JP4120103B2 - Method for treating polyphenylsulfone hollow fiber membrane - Google Patents
Method for treating polyphenylsulfone hollow fiber membrane Download PDFInfo
- Publication number
- JP4120103B2 JP4120103B2 JP22189399A JP22189399A JP4120103B2 JP 4120103 B2 JP4120103 B2 JP 4120103B2 JP 22189399 A JP22189399 A JP 22189399A JP 22189399 A JP22189399 A JP 22189399A JP 4120103 B2 JP4120103 B2 JP 4120103B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- fiber membrane
- treating
- polyphenylsulfone
- polyphenylsulfone hollow
- 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 - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims description 28
- 239000012510 hollow fiber Substances 0.000 title claims description 21
- 229920000491 Polyphenylsulfone Polymers 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- 229920003295 Radel® Polymers 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ポリフェニルスルホン中空糸膜の処理方法に関する。更に詳しくは、限外ロ過膜などとして好適に使用されるものを与え得る、ポリフェニルスルホン中空糸膜の処理方法に関する。
【０００２】
【従来の技術】
ポリフェニルスルホン中空糸膜は、一般的に多く使用されているポリスルホン中空糸膜と比較して、耐薬品性、耐熱性などの点でよりすぐれているものの、膜設計時の配合比率、配合剤、配合条件等の許容範囲が狭く、特に大孔径の中空糸膜を得ることが困難であって、限外ロ過膜などとして好適に使用される中空糸膜が容易に得られないという問題がみられる。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、乾湿式紡糸されたポリフェニルスルホン中空糸膜であって、大孔径を形成し、従って限外ロ過膜などとして好適に使用し得るものを与え得る中空糸膜の処理方法を提供することにある。
【０００４】
【課題を解決するための手段】
かかる本発明の目的は、乾湿式紡糸されたポリフェニルスルホン中空糸膜を濃度 5 〜 50 重量 % のグリセリン水溶液中に浸漬させ、 105 〜 150 ℃で処理する方法によって達成される。
【０００５】
【発明の実施の形態】
ポリフェニルスルホンは、以下に示されるくり返し単位
【０００６】
ポリフェニルスルホンと共に、親水性高分子、例えばポリビニルピロリドン、ポリアルキレングリコール等をブレンドして用いることが好ましい。以上の各成分に加えて、紡糸原液の相状態を調整するために添加される水およびジメチルホルムアミド、ジエチルホルムアミド、ジメチルアセトアミド、N-メチロ-2-ピロリドン等の水溶性の非プロトン性極性溶媒を用いて、紡糸原液が調製される。
【０００７】
調製される紡糸原液(ドープ液)は、重量割合でポリフェニルスルホンが約10〜30%、好ましくは約15〜25%、親水性高分子が約5〜30%、好ましくは約12〜20%、水が約5%以下、好ましくは約1〜3%で、残りが水溶性有機溶媒よりなる。
【０００８】
かかる紡糸原液を用いての乾湿式紡糸は、必要に応じて水によって代表される水性液を芯液として用い、通常の乾湿式紡糸法によって中空糸膜状に紡糸される。
紡糸された中空糸膜は、やはり水によって代表される凝固浴(ゲル化浴)中で凝固され、その後湿潤状態のままグリセリン水溶液による処理に付される。
【０００９】
グリセリン水溶液による処理は、約5〜50重量%、好ましくは約5〜30重量%の水溶液を用い、約105〜150℃、好ましくは約105〜130℃で約20〜90分間程度行われる。グリセリン水溶液の濃度がこれよりも低いものを用いると、本発明の目的とする大孔径化を達成することができず、一方これ以上の濃度のものを用いると、膜表面に残存するグリセリンによって、膜本来の性能が阻害されるようになる。これらの処理条件は、求められる中空糸膜の分画性能などを考慮することによって、最適の条件を任意に選択して決めることができる。
【００１０】
【発明の効果】
乾湿式紡糸法によって得られたポリフェニルスルホン中空糸膜をグリセリン水溶液で浸漬処理するだけで、中空糸膜の基本性能である純水透過係数や分画分子量を改善することができ、かかる大孔径を有するポリフェニルスルホン中空糸膜は限外ロ過膜などとして有効に使用することができる。
【００１１】
【実施例】
次に、実施例について本発明を説明する。
【００１２】
実施例
ジフェニルスルホン 17.8重量部
(テイジンアモコ製品RADEL R5000)
ポリビニルピロリドン(BASF社製品、K-30) 14.9 〃
水 1.0 〃
ジメチルホルムアミド 66.3 〃
上記組成の紡糸原液を、水を芯液として、紡糸速度40m/分で乾湿式紡糸した。得られた中空糸膜(外径1.50mm、内径0.90mm)を、所定濃度のグリセリン水溶液中に浸漬させ、耐圧容器内で121℃で60分間処理した。
【００１３】
このグリセリン処理ジフェニルスルホン中空糸膜について、純水透過係数(1.0Kgf/cm2)および分画分子量(ポリエチレングリコール換算)の測定を行ない、次の表に示されるような結果を得た。
BACKGROUND OF THE INVENTION
The present invention relates to a method for treating a polyphenylsulfone hollow fiber membrane. More specifically, the present invention relates to a method for treating a polyphenylsulfone hollow fiber membrane, which can be used suitably as an ultrafiltration membrane.
[0002]
[Prior art]
Polyphenylsulfone hollow fiber membranes are superior in terms of chemical resistance and heat resistance compared to commonly used polysulfone hollow fiber membranes. In addition, there is a problem that the allowable range such as the blending conditions is narrow, it is particularly difficult to obtain a hollow fiber membrane having a large pore diameter, and a hollow fiber membrane suitably used as an ultrafiltration membrane cannot be easily obtained. Be looked at.
[0003]
[Problems to be solved by the invention]
An object of the present invention is a method for treating a hollow fiber membrane, which is a dry and wet-spun polyphenylsulfone hollow fiber membrane, which has a large pore diameter and can therefore be suitably used as an ultrafiltration membrane. Is to provide.
[0004]
[Means for Solving the Problems]
The object of the present invention is achieved by a method in which a dry and wet-spun polyphenylsulfone hollow fiber membrane is immersed in an aqueous glycerin solution having a concentration of 5 to 50 % by weight and treated at 105 to 150 ° C.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Polyphenylsulfone is a repeating unit shown below
[0006]
It is preferable to use a blend of a hydrophilic polymer such as polyvinyl pyrrolidone and polyalkylene glycol together with polyphenylsulfone. In addition to the above components, water and water-soluble aprotic polar solvents such as dimethylformamide, diethylformamide, dimethylacetamide and N-methylo-2-pyrrolidone are added to adjust the phase state of the spinning dope. Used to prepare a spinning dope.
[0007]
The prepared spinning solution (dope solution) is about 10-30% polyphenylsulfone, preferably about 15-25%, and about 5-30% hydrophilic polymer, preferably about 12-20% by weight. The water is about 5% or less, preferably about 1 to 3%, and the remainder is a water-soluble organic solvent.
[0008]
Dry and wet spinning using such a spinning dope is spun into a hollow fiber membrane by an ordinary dry and wet spinning method using an aqueous liquid typified by water as a core liquid as necessary.
The spun hollow fiber membrane is coagulated in a coagulation bath (gelation bath) also represented by water, and then subjected to a treatment with an aqueous glycerin solution in a wet state.
[0009]
The treatment with the glycerin aqueous solution is performed at about 105 to 150 ° C., preferably about 105 to 130 ° C. for about 20 to 90 minutes, using an aqueous solution of about 5 to 50% by weight, preferably about 5 to 30% by weight. If the concentration of the glycerin aqueous solution is lower than this, it is not possible to achieve the purpose of increasing the pore size of the present invention. On the other hand, if a concentration higher than this is used, the glycerin remaining on the membrane surface The original performance of the membrane is disturbed. These treatment conditions can be determined by arbitrarily selecting the optimum conditions in consideration of the required fractionation performance of the hollow fiber membrane.
[0010]
【The invention's effect】
By simply immersing the polyphenylsulfone hollow fiber membrane obtained by the dry and wet spinning method with an aqueous glycerin solution, the basic performance of the hollow fiber membrane, such as the pure water permeability coefficient and the molecular weight cut off, can be improved. The polyphenylsulfone hollow fiber membrane having the above can be effectively used as an ultrafiltration membrane.
[0011]
【Example】
Next, the present invention will be described with reference to examples.
[0012]
Example 17.8 parts by weight of diphenylsulfone
(Teijin Amoco product RADEL R5000)
Polyvinylpyrrolidone (BASF product, K-30) 14.9 〃
Water 1.0 〃
Dimethylformamide 66.3 〃
The spinning stock solution having the above composition was dry and wet spun at a spinning speed of 40 m / min using water as a core solution. The obtained hollow fiber membrane (outer diameter 1.50 mm, inner diameter 0.90 mm) was immersed in an aqueous glycerin solution having a predetermined concentration and treated in a pressure vessel at 121 ° C. for 60 minutes.
[0013]
The glycerin-treated diphenylsulfone hollow fiber membrane was measured for pure water permeability coefficient (1.0 kgf / cm 2 ) and fractional molecular weight (in terms of polyethylene glycol), and the results shown in the following table were obtained.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22189399A JP4120103B2 (en) | 1999-08-05 | 1999-08-05 | Method for treating polyphenylsulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22189399A JP4120103B2 (en) | 1999-08-05 | 1999-08-05 | Method for treating polyphenylsulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001046848A JP2001046848A (en) | 2001-02-20 |
| JP4120103B2 true JP4120103B2 (en) | 2008-07-16 |
Family
ID=16773832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22189399A Expired - Fee Related JP4120103B2 (en) | 1999-08-05 | 1999-08-05 | Method for treating polyphenylsulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4120103B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289228A (en) * | 2001-03-22 | 2002-10-04 | Nok Corp | Humidifier and its use |
| JP2015221400A (en) * | 2014-05-22 | 2015-12-10 | Nok株式会社 | Manufacturing method of hollow fiber membrane for ultrafiltration membrane |
-
1999
- 1999-08-05 JP JP22189399A patent/JP4120103B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001046848A (en) | 2001-02-20 |
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