JPH026848B2 - - Google Patents
Info
- Publication number
- JPH026848B2 JPH026848B2 JP57191333A JP19133382A JPH026848B2 JP H026848 B2 JPH026848 B2 JP H026848B2 JP 57191333 A JP57191333 A JP 57191333A JP 19133382 A JP19133382 A JP 19133382A JP H026848 B2 JPH026848 B2 JP H026848B2
- Authority
- JP
- Japan
- Prior art keywords
- spinning
- weight
- aromatic polyamide
- dry
- 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 - Lifetime
Links
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 27
- 239000012510 hollow fiber Substances 0.000 claims description 22
- 239000004760 aramid Substances 0.000 claims description 18
- 229920003235 aromatic polyamide Polymers 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000011550 stock solution Substances 0.000 claims description 9
- 238000001891 gel spinning Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000001879 gelation Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000578 dry spinning Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- -1 ligroin Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- REPVNSJSTLRQEQ-UHFFFAOYSA-N n,n-dimethylacetamide;n,n-dimethylformamide Chemical compound CN(C)C=O.CN(C)C(C)=O REPVNSJSTLRQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Description
【発明の詳細な説明】
本発明は、芳香族ポリアミド中空糸の製造法に
関する。更に詳しくは、逆浸透膜、限外ロ過膜な
どの分離用膜として有効に使用される芳香族ポリ
アミド中空糸の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic polyamide hollow fibers. More specifically, the present invention relates to a method for producing aromatic polyamide hollow fibers that are effectively used as separation membranes such as reverse osmosis membranes and ultrafiltration membranes.
主鎖中に芳香族環構造を有するポリアミド、代
表的にはｍ―フエニレンジアミンとイソフタル酸
（クロリド）とを縮重合させて得られるポリアミ
ドは、融点、モジユラスが高く、高温特性が良好
なため、近年耐熱性繊維、タイヤコードなどに用
いられているが、中空状繊維として分離用膜にも
使用されている。 Polyamides having an aromatic ring structure in the main chain, typically polyamides obtained by condensation polymerization of m-phenylenediamine and isophthalic acid (chloride), have a high melting point, high modulus, and good high-temperature properties. In recent years, it has been used in heat-resistant fibers, tire cords, etc., but it is also used as hollow fibers in separation membranes.
かかる芳香族ポリアミドの紡糸は、芳香族ポリ
アミドをジメチルホルムアミド（95％）一塩化リ
チウム（５％）混合液に溶解し、形成された紡糸
原液（ドープ液）を128℃に加熱し、紡糸口金の
細孔を通して225℃の空気中に乾式紡糸し、4.7倍
に延伸し、精練することによつて行われている。 The aromatic polyamide is spun by dissolving the aromatic polyamide in a mixture of dimethylformamide (95%) and lithium monochloride (5%), heating the resulting spinning stock solution (dope solution) to 128°C, and placing it in a spinneret. This is done by dry spinning in air at 225°C through pores, stretching 4.7 times, and scouring.
ところで、逆浸透膜などに使用するため、芳香
族ポリアミドを中空糸に成形するため、乾湿式紡
糸法を適用しようとすると、ゲル化速度が遅く、
そのため種々の障害に遭遇する。 By the way, when trying to apply a dry-wet spinning method to form aromatic polyamide into hollow fibers for use in reverse osmosis membranes, etc., the gelation rate is slow;
Therefore, various obstacles are encountered.
即ち、一般に、乾湿式紡糸法においては、紡糸
口金の細孔から吐出された紡糸原液は、一定距離
（数cm〜数10cm程度）自由落下した後、ゲル化浴
に導かれゲル化する。その後、水平方向に方向変
換させるガイドロールを経て、最終的には巻取ロ
ールで巻取られるが、このガイドロールに接触す
る段階迄にある程度迄ゲル化していないと、中空
糸はここでつぶれて中空繊維状態を保持し得な
い。 That is, in general, in the dry-wet spinning method, the spinning dope discharged from the pores of the spinneret falls freely over a certain distance (about several centimeters to several tens of centimeters), and then is led to a gelling bath and gelled. After that, the hollow fiber passes through a guide roll that changes its direction in the horizontal direction, and is finally wound up with a take-up roll, but if it has not gelled to a certain extent by the time it comes into contact with this guide roll, the hollow fiber will collapse here. The hollow fiber state cannot be maintained.
乾湿式紡糸される重合体の種類によつては、ゲ
ル化速度の遅いものもあり、この場合にはその対
策としてガイドロールへの到達距離を長く設定し
て問題の解決を図つている。しかしながら、この
ような解決法は、紡糸装置全体を大型化し、また
紡糸開始時の糸掛けを困難にするなどの欠点をも
たらす。 Depending on the type of polymer that is wet-dry spun, the gelation rate may be slow, and in this case, as a countermeasure, the distance to the guide rolls is set to be long to solve the problem. However, such a solution has drawbacks such as increasing the overall size of the spinning apparatus and making it difficult to thread the yarn at the start of spinning.
前述の如く、芳香族ポリアミドの乾湿式紡糸の
場合にも、他の重合体の紡糸原液、例えばポリス
ルホンのジメチルホルムアミドまたはジメチルア
セトアミド溶液と比較して、かなりゲル化速度が
遅く、そのために深さが数ｍ程度の深いゲル化浴
を必要としている。 As mentioned above, even in the case of dry-wet spinning of aromatic polyamides, the gelation rate is considerably slower than that of other polymer spinning dope solutions, such as dimethylformamide or dimethylacetamide solutions of polysulfone, and therefore the depth is A deep gelling bath of several meters is required.
そこで、ゲル化のメカニズムについて考える
と、紡糸原液を形成する重合体一溶媒系では重合
体が溶媒中に均一に存在し、そして紡糸原液がゲ
ル化浴、例えば水と接触することによつて水と溶
媒との置換が起り、その結果として重合体が凝集
し、ゲル化が生ずると考えることができ、従つて
ゲル化の速度は重合体／溶媒、溶媒／水および重
合体／水の三者相互間の相溶性によつて支配され
るものと思われる。 Therefore, considering the mechanism of gelation, in a polymer-solvent system that forms the spinning dope, the polymer exists uniformly in the solvent, and when the spinning dope comes into contact with a gelling bath, for example, water, water is released. It can be thought that substitution of the solvent with the solvent occurs, and as a result, the polymer aggregates and gelation occurs. Therefore, the rate of gelation is determined by three factors: polymer/solvent, solvent/water, and polymer/water. It seems to be controlled by mutual compatibility.
かかる考察に基いて、本発明者は芳香族ポリア
ミドおよびそれの良溶媒であるジメチルアセトア
ミドから形成される紡糸原液（孔径調節および良
好な非対称構造を形成せしめるために、塩化リチ
ウムが更に加えられている）に、芳香族ポリアミ
ドの常温での貧溶媒であるジメチルホルムアミド
を加えて用いることにより、そのゲル化速度を高
め得ることを見出した。 Based on these considerations, the present inventor developed a spinning stock solution formed from an aromatic polyamide and its good solvent dimethylacetamide (lithium chloride was further added to control the pore size and form a good asymmetric structure). ) was found to be able to increase its gelation rate by adding dimethylformamide, which is a poor solvent for aromatic polyamides at room temperature.
従つて、本発明は芳香族ポリアミド中空糸の製
造法に係り、芳香族ポリアミド中空糸は、芳香族
ポリアミド、塩化リチウムおよびジメチルアセト
アミド―ジメチルホルムアミド混合溶媒よりなる
紡糸原液を乾湿式紡糸することにより製造され
る。 Therefore, the present invention relates to a method for producing an aromatic polyamide hollow fiber, and the aromatic polyamide hollow fiber is produced by dry-wet spinning a spinning stock solution consisting of an aromatic polyamide, lithium chloride, and a dimethylacetamide-dimethylformamide mixed solvent. be done.
芳香族ポリアミドとしては、ノメツクス（デユ
ポン社製品）、コーネツクス（帝人製品）などの
繊維商品名で知られるものの樹脂状粉末が、紡糸
原液中約13〜20重量％の割合で用いられる。ま
た、塩化リチウムは、一般に約３〜10重量％、好
ましくは約５重量％の割合で用いられる。 As the aromatic polyamide, resinous powders known under fiber trade names such as Nomex (manufactured by Dupont) and Cornex (manufactured by Teijin) are used in an amount of about 13 to 20% by weight in the spinning dope. Additionally, lithium chloride is generally used in a proportion of about 3 to 10% by weight, preferably about 5% by weight.
ジメチルアセトアミドは、約７〜20重量％の割
合で、またジメチルホルムアミドは約60〜73重量
％の割合で用いられる。ジメチルアセトアミドの
割合が、これより少ないと紡糸原液は不均一とな
つて紡糸に適さないようになり、一方これより多
く用いるとゲル化が遅くなつて、中空糸がガイド
ロール部でつぶれてしまうようになる。 Dimethylacetamide is used in a proportion of about 7-20% by weight and dimethylformamide in a proportion of about 60-73% by weight. If the proportion of dimethylacetamide is less than this, the spinning stock solution will become non-uniform and unsuitable for spinning, while if it is used in a larger proportion than this, gelation will be delayed and the hollow fibers may be crushed in the guide rolls. become.
以上の各成分から調製される紡糸原液は、中空
（二重円）環状ノズルから押出し、数cm〜数10cm
の間を自然落下させた後、水またはそれを主成分
とするゲル化浴中に導き、そこでゲル化成形する
ことにより行われる。この際、中空部の内部に
は、紡糸原液に対して非凝固性の液体、例えばリ
グロイン、灯油、ヘキサン、ベンゼン、トルエン
などの液状炭化水素を芯液として注入し、中空部
の維持を図ることが好ましい。 The spinning stock solution prepared from each of the above components is extruded from a hollow (double circular) annular nozzle,
After allowing it to fall naturally between the layers, it is introduced into water or a gelling bath containing water as a main component, and gelling is performed there. At this time, a non-coagulable liquid such as ligroin, kerosene, hexane, benzene, toluene, etc., is injected into the hollow part as a core liquid to maintain the hollow part. is preferred.
ゲル化浴中では、ガイドロールによつて、ゲル
化された紡糸液の方向変換が図られるが、ジメチ
ルアセトアミドに上記割合のジメチルホルムアミ
ドを加え、ゲル化速度の上昇を達成せしめた本発
明の紡糸方法にあつては、ゲル化浴液面からこの
ガイドロール迄の距離を約30〜40cm程度に設定す
ることができ、これは従来法のジメチルアセトア
ミドのみを用いたときの数ｍという設定距離と比
較して大幅に短縮できるので、装置全体のコンパ
クト化にもこれがつながつている。 In the gelling bath, guide rolls change the direction of the gelled spinning solution, and the spinning of the present invention achieves an increase in the gelling rate by adding dimethylformamide in the above ratio to dimethylacetamide. In this method, the distance from the gelling bath liquid level to this guide roll can be set to about 30 to 40 cm, which is different from the distance of several meters when using only dimethylacetamide in the conventional method. Since the time can be significantly shortened in comparison, this also leads to the downsizing of the entire device.
しかも、本発明方法で得られた中空糸は、所望
の中空状繊維形状を形成させているので、逆浸透
膜、限外ロ過膜などの分離用膜として有効に使用
することができる。 Moreover, since the hollow fibers obtained by the method of the present invention have a desired hollow fiber shape, they can be effectively used as separation membranes such as reverse osmosis membranes and ultrafiltration membranes.
次に、実施例について本発明を説明する。 Next, the present invention will be explained with reference to examples.
実施例
図面に示される装置を用い、芳香族ポリアミド
（コーネツクス）15重量％、塩化リチウム５重量
％、ジメチルアセトアミド10重量％およびジメチ
ルホルムアミド70重量％から調製された紡糸原液
の乾湿式紡糸を行なつた。Example Using the apparatus shown in the drawings, a spinning stock solution prepared from 15% by weight of aromatic polyamide (Konex), 5% by weight of lithium chloride, 10% by weight of dimethylacetamide and 70% by weight of dimethylformamide was subjected to dry-wet spinning. Ta.
紡糸原液は、空気圧１によつて加圧された紡糸
原液タンク２から、ギアポンプ３を経由して、中
空（二重円）環状ノズル４に供給され、また芯液
としてのリグロインは、空気圧１′によつて加圧
された芯液タンク５から、液量調節弁６および流
量計７を順次経由して、前記中空環状ノズルに供
給される。紡糸は、この中空環状ノズル（外径４
mm、内径２mm）の外側から12ml／分の吐出量で紡
糸原液を、また内側から４ml／分の吐出量（注入
量）でリグロインをそれぞれ吐出させ、10cm自然
落下させた後、紡糸原液のゲル化浴８中に導くこ
とにより行われる。ゲル化浴中では、液面下40cm
の位置に設けられたガイドロール９よつて方向変
換させた後、更に他のガイドロール10を介して、
巻取ロール１１に22m／分の巻取速度で中空糸を
巻取つた。 The spinning dope is supplied from a spinning dope tank 2 pressurized at an air pressure of 1 to a hollow (double circular) annular nozzle 4 via a gear pump 3, and ligroin as a core liquid is supplied to a spinning dope tank 2 pressurized at an air pressure of 1'. The core liquid is supplied from the pressurized core liquid tank 5 to the hollow annular nozzle via a liquid volume control valve 6 and a flow meter 7 in sequence. Spinning is carried out using this hollow annular nozzle (outer diameter 4
The spinning stock solution was discharged from the outside at a discharge rate of 12 ml/min (inner diameter 2 mm), and the ligroin was discharged from the inside at a discharge rate (injection volume) of 4 ml/min, and after falling naturally for 10 cm, the spinning stock solution gelled. This is carried out by introducing it into a chemical bath 8. In the gelling bath, 40 cm below the liquid surface.
After the direction is changed by the guide roll 9 provided at the position, it is further passed through another guide roll 10,
The hollow fiber was wound around a winding roll 11 at a winding speed of 22 m/min.
得られた中空糸は、外径0.6mm、内径0.3mmの良
好な形状を有する中空状繊維であり、この中空糸
を限外ロ過材料として限外ロ過すると、分子量
20000のポリエチレングリコールの２％水溶液に
適用した場合、溶解していたポリエチレングリコ
ールの99％を排除することができた。 The obtained hollow fiber is a hollow fiber having a good shape with an outer diameter of 0.6 mm and an inner diameter of 0.3 mm. When this hollow fiber is ultrafiltered as an ultrafiltration material, the molecular weight
When applied to a 2% aqueous solution of 20,000 polyethylene glycol, 99% of the dissolved polyethylene glycol could be eliminated.
比較例 １
実施例において、ジメチルアセトアミドを30重
量％、またジメチルホルムアミドを50重量％にそ
れぞれ変更して紡糸原液の調製を行ない、乾湿式
紡糸を行なつた。その結果、ガイドロール９で中
空糸はつぶれた状態となり、目的物を得ることが
できなかつた。Comparative Example 1 In the example, a spinning dope was prepared by changing the dimethylacetamide to 30% by weight and the dimethylformamide to 50% by weight, and performing wet-dry spinning. As a result, the hollow fibers were crushed by the guide roll 9, and the target product could not be obtained.
比較例 ２
実施例において、ジメチルホルムアミドを用い
ずに、ジメチルアセトアミドを80重量％に変更し
て紡糸原液の調製を行ない、乾湿式紡糸を行なつ
た。その結果、ガイドロール９で中空糸はつぶれ
た状態となり、目的物を得ることができなかつ
た。Comparative Example 2 In Example, a spinning dope was prepared by changing the amount of dimethylacetamide to 80% by weight without using dimethylformamide, and wet-dry spinning was performed. As a result, the hollow fibers were crushed by the guide roll 9, and the target product could not be obtained.
図面は、本発明に係る芳香族ポリアミド中空糸
の製造法の一態様を示すそれの概略図である。
符号の説明、２……紡糸原液タンク、４……中
空環状ノズル、５……芯液タンク、８……ゲル化
浴、９……ガイドロール、１１……巻取ロール。
The drawings are schematic diagrams showing one embodiment of the method for producing aromatic polyamide hollow fibers according to the present invention. Explanation of symbols, 2... Spinning dope tank, 4... Hollow annular nozzle, 5... Core liquid tank, 8... Gelling bath, 9... Guide roll, 11... Winding roll.
Claims (1)
セトアミド７〜20重量％、ジメチルホルムアミド
60〜73重量％および塩化リチウム３〜10重量％か
ら調製された紡糸原液を乾湿式紡糸することを特
徴とする芳香族ポリアミド中空糸の製造法。 ２ 紡糸原液非凝固性の芯液を注入して乾湿式紡
糸する特許請求の範囲第１項記載の芳香族ポリア
ミド中空糸の製造法。 ３ 芯液として液状炭化水素を用いる特許請求の
範囲第２項記載の芳香族ポリアミド中空糸の製造
法。[Claims] 1. 13 to 20% by weight of aromatic polyamide, 7 to 20% by weight of dimethylacetamide, and dimethylformamide.
A method for producing aromatic polyamide hollow fibers, which comprises dry-wet spinning a spinning stock solution prepared from 60 to 73% by weight and 3 to 10% by weight of lithium chloride. 2. A method for producing an aromatic polyamide hollow fiber according to claim 1, which comprises injecting a non-coagulable core liquid into a spinning dope and dry-wet spinning. 3. The method for producing an aromatic polyamide hollow fiber according to claim 2, in which a liquid hydrocarbon is used as the core liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19133382A JPS5982407A (en) | 1982-10-29 | 1982-10-29 | Manufacture of aromatic polyamide hollow fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19133382A JPS5982407A (en) | 1982-10-29 | 1982-10-29 | Manufacture of aromatic polyamide hollow fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5982407A JPS5982407A (en) | 1984-05-12 |
| JPH026848B2 true JPH026848B2 (en) | 1990-02-14 |
Family
ID=16272808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19133382A Granted JPS5982407A (en) | 1982-10-29 | 1982-10-29 | Manufacture of aromatic polyamide hollow fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5982407A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104353372B (en) * | 2014-11-07 | 2016-05-11 | 天津工业大学 | A kind of preparation method of aromatic polyamide hollow fiber porous film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS562804A (en) * | 1979-06-19 | 1981-01-13 | Nitto Electric Ind Co Ltd | Preparation of selectively permeable membrane |
-
1982
- 1982-10-29 JP JP19133382A patent/JPS5982407A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS562804A (en) * | 1979-06-19 | 1981-01-13 | Nitto Electric Ind Co Ltd | Preparation of selectively permeable membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5982407A (en) | 1984-05-12 |
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