JPS63302904A - Multi-layered composite hollow fiber containing fluid and its production - Google Patents
Multi-layered composite hollow fiber containing fluid and its productionInfo
- Publication number
- JPS63302904A JPS63302904A JP13902987A JP13902987A JPS63302904A JP S63302904 A JPS63302904 A JP S63302904A JP 13902987 A JP13902987 A JP 13902987A JP 13902987 A JP13902987 A JP 13902987A JP S63302904 A JPS63302904 A JP S63302904A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- polymer
- hollow fiber
- composite hollow
- crystalline polymer
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 239000012530 fluid Substances 0.000 title claims abstract description 23
- 239000012510 hollow fiber Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000012528 membrane Substances 0.000 claims abstract description 83
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 238000009987 spinning Methods 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- -1 polypropylene Polymers 0.000 abstract description 8
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 2
- 230000009477 glass transition Effects 0.000 abstract description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Multicomponent Fibers (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
Ｃ産業上の利用分野〕
本発明は、ボイラー、エンジン等の燃焼効率を北げたり
、燃焼温度を上げたりするために高酸素透過速度が必要
となる分野や、水−アルコール分離の分野等で用いられ
る中空糸状の選択分離膜、およびこの選択分離膜の製造
方法に関する。Detailed Description of the Invention C. Industrial Field of Application The present invention is applicable to fields where a high oxygen permeation rate is required to increase the combustion efficiency or combustion temperature of boilers, engines, etc. - A hollow fiber selective separation membrane used in the field of alcohol separation, etc., and a method for manufacturing this selective separation membrane.
物質を分離する技術は、古くから数多くの方法が開発さ
れ、改良が毛ねられてきた。■り分離技術もその一つで
あるが、その改良の経過をみると。Many methods for separating substances have been developed and improvements have been made since ancient times. ■Separation technology is one such technology, and let's take a look at the progress of its improvements.
優れた膜材料の開発、分離効率を高めるための薄膜化技
術の開発、装置効率を高めるための中空糸膜の開発等が
大きな技術開発の流れとなっている。Major trends in technological development include the development of superior membrane materials, the development of thin membrane technology to increase separation efficiency, and the development of hollow fiber membranes to increase device efficiency.
物質の透過速度を高める素材の開発として、自由体積が
大きく、高分子セグメント間の相互作用が小さいポリマ
ーの開発が一つの方向として進められており、使用温度
で膜の構成素材が液体である液膜が最も透過速度が高い
と考えられる。しかし、従来の液膜は、その素材が隔膜
を通過してしまう等安定性に欠けており、また、薄膜化
も困難であることから実用化が難しい状況にある。One way to develop materials that increase the permeation rate of substances is to develop polymers that have a large free volume and low interaction between polymer segments. The membrane is considered to have the highest permeation rate. However, conventional liquid films lack stability, such as the material passing through the diaphragm, and are also difficult to make into thin films, making it difficult to put them into practical use.
分離膜を形成する方法として、溶融賦形による方法が従
来より知られているが、この方法による薄膜化では、薄
膜素材中に含まれるゴミ、気泡等の影響により、膜厚を
薄くするにつれてピンホール等の膜欠陥による分＃機能
の低下が顕われることが大きな問題となっていた。Melt-forming is a conventionally known method for forming separation membranes, but this method has problems with thinning the membrane as it becomes thinner due to the effects of dust, air bubbles, etc. contained in the membrane material. A major problem has been that the film's functionality deteriorates due to film defects such as holes.
本発明の目的は、非常に薄く、かつ分離操作時の温度で
流体状である素材を分離膜として有する新規な形態の選
択分離膜を提供することにある。An object of the present invention is to provide a novel selective separation membrane having a material that is extremely thin and fluid at the temperature during separation operation.
本発明の他の目的は、透過速度の高い選択分離膜を提供
することにある。Another object of the present invention is to provide a selective separation membrane with a high permeation rate.
本発明のもう一つの目的は、このような選択分＃膜を、
安定した形で製造できる方法を提供することにある。Another object of the present invention is to prepare such selective membranes by
The purpose is to provide a method that allows production in a stable manner.
すなわち、本発明の多層複合中空糸膜は、分離機能を受
け持つ分離膜（Ａ）と、補強機部を受け持つ多孔膜（Ｂ
）とからなる中空繊維状膜であって、分＃膜（Ａ）と多
孔１ｔ！Ｊ （Ｂ）とは交互に積層されており、該中空
繊維状膜の内表面および外表面が多孔膜（Ｂ）からなる
構造を有する多層複合中空糸膜において、該分＃膜（Ａ
）が選択性ｇＩ機俺を有する常温で流体状の高分子（Ａ
ｏ）からなり、多孔膜（Ｂ）が結晶性高分子（Ｂｏ）か
らなり、流体状の高分子（Ａｏ）の分子の大きさが多孔
膜（Ｂ）の孔の大きさよりも大きいものであることを特
徴とする。That is, the multilayer composite hollow fiber membrane of the present invention comprises a separation membrane (A) that takes charge of the separation function, and a porous membrane (B) that takes charge of the reinforcement part.
) is a hollow fibrous membrane consisting of a membrane (A) and a porous 1t! In a multilayer composite hollow fiber membrane having a structure in which the inner and outer surfaces of the hollow fibrous membrane are composed of the porous membrane (B), the membranes (A
) is a polymer (A) that is fluid at room temperature and has selectivity.
o), the porous membrane (B) is made of a crystalline polymer (Bo), and the molecular size of the fluid polymer (Ao) is larger than the pore size of the porous membrane (B). It is characterized by
また、本発明の多層複合中空糸膜の製造方法は、多重円
筒紡糸ノズルに１分離膜（Ａ）を形成する常温で流体状
の高分子（Ａｏ）および多孔膜（Ｂ）を形成する結晶性
高分子（Ｂｏ）を、最外層および最内層に結晶性高分子
（Ｂｏ）が配置され、かつ高分子（Ａｏ）および高分子
（Ｂｏ）が交互にサンドイッチ状に配置されるように供
給して多層複合中空繊維を紡糸する工程と、多孔膜（Ｂ
）の孔の大きさが分離膜（Ａ）の流体状高分子（Ａｏ）
の分子の大きさよりも小さくなるように、得られた多層
複合中空ｍ維を延伸して、結晶性高分子（Ｂｏ）の層を
多孔化する工程とを有することを特徴とする。In addition, the method for producing a multilayer composite hollow fiber membrane of the present invention includes a polymer (Ao) that is fluid at room temperature to form a single separation membrane (A) in a multi-cylindrical spinning nozzle, and a crystalline polymer to form a porous membrane (B). The polymer (Bo) is supplied such that the crystalline polymer (Bo) is arranged in the outermost layer and the innermost layer, and the polymer (Ao) and the polymer (Bo) are arranged alternately in a sandwich shape. The process of spinning multilayer composite hollow fibers and the porous membrane (B
) of the fluid polymer (Ao) of the separation membrane (A).
The method is characterized by comprising a step of making the layer of the crystalline polymer (Bo) porous by stretching the obtained multilayer composite hollow m-fiber so that the size of the crystalline polymer (Bo) is smaller than the molecular size of the crystalline polymer (Bo).
本発明の多層複合中空糸膜は、少なくとも三層構造を有
している。外表面および内表面が、補強材としての多孔
膜（Ｂ）からなっており、中間層が１選択分離機能を有
する流体状のごく薄い分離ｎり（Ａ）からなっている、
基本的には、分＃膜（Ａ）層は一層で充分であるが、目
的に応じて分離膜（Ａ）を二層以上の多層構造としても
よい。The multilayer composite hollow fiber membrane of the present invention has at least a three-layer structure. The outer and inner surfaces are made of a porous membrane (B) as a reinforcing material, and the middle layer is made of a very thin fluid-like separation layer (A) having a one-selection separation function.
Basically, one layer of the separation membrane (A) is sufficient, but depending on the purpose, the separation membrane (A) may have a multilayer structure of two or more layers.
分離膜においては分離機能を受け持つ層が最も重要であ
るが、それが最外層にあると取り扱い時等に損傷するお
それがある。しかし、本発明の中空糸膜では三層以上の
多層構造の中間層に分＃＊能を有する層を配しているた
めにこのような危険性がない。The most important layer in a separation membrane is the layer responsible for the separation function, but if it is the outermost layer, there is a risk of damage during handling. However, in the hollow fiber membrane of the present invention, there is no such danger because the layer having the function is disposed in the middle layer of the multilayer structure of three or more layers.
また、同心円状の多層サンドイッチ構造という特異な構
造のために、層間に接着性が無くても積層構造が安定に
保持できることから、各層の素材の選択について接着性
による制約がないという特徴がある。このことは、モ膜
では達成不可壱であり、中空糸膜の大きな特徴の一つで
ある。他の薄膜形成技術である、蒸着技術、プラズマ重
合技術、コーティング技術等では、いずれにおいても分
離膜と基材との接着性が解決すべき一つの大きな課題と
なっていた。Furthermore, due to the unique structure of a concentric multilayer sandwich structure, the laminated structure can be stably maintained even without adhesiveness between the layers, so there is no restriction on the selection of materials for each layer due to adhesiveness. This cannot be achieved with membranes, and is one of the major features of hollow fiber membranes. In other thin film forming technologies, such as vapor deposition technology, plasma polymerization technology, and coating technology, one major problem that must be solved is the adhesion between the separation membrane and the base material.
本発明において、酸素富化や水−アルコール分＃等の選
択分＃機能を受け持つ分離膜（Ａ）を形成する常温で流
体状の高分子（Ａｏ）としては、シリコン系重合体や、
シリコン系重合体とパーフロロアルキル系フッ素含有重
合体、ポリ−４−ビニルピリジン等の共重合体が挙げら
れる。この流体状分子（Ａｏ）は、室温下で１０−１０
０００ボイズ、より好ましくは １００〜５０００ポイ
ズ程度の粘度を有するものであることが望ましい。In the present invention, the polymer (Ao) which is fluid at room temperature and which forms the separation membrane (A) that takes charge of oxygen enrichment, water-alcohol component function, etc., is a silicon-based polymer,
Examples include copolymers of silicone polymers, perfluoroalkyl fluorine-containing polymers, and poly-4-vinylpyridine. This fluid molecule (Ao) is 10-10 at room temperature.
000 poise, more preferably 100 to 5000 poise.
一方、補強機能を分担する多孔膜（Ｂ）を形成する重合
体としては、各種のものを使用することができるが、延
伸操作によって容易に多孔質化でき、その孔の大きさを
調整できることから結晶性高分子（Ｂｏ）を用いること
が適当である。このような結晶性高分子の代表的なもの
として、ポリエチレン、ポリプロピレン、ポリ−４−メ
チルペンテン−１等のポリオレフィン系ポリマーおよび
ポリフッ化ビニリデン、テトラフロロエチレン等のフッ
素含有ポリマーが挙げられる。On the other hand, various polymers can be used to form the porous membrane (B) that performs the reinforcing function, but since it can be easily made porous by stretching and the size of the pores can be adjusted, It is appropriate to use a crystalline polymer (Bo). Typical examples of such crystalline polymers include polyolefin polymers such as polyethylene, polypropylene, and poly-4-methylpentene-1, and fluorine-containing polymers such as polyvinylidene fluoride and tetrafluoroethylene.
以下、多孔膜（日）層を溶融紡糸、延伸によって多孔化
する方法を例にとり、本発明の多層複合中空Ｒ離脱の製
造方法につき説明する。Hereinafter, the method for manufacturing the multilayer composite hollow R-separated film of the present invention will be explained, taking as an example a method for making a porous membrane layer porous by melt spinning and stretching.
多重円筒型紡糸ノズルを用いて多層複合中空糸を紡糸す
るにあたり、紡糸ノズルに、分＃膜（Ａ）を形成する常
温で流体状の高分子（Ａｏ）および多孔１１！２（Ｂ）
を形成する結晶性高分子（Ｂｏ）を、最外層および最内
層に結晶性高分子（Ｂｏ）が配置され、かっ高分子（Ａ
ｏ）および高分子（Ｂｏ）が交互にサンドイッチ状に配
置されるように供給して紡糸する。紡糸ノズルの多重円
筒は、３層以上の奇数層とされる。紡糸温度は、結晶性
高分子（Ｂｏ）の融点から融点より約８０℃高い温度ま
での範囲とするのが奸ましく、紡糸ドラフトは３０以上
とすることが好ましい、紡糸温度が、結晶性高分子（Ｂ
ｏ）の融点より約８０℃高い温度を超えると安定した紡
糸ができにくくなり、また、紡糸ドラフトが３０未満で
あると、結晶性高分子（Ｂｏ）の配向が低くなり、引き
続き実施される延伸工程で十分延伸できず、その結果、
多孔膜（Ｂ）層に微小空孔が形成されにくくなる。When spinning a multilayer composite hollow fiber using a multi-cylindrical spinning nozzle, the spinning nozzle contains a polymer (Ao) that is fluid at room temperature and pores 11!2 (B) that form a membrane (A).
A crystalline polymer (Bo) is arranged in the outermost layer and an innermost layer to form a crystalline polymer (Bo).
o) and the polymer (Bo) are fed and spun so that they are alternately arranged in a sandwich pattern. The multi-cylinder of the spinning nozzle has an odd number of layers of three or more layers. The spinning temperature is preferably in the range from the melting point of the crystalline polymer (Bo) to a temperature approximately 80°C higher than the melting point, and the spinning draft is preferably 30 or higher. Molecule (B
If the temperature exceeds about 80°C higher than the melting point of o), it becomes difficult to perform stable spinning, and if the spinning draft is less than 30, the orientation of the crystalline polymer (Bo) will become low and the subsequent stretching It could not be stretched sufficiently during the process, and as a result,
Micropores are less likely to be formed in the porous membrane (B) layer.
このとき、薄膜に形成される高分子（Ａｏ）の粘度は極
めて低くなっているのでｌμｓ以下のメツシュを通過さ
せることが可能となり、高分子（Ａｏ）の微少なゴミ、
気泡を除去することができ、薄い分離ｎ１Ａ）の膜欠陥
を大幅に減少させることができる。通常のエラストマー
の溶融賦形ではその粘度が高いのでメツシュを通過させ
て微少なゴミ、気泡を除去することはできないことであ
り、分＃膜（Ａ）に常温で流体状の高分子（八°）を用
いることの大きな特徴である。At this time, the viscosity of the polymer (Ao) formed in the thin film is extremely low, so it is possible to pass through the mesh of less than 1μs, and the minute particles of the polymer (Ao),
Air bubbles can be removed and membrane defects in thin separation n1A) can be significantly reduced. Due to the high viscosity of ordinary melt-forming elastomers, it is impossible to pass them through a mesh to remove minute dust and air bubbles. ) is a major feature of using.
このようにして紡糸して得られた中空糸膜は、所望によ
り結晶性高分子（Ｂｏ）のガラス転移温度以ト融点未満
の温度範囲で７ニール処理された後、０℃から結晶性高
分子（Ｂｏ）の融点より ５℃低い温度までの範囲の温
度下で５〜１５０％延伸し、結晶性高分子（Ｂｏ）から
なる層にミクロクラックを発生させる０次いで上記の延
伸温度より高く結晶性高分子（Ｂｏ）の融点より低い温
度で１段または多段に延伸してミクロクラックにより生
成した孔を拡大し、孔形状を安定化させる。この延伸条
件は、多孔膜（Ｂ）の孔の大きさが分離膜（Ａ）の波体
状高分子（八°）の分子の大きさよりも小さくなるよう
、すなわち多孔膜の細孔から流体状高分子（Ａｏ）が流
れ出ないように選定される。The hollow fiber membrane obtained by spinning in this manner is optionally subjected to a 7-neal treatment in a temperature range below the glass transition temperature of the crystalline polymer (Bo) and below the melting point of the crystalline polymer (Bo). (Bo) is stretched 5 to 150% at a temperature 5°C lower than the melting point of the crystalline polymer (Bo) to generate microcracks in the layer made of crystalline polymer (Bo). The pores generated by microcracks are expanded by stretching in one stage or in multiple stages at a temperature lower than the melting point of the polymer (Bo), and the pore shape is stabilized. This stretching condition is such that the size of the pores of the porous membrane (B) is smaller than the molecular size of the corrugated polymer (8°) of the separation membrane (A), that is, the pores of the porous membrane are It is selected so that the polymer (Ao) does not flow out.
なお、本発明にいう流体状高分子（八゛）の分子の大き
さとは、該分子の両末端距離より算出される値を目安と
するのが適当である。また、多孔膜（Ｂ）の孔の大きさ
とは、細孔の最大孔径をいう。It is appropriate that the size of the molecule of the fluid polymer (8') referred to in the present invention is based on a value calculated from the distance between both ends of the molecule. Moreover, the pore size of the porous membrane (B) refers to the maximum pore diameter of the pores.
流体状高分子の両末端距離は、次式により算出される。The distance between both ends of the fluid polymer is calculated by the following formula.
ただし、（〒２）Ｔ は両末端距離、ｎは重合度、ｌは
結合長、θは結合角、φは回転角を表わし、ＣｏＳφは
ＣＱＳφの平均値を表わす。Here, (〒2)T represents the distance between both ends, n represents the degree of polymerization, l represents the bond length, θ represents the bond angle, φ represents the rotation angle, and CoSφ represents the average value of CQSφ.
本発明の多層複合中空糸膜は、
（１）紡糸、延伸という簡易な操作により流体を挟み込
み、かつ薄膜に賦形できる。The multilayer composite hollow fiber membrane of the present invention can (1) sandwich a fluid and form into a thin film by simple operations such as spinning and stretching;
（２）選択分離機能を受け持つ薄い分離膜が直接外部に
出ていないので損傷の心配がなく安定に存在できる、
（３）分＃、膜を構成する素材が常温で流体であるため
膜中の透過分子拡散速度が非常に大きい、（４）分離膜
層と多孔膜層との居間に接着性が不要なので分離膜を構
成する素材選定の自由度が大きい、
（５）中空糸膜は単位体積当りの膜面積がモ膜に比ベて
大きいので、コンパクトなモジュールが設計可能である
、
という大きな利点がある。(2) The thin separation membrane that performs the selective separation function is not directly exposed to the outside, so it can exist stably without worrying about damage. (3) The material that makes up the membrane is a fluid at room temperature, so the The permeation molecule diffusion rate is very high. (4) There is no need for adhesion between the separation membrane layer and the porous membrane layer, so there is a high degree of freedom in selecting the material that makes up the separation membrane. (5) Hollow fiber membranes have a large unit volume. Since the per membrane area is larger than that of a monomembrane, it has the great advantage of being able to design a compact module.
以下、実施例により本発明を更に詳細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
同心円状に配置された三つの吐出口を有する中空糸製造
用紡糸ノズルに対して、最内層と最外層のポリマー素材
としてポリプロピレン（メルトインデックス１５）、中
間層の流体状高分子素材としてポリジメチルシロキサン
オイル（重量平均分子量＝ ５０００．０００、両末端
距離＝ ０．０２５１Ｌ１１．２０℃での粘度＝２５０
ポイズ）を用い、吐出温度１９５℃、吐出線速度３ｃｍ
／ｗｉｎ、巻取速度Ｓｏｗ／ｓｉｎで紡糸した。得られ
た未延伸糸は内径２００騨であり、最も内側の層から各
々２５．０．２および２５騨の厚さを有する同心円状に
配された三層より成りたっていた。Example 1 For a spinning nozzle for manufacturing hollow fibers having three discharge ports arranged concentrically, polypropylene (melt index 15) was used as the polymer material for the innermost and outermost layers, and polypropylene (melt index 15) was used as the fluid polymer material for the middle layer. Polydimethylsiloxane oil (weight average molecular weight = 5000.000, distance between both ends = 0.0251L11. Viscosity at 20°C = 250
Poise), discharge temperature 195℃, discharge linear velocity 3cm
/win and the winding speed was Sow/sin. The resulting undrawn yarn had an internal diameter of 200 mm and consisted of three concentrically arranged layers having thicknesses of 25 mm, 0.2 mm, and 25 mm, respectively, starting from the innermost layer.
この未延伸中空糸を１４０℃で１時間アニール処理した
。更にアニール糸を室温下で８０％延伸し、引き続き
１２０℃に加熱された加熱炉中で総延伸にが１００％に
なるまで熱延伸を行い複合中空糸膜を得た。得られた複
合中空糸膜は内径が１８０μｓで最も内側の層から２０
． ０．１および２０騨の厚さを有する同心円状に配さ
れた三層から成っており、電子顕微鏡で観察した結果、
内表面と外表面にはスリット状の孔が形成されていた。This undrawn hollow fiber was annealed at 140° C. for 1 hour. Furthermore, the annealed yarn was stretched by 80% at room temperature, and then
Hot stretching was performed in a heating furnace heated to 120° C. until the total stretching was 100% to obtain a composite hollow fiber membrane. The obtained composite hollow fiber membrane has an inner diameter of 180 μs and a distance of 20 μs from the innermost layer.
．． It consists of three layers arranged concentrically with a thickness of 0.1 and 20 mm, and as a result of observation with an electron microscope,
Slit-like holes were formed on the inner and outer surfaces.
スリットのサイズは幅が０．００５〜０．０１０ｕで、
長さが０．０１５〜０．０２０ｇであり、流体状高分子
の両末端距離よりも小さかった。The width of the slit is 0.005~0.010u,
The length was 0.015 to 0.020 g, which was smaller than the distance between both ends of the fluid polymer.
この複合中空糸膜を容器の中に入れ、複合中空糸膜の両
末端に容器と複合中空糸膜を接着するボッティング剤を
流し込み、モジュールを製作した。ただしボッティング
剤には、中空糸両末端から流体状高分子が流れ出ないよ
う流体状高分子と相溶性の良いシリコン系接着剤（ＫＥ
Ｊ６とＣＡＴ−ＲＣの １：ｌ混合物、信越化学株製）
を使用して接着した。このモジュールを用いて複合中空
糸膜の気体透過速度を測定した。その結果、この複合中
空糸ＩＱの酸素透過速度は
６、ＯＸ ＩＯ＝ ［ｃｍ’ （ＳＴＰ）／ｃｓ＋２．
ｓｅｃ１ｃｍＨｇ］ 、窒素透過速度は
２、ｓＸ １０−’ ［ｃｍ’（ＳＴＰ）／ｃｍ２−ｓ
ｅｃｌｃｍＨｇｌ テあり、酸素選択透過性は２．１で
あった。また、膜を透過し洩れ出た流体状高分子はなか
った。This composite hollow fiber membrane was placed in a container, and a botting agent for bonding the container and the composite hollow fiber membrane was poured into both ends of the composite hollow fiber membrane to produce a module. However, the botting agent is a silicone adhesive (KE) that has good compatibility with the fluid polymer to prevent the fluid polymer from flowing out from both ends of the hollow fiber.
1:1 mixture of J6 and CAT-RC, manufactured by Shin-Etsu Chemical Co., Ltd.)
Glued using. Using this module, we measured the gas permeation rate of a composite hollow fiber membrane. As a result, the oxygen permeation rate of this composite hollow fiber IQ was 6, OX IO = [cm' (STP)/cs+2.
sec1cmHg], nitrogen permeation rate is 2, sX 10-'[cm'(STP)/cm2-s
eclcmHgl was present, and the oxygen permselectivity was 2.1. Further, no fluid polymer permeated the membrane and leaked out.
以上のように、流体を挟み込んだ多層複合中空糸膜は、
中間層にピンホールが無く、酸素透過速度が１０−３の
オーダーで、かつ酸素選択性が２．０以トという極めて
優れた酸素富化膜であった。As mentioned above, the multilayer composite hollow fiber membrane sandwiching fluid is
It was an extremely excellent oxygen-enriched membrane with no pinholes in the intermediate layer, an oxygen permeation rate of the order of 10-3, and an oxygen selectivity of 2.0 or more.
Claims (2)
受け持つ多孔膜（Ｂ）とからなる中空繊維状膜であって
、分離膜（Ａ）と多孔膜（Ｂ）とは交互に積層されてお
り、該中空繊維状膜の内表面および外表面が多孔膜（Ｂ
）からなる構造を有する多層複合中空糸膜において、該
分離膜（Ａ）が選択分離機能を有する常温で流体状の高
分子（Ａ’）からなり、多孔膜（Ｂ）が結晶性高分子（
Ｂ’）からなり、流体状の高分子（Ａ’）の分子の大き
さが多孔膜（Ｂ）の孔の大きさよりも大きいものである
ことを特徴とする多層複合中空糸膜。(1) A hollow fibrous membrane consisting of a separation membrane (A) that has a separation function and a porous membrane (B) that has a reinforcing function, where the separation membrane (A) and the porous membrane (B) are alternately laminated. The inner and outer surfaces of the hollow fibrous membrane are made of a porous membrane (B
), the separation membrane (A) is made of a polymer (A') that is fluid at room temperature and has a selective separation function, and the porous membrane (B) is made of a crystalline polymer (A') that has a selective separation function.
A multilayer composite hollow fiber membrane comprising B'), characterized in that the molecular size of the fluid polymer (A') is larger than the pore size of the porous membrane (B).
常温で流体状の高分子（Ａ’）および多孔膜（Ｂ）を形
成する結晶性高分子（Ｂ’）を、最外層および最内層に
結晶性高分子（Ｂ’）が配置され、かつ高分子（Ａ’）
および高分子（Ｂ’）が交互にサンドイッチ状に配置さ
れるように供給して多層複合中空繊維を紡糸する工程と
、多孔膜（Ｂ）の孔の大きさが分離膜（Ａ）の流体状高
分子（Ａ’）の分子の大きさよりも小さくなるように、
得られた多層複合中空繊維を延伸して、結晶性高分子（
Ｂ’）の層を多孔化する工程とを有することを特徴とす
る多層複合中空糸膜の製造方法。(2) In a multi-cylindrical spinning nozzle, the outermost layer and A crystalline polymer (B') is arranged in the innermost layer, and a polymer (A')
and the step of spinning a multilayer composite hollow fiber by supplying the polymers (B') so as to be alternately arranged in a sandwich-like manner, so that it is smaller than the molecule size of the polymer (A'),
The obtained multilayer composite hollow fiber is stretched to form a crystalline polymer (
B') A method for producing a multilayer composite hollow fiber membrane, comprising the step of making the layer porous.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13902987A JPS63302904A (en) | 1987-06-04 | 1987-06-04 | Multi-layered composite hollow fiber containing fluid and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13902987A JPS63302904A (en) | 1987-06-04 | 1987-06-04 | Multi-layered composite hollow fiber containing fluid and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63302904A true JPS63302904A (en) | 1988-12-09 |
Family
ID=15235803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13902987A Pending JPS63302904A (en) | 1987-06-04 | 1987-06-04 | Multi-layered composite hollow fiber containing fluid and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63302904A (en) |
-
1987
- 1987-06-04 JP JP13902987A patent/JPS63302904A/en active Pending
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