JPH0829235B2 - Hydrophilic microporous membrane - Google Patents
Hydrophilic microporous membraneInfo
- Publication number
- JPH0829235B2 JPH0829235B2 JP63047871A JP4787188A JPH0829235B2 JP H0829235 B2 JPH0829235 B2 JP H0829235B2 JP 63047871 A JP63047871 A JP 63047871A JP 4787188 A JP4787188 A JP 4787188A JP H0829235 B2 JPH0829235 B2 JP H0829235B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrophilic
- microporous membrane
- compound
- hydrophilic microporous
- micropore
- 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
- 239000012982 microporous membrane Substances 0.000 title claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- -1 amine compound Chemical class 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は精密ろ過用フィルターなどに用いられる、ポ
リ弗化ビニリデンを微孔形成剤とした親水性微孔膜に関
するものである。TECHNICAL FIELD The present invention relates to a hydrophilic microporous membrane containing polyvinylidene fluoride as a micropore-forming agent, which is used in a filter for microfiltration and the like.
従来技術とその問題点 親水性微孔膜を用いた精密ろ過用フィルターは電子工
業、医薬品工業および食品工業における液体のろ過に用
いられている。Prior art and its problems Microfiltration filters using hydrophilic microporous membranes are used for filtering liquids in the electronic industry, pharmaceutical industry and food industry.
このような用途に用いられる親水性微孔膜としては、
疎水性のポリ弗化ビニリデンを親水化処理したものを微
孔形成剤として用いている。この親水化処理は、従来、
アニオン界面活性剤、ノニオン界面活性剤および水溶性
ポリマー等の親水性のエージェントを微孔の表面に塗布
する方法や微孔膜を製造する前の調整液中に親水性のエ
ージェントを溶解させておく方法が知られていた。As the hydrophilic microporous membrane used for such applications,
Hydrophobicized polyvinylidene fluoride is used as a micropore forming agent. This hydrophilic treatment is conventionally
Method of applying hydrophilic agents such as anionic surfactants, nonionic surfactants and water-soluble polymers to the surface of micropores, or dissolving the hydrophilic agent in the preparation liquid before producing the microporous membrane. The method was known.
このように親水化処理ものは、親水性のエージェント
が物理的に微孔表面に吸着しているか、微孔形成剤中に
包含されているかのいずれかであり、実際に液体のろ過
に用いた場合、この液体中に親水性のエージェントが溶
出してろ液を汚染するという問題があるため、液体のろ
過を行う前に親水性のエージェントを完全に洗い流す必
要があった。As described above, in the hydrophilization treatment, the hydrophilic agent was either physically adsorbed on the surface of the micropores or contained in the micropore-forming agent, and was actually used for filtering the liquid. In this case, since there is a problem that the hydrophilic agent is eluted in the liquid and contaminates the filtrate, it is necessary to completely wash out the hydrophilic agent before filtering the liquid.
しかしながら、親水性のエージェントを完全に洗い流
すことは不可能であり、実用的でないという問題があっ
た。However, there is a problem that it is impossible to completely wash out the hydrophilic agent, which is not practical.
発明の目的 本発明は、上記した問題に鑑みてなされたもので、ろ
液を汚染させることのない、親水性を持続させることの
できる親水性微孔膜を提供することを目的とするもので
ある。OBJECT OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a hydrophilic microporous membrane capable of maintaining hydrophilicity without contaminating the filtrate. is there.
発明の構成 本発明は、上記した目的を達成するために、微孔形成
剤としてのポリ弗化ビニリデンと、親水性のアミノ基を
有するアミン化合物としてのジエチレントリアミン、ト
リエチレンテトラミン、テトラエチレンペンタミンまた
はペンタエチレンヘキサミンとを化学的に結合したこと
を特徴とする。The present invention, in order to achieve the above-mentioned object, polyvinylidene fluoride as a micropore forming agent, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine or an amine compound having a hydrophilic amino group. It is characterized in that it is chemically bonded to pentaethylenehexamine.
すなわち、上記のように、微孔形成剤としてのポリ弗
化ビニリデンと、親水性のアミノ基を有するアミノ化合
物とを化学的に結合することにより、親水性のアミノ基
によって親水性を持続させることのできる親水性微孔膜
を得ることができる。That is, as described above, by chemically bonding polyvinylidene fluoride as a micropore-forming agent and an amino compound having a hydrophilic amino group, the hydrophilicity is maintained by the hydrophilic amino group. It is possible to obtain a hydrophilic microporous membrane that can be obtained.
上記した、親水性のアミノ基を有するアミン化合物と
を化学的に結合する方法としては、液体状アミン化合
物を直接接触させる方法、液体状、固体状アミン化合
物を溶解した溶液に含浸する方法、アミン化合物をガ
ス状にして反応させる方法等があるが、の方法がアミ
ン化合物の濃度によって反応速度を制御することができ
るという点で有利である。この場合、アミン化合物を溶
解する溶剤としては水やアルコール系のものがよく、特
にアルコール系のものは微孔形成剤としてのポリ弗化ビ
ニリデンを侵すことなく、微孔中にすばやくアミン化合
物を導入することができるという点ですぐれている。な
お、ここで用いるアミン化合物は、以下の化学構造で示
される化合物Ｉのポリエチレンポリアミン、化合物IIの
ポリメチレンジアミン、化合物IIIのアルキルモノアミ
ン、芳香族系アミンなどがあるが、化合物Ｉのｎ＝０〜
４のものが反応性の点で有利で、具体的にはジエチレン
トリアミン、トリエチレンテトラミン、テトラエチレン
ペンタミンまたはペンタエチレンヘキサミンが好まし
い。As the above-mentioned method of chemically bonding with the amine compound having a hydrophilic amino group, a method of directly contacting a liquid amine compound, a method of impregnating a liquid or solid amine compound in a solution, an amine There is a method of reacting the compound in a gaseous state, and the method is advantageous in that the reaction rate can be controlled by the concentration of the amine compound. In this case, the solvent for dissolving the amine compound is preferably water or an alcohol-based solvent, and particularly the alcohol-based solvent does not attack polyvinylidene fluoride as a micropore-forming agent and quickly introduces the amine compound into the micropores. It is excellent in that it can be done. The amine compounds used here include polyethylene polyamine of compound I, polymethylene diamine of compound II, alkylmonoamine of compound III, aromatic amine, and the like, which are represented by the following chemical structures. ~
4 is advantageous in terms of reactivity, and specifically, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine is preferable.
化合物I:H2N−C2H4−（−NH−C2H4−）ｎ−NH2 化合物II:H2N−（−CH2−）ｍ−NH2 化合物III:H3C−（−CH2−）ｌ−NH2 実施例 以下、本発明の詳細を実施例に基づいて説明する。Compound I: H 2 N-C 2 H 4 - (- NH-C 2 H 4 -) n -NH 2 compound II: H 2 N - (- CH 2 -) m -NH 2 Compound III: H 3 C- (—CH 2 —) 1 —NH 2 Example Hereinafter, details of the present invention will be described based on examples.
まず、ポリ弗化ビニリデン15重量部をジメチルホルム
アミド85重量部に溶解し、ドクターブレードによりガラ
ス板上に流延し、ジメチルホルムアミドを70パーセント
含む水溶液に浸漬して凝固させる。次に、この凝固させ
た膜をガラス板より剥離し、水で洗浄してジメチルホル
ムアミドを除去して乾燥させる。次に、この乾燥させた
膜を、ジエチレントリアミン、トリエチレンテトラミ
ン、テトラエチレンペンタミンまたはペンタエチレンヘ
キサミンを70重量部溶解したイソプロピルアルコール中
に浸漬し、25℃の温度下で24時間させた後、水洗、乾燥
して本発明の親水性微孔膜を得た。このときの膜の厚み
はいずれも0.15mmで、70cm・Hgにおける透水速度、バブ
ルポイントは以下の表のとおりであった。First, 15 parts by weight of polyvinylidene fluoride is dissolved in 85 parts by weight of dimethylformamide, cast on a glass plate with a doctor blade, and immersed in an aqueous solution containing 70% of dimethylformamide for coagulation. Next, the solidified film is peeled from the glass plate, washed with water to remove dimethylformamide, and dried. Next, the dried film was immersed in isopropyl alcohol in which 70 parts by weight of diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine was dissolved, and the mixture was allowed to stand at a temperature of 25 ° C for 24 hours and then washed with water. Then, it was dried to obtain the hydrophilic microporous membrane of the present invention. The thickness of each film at this time was 0.15 mm, and the water permeation rate and bubble point at 70 cm · Hg were as shown in the table below.
上記した透水速度とバブルポイントの測定は膜を純水
に含浸させることによって測定したもので、水洗、乾燥
を反復させてもほとんど変化は生じなかった。 The measurement of the water permeation rate and the bubble point described above was carried out by impregnating the membrane with pure water, and there was almost no change even after repeated washing and drying.
発明の効果 上記した如く、本発明の親水性微孔膜は、ろ液を汚染
させることのない、親水性を持続させることのできるも
のであるから、その工業的価値はきわめて大である。EFFECTS OF THE INVENTION As described above, the hydrophilic microporous membrane of the present invention is capable of maintaining the hydrophilicity without contaminating the filtrate, and therefore its industrial value is extremely large.
Claims (1)
と、親水性のアミノ基を有するアミン化合物としてのジ
エチレントリアミン、トリエチレンテトラミン、テトラ
エチレンペンタミンまたはペンタエチレンヘキサミンと
を化学的に結合したことを特徴とする親水性微孔膜。1. Polyvinylidene fluoride as a micropore-forming agent and chemically bonded diethylenetriamine, triethylenetetramine, tetraethylenepentamine or pentaethylenehexamine as an amine compound having a hydrophilic amino group. A hydrophilic microporous membrane characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047871A JPH0829235B2 (en) | 1988-03-01 | 1988-03-01 | Hydrophilic microporous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047871A JPH0829235B2 (en) | 1988-03-01 | 1988-03-01 | Hydrophilic microporous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01224002A JPH01224002A (en) | 1989-09-07 |
| JPH0829235B2 true JPH0829235B2 (en) | 1996-03-27 |
Family
ID=12787444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63047871A Expired - Lifetime JPH0829235B2 (en) | 1988-03-01 | 1988-03-01 | Hydrophilic microporous membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0829235B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169512A (en) * | 1983-03-14 | 1984-09-25 | Nok Corp | Preparation of ultrafiltration membrane |
| JPS60110306A (en) * | 1983-11-16 | 1985-06-15 | Nok Corp | Production of permselective membrane |
| JPS60114305A (en) * | 1983-11-22 | 1985-06-20 | Nok Corp | Treatment of hollow fiber module |
-
1988
- 1988-03-01 JP JP63047871A patent/JPH0829235B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01224002A (en) | 1989-09-07 |
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