JP4075236B2 - Production method of polyphenylsulfone hollow fiber membrane - Google Patents
Production method of polyphenylsulfone hollow fiber membrane Download PDFInfo
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- JP4075236B2 JP4075236B2 JP22189299A JP22189299A JP4075236B2 JP 4075236 B2 JP4075236 B2 JP 4075236B2 JP 22189299 A JP22189299 A JP 22189299A JP 22189299 A JP22189299 A JP 22189299A JP 4075236 B2 JP4075236 B2 JP 4075236B2
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- JP
- Japan
- Prior art keywords
- polyphenylsulfone
- hollow fiber
- fiber membrane
- weight
- polyvinylpyrrolidone
- 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.)
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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製造法に関する。更に詳しくは、限外ロ過膜などとして好適に使用されるポリフェニルスルホン中空糸膜の製造法に関する。
【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、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、強度の低下やピンホール発生の原因となり得るフィンガー構造やボイド構造を全く含まず、限外ロ過膜などとして好適に用いられるポリフェニルスルホン中空糸膜の製造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、ポリフェニルスルホンおよび親水性ポリビニルピロリドンの水溶性有機溶媒溶液よりなる紡糸原液を用い、中空糸膜を製造するに際し、ポリフェニルスルホンに対するポリビニルピロリドンの配合比率が80重量%以上であり、かつ親水性有機溶媒がジメチルホルムアミドである紡糸原液を用いてポリフェニルスルホン中空糸膜を製造すること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を製膜成分とする紡糸原液は、そこに親水性ポリビニルピロリドンおよび水溶性有機溶媒が配合され、本発明においては水溶性有機溶媒としてジメチルホルムアミドが用いられる。ジメチルホルムアミドと同様に、この種の紡糸原液の水溶性有機溶媒として用いられているジメチルアセトアミドを用いると、本発明で規定されているようなポリビニルピロリドン/ポリフェニルスルホン比が用いられても、断面にボイド構造を有する中空糸膜しか得られず、限外ロ過膜として使用することはできない。
【０００７】
紡糸原液は、ポリフェニルスルホンが約10〜30重量%、好ましくは約15〜25重量%、ポリビニルピロリドンが約8〜30重量%、好ましくは約12〜20重量%を占めるような配合割合のものが用いられ、更にそこに約5重量%以下、好ましくは約1〜3重量%を占めるような割合の水を配合して用いることができる。
【０００８】
このような配合組成を有する紡糸原液において、用いられるポリビニルピロリドンの平均分子量にもよるが、一般にはポリフェニルスルホンに対するポリビニルピロリドンの配合比率が80重量%以上、好ましくは80〜90重量%となるような配合割合で用いられる。この配合比率がこれ以下では、膜断面にフィンガー構造やボイド構造の生成が避けられない。
【０００９】
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)中で凝固される。
【００１０】
【発明の効果】
耐薬品性、耐熱性などにすぐれたポリフェニルスルホンを製膜原液として用い、断面構造が完全に網目状になっており、強度の低下やピンホールの発生原因となり得るフィンガー構造やボイド構造を全く形成させず、従って限外ロ過膜としての各基本性能を十分に満足させるポリフェニルスルホン中空糸膜を、本発明方法によって製造することができる。
【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
(a)ポリフェニルスルホン 17.8重量部
(テイジンアモコ製品RADEL R5000)
(b)ポリビニルピロリドン K-30 14.9 〃
(BASF社製品;平均分子量約40000)
(c)水 1.0 〃
(d)ジメチルホルムアミド 66.3 〃
以上の各成分よりなり、(b)成分/(a)成分の比が83.7%の紡糸原液を用い、水を芯液として、線速40m/分で乾湿式紡糸を行ない、得られた中空糸膜を121℃の加圧熱水で1時間洗浄し、乾燥させた。
【００１３】
得られたポリフェニルスルホン中空糸膜(外径1.50mm、内径0.90mm)について、電子顕微鏡でその断面を観察すると、完全に網目状となっていて、強度の低下やピンホール発生の原因となり得るフィンガー構造やボイド構造を全く含まず、またその純水透過係数は6.5ml/cm2/hrであり、分画分子量(ポリエチレングリコール換算)は20000、引張強さは550g/本であった。
【００１４】
比較例１〜３
実施例において、紡糸原液の組成が次のように変更された。ただし、比較例3では(d)成分としてジメチルホルムアミドの代りに、ジメチルアセトアミドが用いられた。得られたポリフェニルスルホン中空糸膜(外径1.50mm、内径0.90mm)について、実施例と同様に断面の観察および測定が行われた。
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyphenylsulfone hollow fiber membrane. More specifically, the present invention relates to a method for producing a polyphenylsulfone hollow fiber membrane that is suitably used 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. However, there is a problem that a hollow fiber membrane that is suitably used as an ultrafiltration membrane or the like cannot be easily obtained due to a narrow allowable range of blending conditions and the like.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a polyphenylsulfone hollow fiber membrane that does not include any finger structure or void structure that may cause strength reduction or pinhole generation, and that can be suitably used as an ultrafiltration membrane or the like. There is.
[0004]
[Means for Solving the Problems]
An object of the present invention is to use a spinning stock solution comprising a water-soluble organic solvent solution of polyphenylsulfone and hydrophilic polyvinylpyrrolidone, and in the production of a hollow fiber membrane, the blending ratio of polyvinylpyrrolidone to polyphenylsulfone is 80% by weight or more. And a polyphenylsulfone hollow fiber membrane is produced using a spinning stock solution in which the hydrophilic organic solvent is dimethylformamide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Polyphenylsulfone is a repeating unit shown below
[0006]
A spinning stock solution containing polyphenylsulfone as a film-forming component is blended with hydrophilic polyvinylpyrrolidone and a water-soluble organic solvent. In the present invention, dimethylformamide is used as the water-soluble organic solvent. Similar to dimethylformamide, using dimethylacetamide, which is used as a water-soluble organic solvent for this type of spinning stock solution, even if the polyvinylpyrrolidone / polyphenylsulfone ratio as defined in the present invention is used, Only a hollow fiber membrane having a void structure can be obtained, and cannot be used as an ultrafiltration membrane.
[0007]
The spinning dope has a blending ratio such that polyphenylsulfone accounts for about 10 to 30% by weight, preferably about 15 to 25% by weight, and polyvinylpyrrolidone accounts for about 8 to 30% by weight, preferably about 12 to 20% by weight. Further, water can be blended and used in such a proportion that it accounts for about 5% by weight or less, preferably about 1 to 3% by weight.
[0008]
In the spinning dope having such a composition, depending on the average molecular weight of the polyvinylpyrrolidone used, generally the blending ratio of polyvinylpyrrolidone to polyphenylsulfone is 80% by weight or more, preferably 80 to 90% by weight. Used in various proportions. If the blending ratio is less than this, it is inevitable that a finger structure or a void structure is generated in the film cross section.
[0009]
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) represented by water.
[0010]
【The invention's effect】
Polyphenylsulfone, which has excellent chemical resistance and heat resistance, is used as a film-forming stock solution, and the cross-sectional structure is completely reticulated, completely having a finger structure and void structure that can cause strength reduction and pinholes. A polyphenylsulfone hollow fiber membrane which is not formed and thus sufficiently satisfies each basic performance as an ultrafiltration membrane can be produced by the method of the present invention.
[0011]
【Example】
Next, the present invention will be described with reference to examples.
[0012]
Example
(a) 17.8 parts by weight of polyphenylsulfone
(Teijin Amoco product RADEL R5000)
(b) Polyvinylpyrrolidone K-30 14.9
(BASF products; average molecular weight of about 40,000)
(c) Water 1.0 〃
(d) Dimethylformamide 66.3
The hollow fiber obtained by using the above-mentioned components, using a spinning stock solution in which the ratio of (b) component / (a) component is 83.7%, using water as the core solution, and performing dry and wet spinning at a linear speed of 40 m / min. The membrane was washed with pressurized hot water at 121 ° C. for 1 hour and dried.
[0013]
When the cross section of the obtained polyphenylsulfone hollow fiber membrane (outer diameter 1.50 mm, inner diameter 0.90 mm) is observed with an electron microscope, it is completely reticulated, which may cause strength reduction and pinhole generation. It contained no finger structure or void structure, had a pure water permeability coefficient of 6.5 ml / cm 2 / hr, a molecular weight cut-off (in terms of polyethylene glycol) of 20000, and a tensile strength of 550 g / tube.
[0014]
Comparative Examples 1-3
In the examples, the composition of the spinning dope was changed as follows. However, in Comparative Example 3, dimethylacetamide was used in place of dimethylformamide as the component (d). The obtained polyphenylsulfone hollow fiber membrane (outer diameter 1.50 mm, inner diameter 0.90 mm) was observed and measured in the same manner as in the examples.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22189299A JP4075236B2 (en) | 1999-08-05 | 1999-08-05 | Production method of polyphenylsulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22189299A JP4075236B2 (en) | 1999-08-05 | 1999-08-05 | Production method of polyphenylsulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001046847A JP2001046847A (en) | 2001-02-20 |
| JP4075236B2 true JP4075236B2 (en) | 2008-04-16 |
Family
ID=16773817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22189299A Expired - Fee Related JP4075236B2 (en) | 1999-08-05 | 1999-08-05 | Production method of polyphenylsulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4075236B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100493113B1 (en) * | 2001-12-07 | 2005-05-31 | 주식회사 코오롱 | A braid-reinforced hollow fiber membrane |
| JP2015221400A (en) * | 2014-05-22 | 2015-12-10 | Nok株式会社 | Manufacturing method of hollow fiber membrane for ultrafiltration membrane |
| US20190374909A1 (en) * | 2017-03-01 | 2019-12-12 | Nok Corporation | Method for producing a polyphenylsulfone porous hollow fiber membrane |
-
1999
- 1999-08-05 JP JP22189299A patent/JP4075236B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP2001046847A (en) | 2001-02-20 |
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