸のエステル、ジアミノブチルホスホン酸のエステルなどが挙げられる。具体的には、３，５−ジアミノ安息香酸メチル、３，４−ジアミノ安息香酸メチル、２，５−ジアミノ安息香酸メチル、３，５−ジアミノ安息香酸エチル、３，４−ジアミノ安息香酸エチル、２，５−ジアミノ安息香酸エチル、２，４−ジアミノベンゼンスルホン酸メチル、３，４−ジアミノベンゼンスルホン酸メチル、２，４−ジアミノベンゼンスルホン酸エチル、３，４−ジアミノベンゼンスルホン酸エチル、１，４−ジアミノブチルホスホン酸ジメチルなどが挙げられる。
Examples of the polyfunctional amine monomer obtained by esterifying an anionic charged group with a compound having a hydroxy group include an ester of diaminobenzoic acid, an ester of diaminobenzenesulfonic acid, an ester of diaminobenzenephosphonic acid, and an ester of diaminobutylphosphonic acid. Can be mentioned. Specifically,
エステル化した多官能アミンモノマー水溶液中のエステル化した多官能アミンモノマーの濃度は０．１〜５ｗｔ％、特に０．２〜２ｗｔ％程度が好ましい。透水性基材の表面に付着させるエステル化した多官能アミンモノマーの量は０．０１〜２ｍｇ／ｃｍ２、特に０．０２〜１ｍｇ／ｃｍ２程度が好ましいが、これに限定されない。
The concentration of the esterified polyfunctional amine monomer in the esterified polyfunctional amine monomer aqueous solution is preferably 0.1 to 5 wt%, particularly preferably about 0.2 to 2 wt%. The amount of the esterified polyfunctional amine monomer attached to the surface of the water-permeable substrate is preferably 0.01 to 2 mg /
上記アニオン性荷電基をヒドロキシ基を有する化合物でエステル化させた多官能アミンモノマーとその他の多官能アミンモノマーを混在させても良い。その他の多官能アミンモノマーとしては、１，２−ジアミノベンゼン、１，３−ジアミノベンゼン、１，４−ジアミノベンゼン、エチレンジアミン、１，３−ジアミノプロパン、１，２−ジアミノプロパン、ヘキサメチレンジアミン、ピペラジンなどが挙げられる。 A polyfunctional amine monomer in which the anionic charged group is esterified with a compound having a hydroxy group and another polyfunctional amine monomer may be mixed. Other polyfunctional amine monomers include 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, hexamethylenediamine, etc. Examples include piperazine.
多官能酸クロライドモノマーとしては、トリメシン酸、フタル酸、フマル酸の酸クロライドなどが挙げられる。具体的には、トリメシン酸クロライド（１，３，５−ベンゼントリカルボニルトリクロライド）、１，３−ベンゼンジカルボニルジクロライド、１，４−ベンゼンジカルボニルジクロライド、フマリルクロライドなどである。 Examples of the polyfunctional acid chloride monomer include trimesic acid, phthalic acid, and acid chloride of fumaric acid. Specific examples thereof include trimesic acid chloride (1,3,5-benzenetricarbonyltrichloride), 1,3-benzenedicarbonyldichloride, 1,4-benzenedicarbonyldichloride, and fumalyl chloride.
多官能酸クロライドモノマーを溶解させる溶媒は、ヘキサンの他、ヘプタン、ベンゼン、トルエン、イソプロピルアルコール等も用いることができる。多官能酸クロライドモノマー溶液の濃度は０．０１〜１ｗｔ％程度が好ましい。エステル化した多官能アミンモノマー１モルに対して供給する多官能酸クロライドモノマーのモル量は０．０１〜１モル程度が好ましい。 As the solvent for dissolving the polyfunctional acid chloride monomer, heptane, benzene, toluene, isopropyl alcohol and the like can be used in addition to hexane. The concentration of the polyfunctional acid chloride monomer solution is preferably about 0.01 to 1 wt%. The molar amount of the polyfunctional acid chloride monomer supplied with respect to 1 mol of the esterified polyfunctional amine monomer is preferably about 0.01 to 1 mol.
エステル化されている部分の加水分解を行うためのアルカリ水溶液としては、ＮａＯＨ、ＫＯＨなどの０．０１〜１Ｎ程度の水溶液が好適である。加水分解を行うための酸水溶液としては、ＨＣｌ、ＨＮＯ３、Ｈ２ＳＯ４などの０．０１〜１Ｎ程度の水溶液が好適である。 As the alkaline aqueous solution for hydrolyzing the esterified portion, an aqueous solution of about 0.01 to 1N such as NaOH and KOH is suitable. As the acid aqueous solution for hydrolyzing, an aqueous solution of about 0.01 to 1N such as HCl, HNO 3 , H 2 SO 4 is suitable.
アルカリ水溶液又は酸水溶液によってエステルの加水分解を行うには、上記重合反応によりポリマー層が形成された基材表面にアルカリ又は酸水溶液を接触させる。アルカリ又は酸水溶液を接触させる方法としては、非加圧接触方法が好適である。この非加圧接触方法は、膜を所定の溶液に浸漬したり、セルやベッセルに設置された膜に所定の溶液を通液、静置することにより行われる。 In order to hydrolyze the ester with an alkaline aqueous solution or an acid aqueous solution, the alkali or acid aqueous solution is brought into contact with the surface of the base material on which the polymer layer is formed by the above polymerization reaction. As a method of contacting an alkaline or acid aqueous solution, a non-pressurized contact method is preferable. This non-pressurized contact method is performed by immersing the membrane in a predetermined solution, or passing a predetermined solution through a membrane installed in a cell or vessel and allowing it to stand.
塩阻止性を向上させるために、上述の方法で、膜表面にアニオン荷電を導入した後にカチオン性高分子を吸着させ、カチオン荷電層を形成させてもよい。カチオン性高分子としては、ポリエチレンイミン、ポリジアリルジメチルアンモニウム、ボリビジルアミジンなどが挙げられる。 In order to improve the salt blocking property, the cationic polymer may be adsorbed after introducing anionic charge on the membrane surface by the above-mentioned method to form a cationically charged layer. Examples of the cationic polymer include polyethyleneimine, polydiallyldimethylammonium, and bolividylamidine.
塩阻止性を向上させるために、上述の方法で、膜表面にアニオン荷電やカチオン荷電を導入した後に、チャネル物質を含有する脂質二分子膜を形成させてもよい。 In order to improve the salt blocking property, a lipid bilayer membrane containing a channel substance may be formed after introducing anionic charges or cationic charges on the membrane surface by the above-mentioned method.
脂質には、カチオン性、アニオン性、中性脂質があり、カチオン性脂質としては、特に限定されるものではないが、１，２−ジオレオイル−３−トリメチルアンモニウムプロパン、１−パルミトイル−２−オレオイル−ｓｎ−グリセロ−３−エチルホスホコリン、３β−［Ｎ−（Ｎ’，Ｎ’−ジメチルアミノエタン）−カルバモイル］コレステロール塩酸塩などを用いることができる。アニオン性脂質としては、特に限定されるものではないが、１−パルミトイル−２−オレオイルホスファチジルグリセロール、１−パルミトイル−２−オレオイルホスファチジン酸、１−パルミトイル−２−オレオイルホスファチジルセリンなどを用いることができる。中性脂質としては、特に限定されるものではないが、１−パルミトイル−２−オレオイルホスファチジルコリン、１，２−ジオレオイルホスファチジルコリン、１，２−ジパルミトイルホスファチジルコリン、１−パルミトイル−２−オレオイルホスファチジルエタノールアミン、コレステロール、エルゴステロールなどを用いることができる。 Lipids include cationic, anionic, and neutral lipids, and the cationic lipids are not particularly limited, but 1,2-dioreoil-3-trimethylammonium propane and 1-palmitoyl-2-ole. Oil-sn-glycero-3-ethylphosphocholine, 3β- [N- (N', N'-dimethylaminoethane) -carbamoyl] cholesterol hydrochloride and the like can be used. The anionic lipid is not particularly limited, but 1-palmitoyl-2-oleoylphosphatidylglycerol, 1-palmitoyl-2-oleoylphosphatidylate, 1-palmitoyl-2-oleoil phosphatidylserine and the like are used. be able to. The neutral lipid is not particularly limited, but 1-palmitoyl-2-oleoylphosphatidylcholine, 1,2-dioreoil phosphatidylcholine, 1,2-dipalmitoylphosphatidylcholine, 1-palmitoyl-2-oleoyl. Phosphatidylethanolamine, cholesterol, ergosterol and the like can be used.
チャネル物質としては、例えば、アクアポリン、グラミシジン、アムホテリシンＢ、あるいはそれらの誘導体などを用いることができる。 As the channel substance, for example, aquaporin, grammicidin, amphotericin B, or a derivative thereof can be used.
チャネル物質の脂質二分子膜への導入方法としては、リポソーム調製段階にあらかじめ混合する方法や、製膜後に添加する方法などを用いることができる。 As a method for introducing the channel substance into the lipid bilayer membrane, a method of mixing in advance at the liposome preparation stage, a method of adding the channel substance after the membrane formation, or the like can be used.
［実施例１］
下記の基材の表面に下記の多官能アミンモノマー水溶液を付着させ、次いで下記の多官能酸クロライドヘキサン溶液を供給し、下記手順で界面重合反応及び脱エステル化反応させて選択性透過膜を製造し、膜性能評価した。
[Example 1]
The following polyfunctional amine monomer aqueous solution is adhered to the surface of the following base material, then the following polyfunctional acid chloride hexane solution is supplied, and the interfacial polymerization reaction and deesterification reaction are carried out according to the following procedure to produce a selective permeable membrane. Then, the membrane performance was evaluated.
＜透水性基材＞
ポリスルホン製限外濾過膜ＣＦ−３０（日東電工）
<Water permeable base material>
Polysulfone ultrafiltration membrane CF-30 (Nitto Denko)
＜多官能アミンモノマー水溶液＞
１，３−ジアミノベンゼン １．０ｗｔ％
ジアミノ安息香酸メチル １．０ｗｔ％
（多官能アミンモノマーとして合計２．０ｗｔ％）
ドデシル硫酸ナトリウム ０．２５ｗｔ％
イソプロピルアルコール ５．０Ｗｔ％
<Aqueous solution of polyfunctional amine monomer>
1,3-Diaminobenzene 1.0 wt%
Methyl diaminobenzoate 1.0 wt%
(Total 2.0 wt% as polyfunctional amine monomer)
Sodium dodecyl sulfate 0.25 wt%
Isopropyl alcohol 5.0 Wt%
＜多官能酸クロライドヘキサン溶液＞
トリメシン酸クロライド ０．１５ｗｔ％
<Polyfunctional acid chloride hexane solution>
Trimesic acid chloride 0.15 wt%
＜界面重合反応手順＞
上記多官能アミンモノマー水溶液に上記基材を１ｍｉｎ浸漬した後、水溶液をドレンし、エアーブローすることにより過剰な水溶液を膜面から除去した。次いで、この基材を多官能酸クロライドヘキサン溶液に１５ｓ浸漬した後、ヘキサン溶液をドレンすることにより過剰な該多官能酸クロライドヘキサン溶液を膜面から除去した。次いで、加熱処理を１００℃で１０ｍｉｎ行った。
<Interfacial polymerization reaction procedure>
After immersing the base material in the polyfunctional amine monomer aqueous solution for 1 min, the aqueous solution was drained and air blown to remove the excess aqueous solution from the membrane surface. Next, this base material was immersed in a polyfunctional acid chloride hexane solution for 15 seconds, and then the excess polyfunctional acid chloride hexane solution was removed from the membrane surface by draining the hexane solution. Next, the heat treatment was carried out at 100 ° C. for 10 minutes.
＜脱エステル加水分解反応＞
このようにしてポリマー層が形成された基材表面に０．１ＮＮａＯＨ水溶液を１日間、非加圧接触（具体的には、セルに設置した膜に該水溶液を通液する。）させた後、純水で洗浄することにより選択性透過膜を得た。
<Deester hydrolysis reaction>
A 0.1 N NaOH aqueous solution is brought into non-pressurized contact (specifically, the aqueous solution is passed through a film placed in a cell) on the surface of the base material on which the polymer layer is formed for one day. A selective permeable membrane was obtained by washing with pure water.
［実施例２］
多官能アミンモノマーとして、ピペラジン１．０ｗｔ％と３，５−ジアミノ安息香酸メチル１．０ｗｔ％を用いたこと、及び脱エステル加水分解反応のＮａＯＨ水溶液の非加圧接触日数を４日としたこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Example 2]
As the polyfunctional amine monomer, 1.0 wt% of piperazine and 1.0 wt% of
［実施例３］
多官能アミンモノマーとして、ピペラジン０．５ｗｔ％と３，５−ジアミノ安息香酸メチル１．５ｗｔ％を用いたこと、及び脱エステル加水分解反応のＮａＯＨ水溶液の非加圧接触日数を４日としたこと以外は実施例１と同様にして選択性透過膜を製造し性能評価を行った。
[Example 3]
As the polyfunctional amine monomer, 0.5 wt% of piperazine and 1.5 wt% of
［比較例１］
市販のスルホン化ポリエーテルスルホンＮＦ膜ＮＴＲ−７４５０（日東電工）を用い、性能評価を行った。
[Comparative Example 1]
Performance evaluation was performed using a commercially available sulfonated polyether sulfone NF membrane NTR-7450 (Nitto Denko).
［比較例２］
多官能アミンモノマーとして、１，３−ジアミノベンゼン２ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 2]
A selective permeable membrane was produced in the same manner as in Example 1 except that 1,3-diaminobenzene (2 wt%) was used as the polyfunctional amine monomer and the desester hydrolysis reaction was not carried out, and the performance was evaluated. went.
［比較例３］
多官能アミンモノマーとして、ピペラジン２ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 3]
A selective permeable membrane was produced in the same manner as in Example 1 except that 2 wt% of piperazine was used as the polyfunctional amine monomer and the desester hydrolysis reaction was not carried out, and the performance was evaluated.
［比較例４］
多官能アミンモノマーとして、１，３−ジアミノベンゼン１．０ｗｔ％と３，５−ジアミノ安息香酸１．０ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 4]
Example 1 and Example 1 except that 1.0 wt% of 1,3-diaminobenzene and 1.0 wt% of 3,5-diaminobenzoic acid were used as the polyfunctional amine monomer, and the desester hydrolysis reaction was not carried out. A selective permeable film was produced in the same manner, and its performance was evaluated.
［比較例５］
多官能アミンモノマーとして、ピペラジン１．０ｗｔ％と１，３−ジアミノベンゼン１．０ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 5]
Selective permeation in the same manner as in Example 1 except that 1.0 wt% of piperazine and 1.0 wt% of 1,3-diaminobenzene were used as the polyfunctional amine monomer and no desester hydrolysis reaction was carried out. A film was manufactured and its performance was evaluated.
［比較例６］
多官能アミンモノマーとして、ピペラジン０．５ｗｔ％と１，３−ジアミノベンゼン１．５ｗｔ％を用いたこと、及び脱エステル加水分解反応を行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 6]
Selective permeation in the same manner as in Example 1 except that 0.5 wt% of piperazine and 1.5 wt% of 1,3-diaminobenzene were used as the polyfunctional amine monomer and no deester hydrolysis reaction was carried out. A film was manufactured and its performance was evaluated.
［比較例７］
多官能アミンモノマーとして、１，３−ジアミノベンゼン１．０ｗｔ％と３，５−ジアミノ安息香酸メチル１．０ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 7]
Example 1 except that 1.0 wt% of 1,3-diaminobenzene and 1.0 wt% of
［比較例８］
多官能アミンモノマーとして、ピペラジン１．０ｗｔ％と３，５−ジアミノ安息香酸メチル１．０ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 8]
Selected in the same manner as in Example 1 except that 1.0 wt% of piperazine and 1.0 wt% of
［比較例９］
多官能アミンモノマーとして、ピペラジン０．５ｗｔ％と３，５−ジアミノ安息香酸メチル１．５ｗｔ％を用いたこと、及び脱エステル加水分解反応は行わなかったこと以外は実施例１と同様にして選択性透過膜を製造し、性能評価を行った。
[Comparative Example 9]
Selected in the same manner as in Example 1 except that 0.5 wt% of piperazine and 1.5 wt% of
［膜性能評価試験］
図１，２に示す試験装置により、膜性能を評価した。
[Membrane performance evaluation test]
The film performance was evaluated by the test apparatus shown in FIGS. 1 and 2.
この試験装置において、膜供給水は、配管１よりポンプ２で、密閉容器３の平膜セル４の下側の原水室５に供給される。原水室５内はスターラー６で撹拌子を回転させることにより撹拌される。膜透過水は平膜セル４の上側の透過水室７を経て配管８より取り出される。濃縮水は配管９より取り出される。密閉容器３内の圧力は、配管９に設けた圧力計１０と、濃縮水取出配管９に設けた圧力調整バルブ１１により調整される。
In this test apparatus, the membrane supply water is supplied from the pipe 1 to the
操作圧力０．７５ＭＰａで純水を供給水として透過流束を測定した。また、５００ｍｇ／ＬのＮａＣｌ水溶液を供給水としたときの透過水の電気伝導度と濃縮水の電気伝導度から、下記式でＮａＣｌの阻止率を求めた。 The permeation flux was measured using pure water as the supply water at an operating pressure of 0.75 MPa. Further, the inhibition rate of NaCl was determined by the following formula from the electric conductivity of the permeated water and the electric conductivity of the concentrated water when a 500 mg / L NaCl aqueous solution was used as the feed water.
ＮａＣｌ阻止率［％］＝（１−透過水の電気伝導度／濃縮水の電気伝導度）×１００ NaCl blocking rate [%] = (1-electric conductivity of permeated water / electric conductivity of concentrated water) x 100
［結果及び考察］
実施例１〜３及び比較例１〜９の性能評価結果を表１に示す。
[Results and discussion]
Table 1 shows the performance evaluation results of Examples 1 to 3 and Comparative Examples 1 to 9.
実施例１、２、３と比較例７、８、９の比較より、脱エステル加水分解反応により透水性が大幅に向上することが認められる。また、比較例５、６の通り、多官能アミンモノマーとしてアニオン性荷電基をヒドロキシ基を有する化合物でエステル化させた多官能アミンモノマーを用いない場合、脱エステル加水分解反応による透水性の向上は見られなかったことから、ポリアミドのアミド結合が脱エステル加水分解反応により切断されないことが認められる。 From the comparison between Examples 1, 2 and 3 and Comparative Examples 7, 8 and 9, it is confirmed that the water permeability is significantly improved by the deesteration hydrolysis reaction. Further, as in Comparative Examples 5 and 6, when a polyfunctional amine monomer obtained by esterifying an anionic charged group with a compound having a hydroxy group is not used as the polyfunctional amine monomer, the water permeability is improved by the deesteration hydrolysis reaction. Since it was not observed, it is recognized that the amide bond of polyamide is not cleaved by the deester hydrolysis reaction.
さらに、実施例１と比較例４の比較より、比較例４のカルボキシ基を有しカルボキシ基がエステル化されていない多官能アミンモノマーを用いた場合は、実施例１の脱エステル加水分解反応によりカルボキシ基を生成させた場合と比べ、透水性が著しく低く、あらかじめカルボキシ基をエステル化することが透水性向上に有効であることが認められる。 Further, from the comparison between Example 1 and Comparative Example 4, when a polyfunctional amine monomer having a carboxy group of Comparative Example 4 and the carboxy group was not esterified was used, the deesterification hydrolysis reaction of Example 1 was carried out. Compared with the case where the carboxy group is generated, the water permeability is remarkably low, and it is recognized that esterifying the carboxy group in advance is effective in improving the water permeability.
上記の各比較例と実施例の純水透過流束（Ｆｌｕｘ）とＮａＣｌ阻止率の関係を図３に示す。図３の通り、実施例１〜３では比較例１〜９で示される純水透過流束とＮａＣｌ阻止率のトレードオフの関係線よりも高い透水性と塩阻止性が得られている。 The relationship between the pure water permeation flux (Flux) and the NaCl inhibition rate of each of the above Comparative Examples and Examples is shown in FIG. As shown in FIG. 3, in Examples 1 to 3, water permeability and salt blocking property higher than the relationship line of the trade-off between the pure water permeation flux and the NaCl blocking rate shown in Comparative Examples 1 to 9 are obtained.
２ ポンプ
３ 密閉容器
４ 平膜セル
５ 原水室
６ スターラー
７ 透過水室
１０ 圧力計
2
Claims (9)
界面重合の際の多官能アミンモノマーの少なくとも一部がヒドロキシ基を有する有機化合物によってエステル化されたものであり、
界面重合の後にエステル結合を加水分解させることにより該緻密層に荷電基を与える加水分解工程を有することを特徴とする選択性透過膜の製造方法。 A method for producing a selective permeable membrane, which comprises a step of forming a dense layer on the surface of a water-permeable base material by interfacially polymerizing a polyfunctional amine monomer and a polyfunctional acid chloride monomer on the surface of the water-permeable base material.
At least a part of the polyfunctional amine monomer during interfacial polymerization is esterified with an organic compound having a hydroxy group.
A method for producing a selective permeable membrane, which comprises a hydrolysis step of imparting a charged group to the dense layer by hydrolyzing an ester bond after interfacial polymerization.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115155342A (en) * | 2022-05-31 | 2022-10-11 | 南京信息工程大学 | Environment-friendly super-hydrophilic copolymer and preparation method of environment-friendly super-hydrophilic copolymer for oil-water separation net film |
| CN115318113A (en) * | 2022-08-03 | 2022-11-11 | 清华大学 | Nanofiltration membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155342A (en) * | 2022-05-31 | 2022-10-11 | 南京信息工程大学 | Environment-friendly super-hydrophilic copolymer and preparation method of environment-friendly super-hydrophilic copolymer for oil-water separation net film |
| CN115155342B (en) * | 2022-05-31 | 2023-04-25 | 南京信息工程大学 | Environment-friendly super-hydrophilic copolymer and preparation method thereof for oil-water separation net film |
| CN115318113A (en) * | 2022-08-03 | 2022-11-11 | 清华大学 | Nanofiltration membrane and preparation method and application thereof |
| CN115318113B (en) * | 2022-08-03 | 2023-10-31 | 清华大学 | Nanofiltration membrane and preparation method and application thereof |
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