JP2017110311A - Manufacturing method of syndiotactic polystyrene fiber - Google Patents
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- 239000000835 fiber Substances 0.000 title claims abstract description 53
- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 45
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- 229920000642 polymer Polymers 0.000 description 13
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Abstract
Description
本発明はナノポーラス結晶構造を有するシンジオタクチックポリスチレン繊維の製造方法に関する。 The present invention relates to a method for producing syndiotactic polystyrene fibers having a nanoporous crystal structure.
従来、ガス又は液体中から有機物質の分離、除去方法として、有機物質含有ガス又は液体を活性炭などの吸着材に吸着させ、吸着された有機物質を加熱ガスにて吸着材から脱着し、除去する方法が採用されている。しかしながら、上記で使用されている活性炭などの多孔性物質は、細孔構造への物理吸着が主であるために、吸着できる有機化合物の大きさ、分子形状が類似している場合、選択的に吸着できないという欠点がある。 Conventionally, as a method for separating and removing organic substances from gas or liquid, organic substance-containing gas or liquid is adsorbed on an adsorbent such as activated carbon, and the adsorbed organic substance is desorbed and removed from the adsorbent with heated gas. The method is adopted. However, since the porous materials such as activated carbon used above are mainly physically adsorbed to the pore structure, the organic compounds that can be adsorbed are similar in size and molecular shape. There is a disadvantage that it cannot be adsorbed.
シンジオタクチックポリスチレン（以下、ｓＰＳともいう）は有機化合物との複合構造を形成することが知られている。その有機化合物を特定の溶媒を用いて抽出することで得られるナノポーラス結晶ｓＰＳは有機化合物を選択的に効率よく吸着できることが見出されている（特許文献１）。その複合構造は、２θ（ＣｕＫα）≒８．４°、１０．６°、１３．６°、１７．２°、２０．８°、２３．６°で高強度反射を与えるＸ線回折像を示すことが報告されている（特許文献２）。 Syndiotactic polystyrene (hereinafter also referred to as sPS) is known to form a composite structure with an organic compound. It has been found that nanoporous crystals sPS obtained by extracting the organic compound using a specific solvent can selectively and efficiently adsorb the organic compound (Patent Document 1). The composite structure shows X-ray diffraction images that give high-intensity reflection at 2θ (CuKα) ≈8.4 °, 10.6 °, 13.6 °, 17.2 °, 20.8 °, and 23.6 °. It has been reported to show (Patent Document 2).
有機溶媒と複合構造を形成したゲル状のｓＰＳを超臨界二酸化炭素によって溶媒を除去させるとエアロゲル状となり、吸着速度が向上することが報告されている（特許文献２）。しかしながら、上記のエアロゲルは円柱状であり取り扱い性に問題がある。一方で、特許文献３では繊維状ナノポーラス結晶を有するｓＰＳの製造について報告されており、繊維状であるため取り扱い性に優れると考えらえる。しかしながら、この方法では非晶質ｓＰＳ繊維の作製と非晶質ｓＰＳ繊維の複合構造作製という２段階の製法が必要であり、工程数が多いためにコストが高く、また結晶化度が３０％以下と低いため、吸着性能が不足する問題を有している。 It has been reported that when a gel-like sPS that forms a composite structure with an organic solvent is removed with supercritical carbon dioxide, it becomes an airgel and the adsorption rate is improved (Patent Document 2). However, the above-mentioned airgel is cylindrical and has a problem in handleability. On the other hand, in patent document 3, it reports about manufacture of sPS which has a fibrous nanoporous crystal, and since it is fibrous, it is thought that it is excellent in handleability. However, this method requires a two-stage production method of producing amorphous sPS fibers and a composite structure of amorphous sPS fibers, which is costly due to the large number of processes and has a crystallinity of 30% or less. Therefore, the adsorption performance is insufficient.
ｓＰＳを有機化合物の吸着剤として使用する場合、有機化合物はナノポーラス結晶へ吸着されるため、ナノポーラス結晶の結晶化度が高いほど吸着性能が良くなる。また、有機化合物の吸着速度は、吸着材の形態に強く依存することが知られている。そのため、効率的に有機化合物を吸着するにあたり表面積を向上させつつ、結晶化度を高くすることが必要である。 When sPS is used as an adsorbent for an organic compound, the organic compound is adsorbed to the nanoporous crystal. Therefore, the higher the crystallinity of the nanoporous crystal, the better the adsorption performance. Moreover, it is known that the adsorption rate of an organic compound strongly depends on the form of the adsorbent. Therefore, in order to adsorb organic compounds efficiently, it is necessary to increase the crystallinity while improving the surface area.
本発明の目的は簡便な方法によってナノポーラス結晶構造を有する、ｓＰＳ繊維を製造する方法を提供することにある。 An object of the present invention is to provide a method for producing an sPS fiber having a nanoporous crystal structure by a simple method.
本発明者らは上記した課題について鋭意検討した結果、特定の溶媒を用いて溶液紡糸することによりナノポーラス結晶構造を有する、ｓＰＳ繊維を作製する方法を見出した。
その発明は次の通りである。
１．シンジオタクチックポリスチレンを溶媒に溶解し、溶液紡糸方法によって繊維を形成する、シンジオタクチックポリスチレン繊維の製造方法。
２．シンジオタクチックポリスチレンを３０ｗｔ％以上溶解可能である溶媒を用いることを特徴とする、上記１記載のシンジオタクチックポリスチレン繊維の製造方法。
３．シンジオタクチックポリスチレンが３０ｗｔ％以上溶解された溶液を用い、溶液紡糸方法によって繊維を製造することを特徴とする、上記１、２いずれかに記載のシンジオタクチックポリスチレン繊維の製造方法。
４．シンジオタクチックポリスチレンを溶媒に溶解することで、溶媒との複合構造を形成することを特徴とする、上記１〜３いずれかに記載のシンジオタクチックポリスチレン繊維の製造方法。
５．溶媒との複合構造を形成後、溶媒を除去することによって得られるナノポーラス結晶構造を有する、上記４に記載のシンジオタクチックポリスチレン繊維の製造方法。
６．ナノポーラス結晶構造を有するシンジオタクチックポリスチレン繊維の繊維径が１０μｍ以上、１００μｍ以下である上記４、５いずれかに記載のシンジオタクチックポリスチレン繊維の製造方法。
７．ナノポーラス結晶の結晶化度が３０％以上、８０％以下である上記４〜６いずれかに記載のシンジオタクチックポリスチレン繊維の製造方法。
As a result of intensive studies on the above-described problems, the present inventors have found a method for producing an sPS fiber having a nanoporous crystal structure by solution spinning using a specific solvent.
The invention is as follows.
1. A method for producing syndiotactic polystyrene fibers, comprising dissolving syndiotactic polystyrene in a solvent and forming fibers by a solution spinning method.
2. 2. The method for producing syndiotactic polystyrene fibers according to 1 above, wherein a solvent capable of dissolving 30 wt% or more of syndiotactic polystyrene is used.
3. 3. The method for producing syndiotactic polystyrene fibers according to any one of the above 1 and 2, wherein a fiber is produced by a solution spinning method using a solution in which syndiotactic polystyrene is dissolved by 30 wt% or more.
4). 4. The method for producing a syndiotactic polystyrene fiber according to any one of the above 1 to 3, wherein the composite structure with the solvent is formed by dissolving the syndiotactic polystyrene in the solvent.
5). 5. The method for producing a syndiotactic polystyrene fiber according to 4 above, which has a nanoporous crystal structure obtained by removing the solvent after forming a composite structure with the solvent.
6). 6. The method for producing a syndiotactic polystyrene fiber according to any one of the above 4 and 5, wherein the fiber diameter of the syndiotactic polystyrene fiber having a nanoporous crystal structure is 10 μm or more and 100 μm or less.
7). The method for producing a syndiotactic polystyrene fiber according to any one of the above 4 to 6, wherein the crystallinity of the nanoporous crystal is 30% or more and 80% or less.
本発明により、ｓＰＳを取り扱い性に優れる繊維状に成型すると同時に溶媒との複合構造を作製でき、結晶化度が高いために、吸着効率の高い吸着材を効率良く生産できる。 According to the present invention, sPS can be molded into a fiber having excellent handleability, and at the same time a composite structure with a solvent can be produced. Since the degree of crystallization is high, an adsorbent with high adsorption efficiency can be produced efficiently.
本発明でいう複合構造とは、ｓＰＳと溶媒が形成した結晶構造であり、ＴＴＧＧ構造を特徴としており、２θ（ＣｕＫα）≒８．４°、１０．６°、１３．６°、１７．２°、２０．８°、２３．６°で高強度反射を与えるＸ線回折像で定義される。ナノポーラスを有するｓＰＳは上記複合構造からアセトン、超臨界二酸化炭素などによって溶媒を除去することによっても得られる。 The composite structure referred to in the present invention is a crystal structure formed by sPS and a solvent and is characterized by a TTGG structure. 2θ (CuKα) ≈8.4 °, 10.6 °, 13.6 °, 17.2 It is defined by an X-ray diffraction image that gives high-intensity reflection at 20.8 ° and 23.6 °. The nanoporous sPS can also be obtained by removing the solvent from the above composite structure with acetone, supercritical carbon dioxide or the like.
本発明に係るｓＰＳとは、シンジオタクチック構造を有するスチレン系重合体である。シンジオタクチック構造とはポリスチレンの主鎖に対して芳香環が規則的に交互に配置する構造をとったものである。本発明に用いるシンジオタクチック構造を有するスチレン系重合体（以下シンジオタクチックポリスチレン系重合体ともいう）としては、シンジオタクチック構造として側鎖のフェニル基又は置換フェニル基が核磁気共鳴法により定量されるタクティシティがダイアッド（構成単位が２個）で８５％以上、ペンタッド（構成単位が５個）で５０％以上のシンジオタクチック構造であるポリスチレン、ポリ（ｐ−、ｍ−またはｏ−メチルスチレン）、ポリ（２，４−、２，５−、３，４−または３，５−ジメチルスチレン）、ポリ（ｐ−ターシャリーブチルスチレン）などのポリ（アルキルスチレン）、ポリ（ｐ−、ｍ−またはｏ−クロロスチレン）、ポリ（ｐ−、ｍ−またはｏ−ブロモスチレン）、ポリ（ｐ−、ｍ−またはｏ−フルオロスチレン）、ポリ（ｏ−メチル−ｐ−フルオロスチレン）などのポリ（ハロゲン化スチレン）、ポリ（ｐ−、ｍ−またはｏ−クロロメチルスチレン）などのポリ（ハロゲン置換アルキルスチレン）、ポリ（ｐ−、ｍ−またはｏ−メトキシスチレン）、ポリ（ｐ−、ｍ−またはｏ−エトキシスチレン）などのポリ（アルコキシスチレン）、ポリ（ｐ−、ｍ−またはｏ−カルボキシメチルスチレン）などのポリ（カルボキシアルキルスチレン）、ポリ（ｐ−ビニルベンジルプロピル）などのポリ（アルキルエーテルスチレン）、ポリ（ｐ−トリメチルシリルスチレン）などのポリ（アルキルシリルスチレン）、さらにはポリ（ビニルベンジルジメトキシホスファイド）などが挙げられる。特にシンジオタクチックポリスチレンが好適である。 The sPS according to the present invention is a styrene polymer having a syndiotactic structure. The syndiotactic structure is a structure in which aromatic rings are regularly arranged alternately with respect to the main chain of polystyrene. As a styrene polymer having a syndiotactic structure used in the present invention (hereinafter also referred to as a syndiotactic polystyrene polymer), a side chain phenyl group or a substituted phenyl group is quantified by a nuclear magnetic resonance method as a syndiotactic structure. Polystyrene, poly (p-, m-, or o-methyl) having a syndiotactic structure with a tacticity of 85% or more for dyad (2 structural units) and 50% or more for pentad (5 structural units) Styrene), poly (2,4-, 2,5-, 3,4- or 3,5-dimethylstyrene), poly (alkylstyrene) such as poly (p-tertiarybutylstyrene), poly (p-, m- or o-chlorostyrene), poly (p-, m- or o-bromostyrene), poly (p-, m- or o-fluorostyrene). ), Poly (halogenated styrene) such as poly (o-methyl-p-fluorostyrene), poly (halogen-substituted alkylstyrene) such as poly (p-, m- or o-chloromethylstyrene), poly (p -, M- or o-methoxystyrene), poly (alkoxystyrene) such as poly (p-, m- or o-ethoxystyrene), poly (alkoxystyrene) such as poly (p-, m- or o-carboxymethylstyrene) Carboxyalkyl styrene), poly (alkyl ether styrene) such as poly (p-vinylbenzylpropyl), poly (alkylsilyl styrene) such as poly (p-trimethylsilyl styrene), and poly (vinyl benzyl dimethoxy phosphide). Can be mentioned. In particular, syndiotactic polystyrene is suitable.
本発明に用いるシンジオタクチック構造を有するスチレン系重合体は、必ずしも単一化合物である必要はなく、アタクチック構造やアイソタクチック構造のポリスチレン系重合体との混合物や、共重合体およびそれらの混合物でもよいが、少なくとも４０重量％以上はシンジオタクチック構造を有するスチレン系重合体から成るものである。 The styrenic polymer having a syndiotactic structure used in the present invention is not necessarily a single compound, but is a mixture with a polystyrene polymer having an atactic structure or an isotactic structure, a copolymer, and a mixture thereof. However, at least 40% by weight or more is made of a styrenic polymer having a syndiotactic structure.
また、本発明に用いるシンジオタクチックポリスチレン系重合体は、重量平均分子量が１０，０００以上、さらに好ましくは５０，０００以上である。重量平均分子量が１０，０００未満のものでは、強伸度特性に優れた繊維を得ることができない。重量平均分子量の上限については特に限定されるものではないが、１，５００，０００を超えると押出機の負荷の増加、延伸張力の増加に伴う破断の発生などが生じるため好ましくない。 The syndiotactic polystyrene polymer used in the present invention has a weight average molecular weight of 10,000 or more, more preferably 50,000 or more. If the weight average molecular weight is less than 10,000, it is not possible to obtain a fiber having excellent strength and elongation characteristics. The upper limit of the weight average molecular weight is not particularly limited, but if it exceeds 1,500,000, it is not preferable because an increase in the load on the extruder and the occurrence of breakage due to an increase in stretching tension occur.
本発明のｓＰＳ繊維は、ｓＰＳポリマーを含有するドープより製造されるが、当該ドープを調整するための好適な溶媒としては、テトラリン、オクチルベンゼン、クロロホルム、トルエン、キシレン、ベンジルメタクリレート、ニトロベンゼン、ジニトロベンゼン、ジベンゾフラン、ｐ−ニトロアニリン、１，２−ジクロロエタン、１，４−ジメチルナフタレン、１，３，５−トリメチルベンゼン、ｐ−クロロトルエン、クロロベンゼン、１，１，２−トリクロロエタン、ベンゼン、ナフタレン、１，２−ジクロロプロパン、１−クロロプロパン、ジクロロメタン、ｏ−ジクロロベンゼン、エチルベンゼン、１，１，２，２−テトラクロロエタン、Ｎ−メチルピロリドン、１，４−ジオキサンなどが挙げられるが環境への負荷からベンゼン系の溶媒であるテトラリン、トルエン、オクチルベンゼン、キシレン、ベンジルメタクリレート、ニトロベンゼン、ジニトロベンゼン、ｐ−ニトロアニリン、１，４−ジメチルナフタレン、１，３，５−トリメチルベンゼン、ベンゼン、ナフタレン、エチルベンゼンやＮ−メチルピロリドンが好ましい。ｓＰＳを３０重量％以上溶解可能なテトラリンやＮ−メチルピロリドンが好ましく、ｓＰＳをより多く溶解可能なテトラリンが特に好ましい。 The sPS fiber of the present invention is produced from a dope containing an sPS polymer. Suitable solvents for adjusting the dope include tetralin, octylbenzene, chloroform, toluene, xylene, benzyl methacrylate, nitrobenzene, and dinitrobenzene. , Dibenzofuran, p-nitroaniline, 1,2-dichloroethane, 1,4-dimethylnaphthalene, 1,3,5-trimethylbenzene, p-chlorotoluene, chlorobenzene, 1,1,2-trichloroethane, benzene, naphthalene, 1 , 2-dichloropropane, 1-chloropropane, dichloromethane, o-dichlorobenzene, ethylbenzene, 1,1,2,2-tetrachloroethane, N-methylpyrrolidone, 1,4-dioxane, and the like. Benzene Solvents tetralin, toluene, octylbenzene, xylene, benzyl methacrylate, nitrobenzene, dinitrobenzene, p-nitroaniline, 1,4-dimethylnaphthalene, 1,3,5-trimethylbenzene, benzene, naphthalene, ethylbenzene and N-methyl Pyrrolidone is preferred. Tetraline and N-methylpyrrolidone capable of dissolving sPS by 30% by weight or more are preferred, and tetralin capable of dissolving more sPS is particularly preferred.
ドープ中のポリマー濃度は、好ましくは３０質量％以上であり、より好ましくは５０質量％以上である。最大濃度は、例えポリマーの溶解性やドープ粘度といった実際上の取り扱い性により限定される。それらの限界要因のために、ポリマー濃度の上限は９０質量％である。３０重量％未満の場合、ドープの曳糸性が悪いため、良好な繊維が得られない。 The polymer concentration in the dope is preferably 30% by mass or more, more preferably 50% by mass or more. The maximum concentration is limited by practical handling properties such as polymer solubility and dope viscosity. Due to these limiting factors, the upper limit of polymer concentration is 90% by weight. If it is less than 30% by weight, the dope spinnability is poor, so that good fibers cannot be obtained.
このようにして得られるドープを紡糸口金から押し出し、空間で引き伸ばして溶媒を含む液状フィラメント状物が形成される。 The dope thus obtained is extruded from a spinneret and stretched in space to form a liquid filament containing a solvent.
続いて溶媒を含む液状フィラメント状物を冷却することによりゲル状のフィラメント状物を形成する。ゲル化させるためには、冷却することが好ましく、空気、窒素などの媒体による、いわゆる空冷による冷却方法が用いられる。ドープ中の溶媒が過度に除去されない条件であれば、水などの液体中を通過させ、冷却しても良い。ゲル状フィラメントの形成工程で一部溶媒が減少するが、ゲル状のフィラメント中に含まれる溶媒の割合は１０重量％以上、５０重量％以下であることが好ましく、２０重量％以上、４０重量％以下であることがより好ましい。溶媒の割合が１０重量％未満となる場合、上記複合構造を十分に形成するための溶媒が不足するために、ナノポーラス構造を形成しにくくなる。溶媒残量が５０重量％以上となる場合、冷却によって十分にゲル化しないため次工程での取り扱いが困難となり、好ましくない。 Subsequently, the liquid filamentous material containing the solvent is cooled to form a gel filamentous material. In order to make it gelatinize, it is preferable to cool and the cooling method by what is called air cooling using media, such as air and nitrogen, is used. As long as the solvent in the dope is not excessively removed, it may be cooled by passing it through a liquid such as water. The solvent is partially reduced in the gel filament formation process, but the ratio of the solvent contained in the gel filament is preferably 10% by weight or more and 50% by weight or less, and more preferably 20% by weight or more and 40% by weight. The following is more preferable. When the proportion of the solvent is less than 10% by weight, it becomes difficult to form the nanoporous structure because the solvent for sufficiently forming the composite structure is insufficient. When the remaining amount of the solvent is 50% by weight or more, it is not preferable because it is not sufficiently gelled by cooling, which makes it difficult to handle in the next step.
一般的な溶液紡糸における紡糸工程においては、乾燥工程による溶媒の除去によりフィラメントの形成が行われるが、本発明は、乾燥を積極的に行う必要はなく、所定の溶媒量を残す必要がある。すなわち、上記溶媒の割合を有するゲル状フィラメントを形成することで、紡糸−冷却工程において溶媒との複合構造の形成が可能となることを見いだしたものである。冷却工程を経て溶媒残量が所定量を下回ると結晶化度が減少し、所望するナノポーラス構造が形成されない。 In a spinning process in general solution spinning, a filament is formed by removing a solvent in a drying process. However, in the present invention, it is not necessary to actively perform drying, and it is necessary to leave a predetermined amount of solvent. That is, it has been found that by forming a gel filament having the above-mentioned solvent ratio, a composite structure with a solvent can be formed in the spinning-cooling step. When the remaining amount of the solvent falls below a predetermined amount after the cooling step, the degree of crystallinity decreases, and the desired nanoporous structure is not formed.
ゲル状のフィラメント状物より抽出溶媒を用いることでナノポーラス構造を形成するために用いた溶媒が置換、除去される。このとき、抽出に使用される抽出溶媒として、従来公知の方法、例えば沸騰アセトンや超臨界二酸化炭素、エタノールなどを用いることが出来る。次いで、フィラメントから抽出溶媒を除去することでナノポーラス構造を有する繊維が得られる。抽出溶媒を除去する方法は特に限定されないが、特に減圧乾燥が好ましく用いられる。 By using an extraction solvent from the gel filament, the solvent used to form the nanoporous structure is replaced and removed. At this time, conventionally known methods such as boiling acetone, supercritical carbon dioxide, ethanol and the like can be used as an extraction solvent used for extraction. Next, a fiber having a nanoporous structure is obtained by removing the extraction solvent from the filament. The method for removing the extraction solvent is not particularly limited, but vacuum drying is particularly preferably used.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、明細書本文および実施例にて用いる測定は次のように行った。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited only to these Examples. In addition, the measurement used in a specification text and an Example was performed as follows.
（１）繊維内の残溶媒率：熱量計測定装置における重量変化から測定した。 (1) Residual solvent ratio in fiber: measured from weight change in calorimeter measuring device.
（２）ナノポーラス結晶の結晶化度：株式会社リガクのＸ線装置Ｒｉｎｔを用いたＸ線構造解析により、（ナノポーラス結晶の面積／全ピーク面積）から算出した。 (2) Crystallinity of nanoporous crystal: Calculated from (area of nanoporous crystal / total peak area) by X-ray structural analysis using Rigaku Corporation's X-ray apparatus Rint.
（３）繊維断面図及び繊維径：電子顕微鏡における繊維の断面写真から算出した。 (3) Fiber cross-sectional view and fiber diameter: calculated from a cross-sectional photograph of the fiber in an electron microscope.
［実施例１］
シンジオタクチックポリスチレン単独重合体は、出光興産株式会社製ＸＡＲＥＣ３００ＺＣを用いた。重合体を窒素雰囲気下１９０℃でテトラリン中にｓＰＳが６０重量％溶解されたドープを作製した。ドープは押し出し装置により、圧力をかけた状態で金属網状の濾材を通過させ、重合体溶液温度を１９５℃の条件で、１９５℃に設定した紡糸口金から０．４ｃｃ／ｍｉｎの単孔吐出量で紡出させた。吐出したフィラメントは室温の冷却風を用いて冷却した後、５０ｍ／ｍｉｎの速度で巻き取った。冷却の際に冷却風により一部溶媒が除去され、巻き取ったゲル状フィラメント状物の溶媒残量は１９重量％であった。このゲル状フィラメント状物を抽出溶媒である沸騰アセトン中に６時間浸漬させテトラリンと置換させた。このアセトンを多く含むフィラメント状物を６０℃で２時間、減圧乾燥により溶媒を除去した。こうして得られた繊維は８．４°、１０．６°、１３．６°、１７．２°、２０．８°、２３．６°で高強度反射を与えるＸ線回折像を有した。得られた繊維の繊維径は６８μｍであり、ナノポーラス結晶構造を有するだけでなく図２の繊維断面図に示すように繊維内部がマクロな多孔構造となっていた。得られた繊維の強度は０．６５ｃＮ／ｄｔｅｘ、伸度１．４％であった。
[Example 1]
As a syndiotactic polystyrene homopolymer, XAREC300ZC manufactured by Idemitsu Kosan Co., Ltd. was used. A dope was prepared by dissolving 60% by weight of sPS in tetralin at 190 ° C. in a nitrogen atmosphere. The dope is passed through a metal net-like filter medium under pressure by an extrusion device, and the polymer solution temperature is set to 195 ° C., and the spinneret set at 195 ° C. has a single hole discharge rate of 0.4 cc / min. Spinned. The discharged filament was cooled using room temperature cooling air and then wound up at a speed of 50 m / min. During cooling, a part of the solvent was removed by cooling air, and the remaining amount of the solvent in the wound gel filament was 19% by weight. This gel-like filament was immersed in boiling acetone as an extraction solvent for 6 hours to replace tetralin. The filament-like material containing a large amount of acetone was dried under reduced pressure at 60 ° C. for 2 hours to remove the solvent. The fibers thus obtained had X-ray diffraction images giving high intensity reflection at 8.4 °, 10.6 °, 13.6 °, 17.2 °, 20.8 ° and 23.6 °. The obtained fiber had a fiber diameter of 68 μm, and had not only a nanoporous crystal structure but also a macro porous structure inside the fiber as shown in the fiber cross-sectional view of FIG. The strength of the obtained fiber was 0.65 cN / dtex, and the elongation was 1.4%.
［比較例１］
テトラリンを１９重量％含むゲル状フィラメント状物を沸騰アセトンで処理することなく、常温常圧中に１週間静置することによって溶媒を除去（溶媒残量０重量％）した以外は実施例１と同様に行った。Ｘ線回折像における２θが９．５°、１６．３°、２０．４°に高強度反射を与えるＸ線回折像を有する繊維が得られ、ナノポーラス構造が存在しなかった。
[Comparative Example 1]
Example 1 except that the gel-like filamentous material containing 19% by weight of tetralin was left at room temperature and normal pressure for 1 week without treating with boiling acetone, and the solvent was removed (residual amount of solvent 0% by weight). The same was done. A fiber having an X-ray diffraction image giving high-intensity reflection at 2θ of 9.5 °, 16.3 °, and 20.4 ° in the X-ray diffraction image was obtained, and no nanoporous structure was present.
［比較例２］
シンジオタクチックポリスチレン単独重合体は、出光興産株式会社製ＸＡＲＥＣ３００ＺＣを用いた。ｓＰＳ重合体を窒素雰囲気下１９０℃でテトラリン中に溶解させ、ｓＰＳが２５重量％溶解されたドープを作製した以外は実施例１と同様の方法で繊維化を試みた。得られたゲル状フィラメント状物中のテトラリン溶媒残量は５１％であった。ドープ中のｓＰＳ濃度を２５重量％としたため、冷却風により溶媒が除去された後でも残存溶媒量が多いために十分ゲル化せず、可紡性が悪く繊維化が困難であった。
[Comparative Example 2]
As a syndiotactic polystyrene homopolymer, XAREC300ZC manufactured by Idemitsu Kosan Co., Ltd. was used. Fiber formation was attempted in the same manner as in Example 1 except that the sPS polymer was dissolved in tetralin at 190 ° C. in a nitrogen atmosphere to prepare a dope in which 25 wt% of sPS was dissolved. The residual amount of tetralin solvent in the obtained gel filament was 51%. Since the sPS concentration in the dope was 25% by weight, even after the solvent was removed by cooling air, the remaining solvent amount was large, so that the gel was not sufficiently gelled, and the spinnability was poor and fiberization was difficult.
実施例１、比較例１、２の結果を表１に示す。実施例１の繊維は可紡性もよく、ナノポーラスの結晶化度も４４．５％と高く、好ましい繊維が得られた。 The results of Example 1 and Comparative Examples 1 and 2 are shown in Table 1. The fiber of Example 1 had good spinnability and the nanoporous crystallinity was as high as 44.5%, and a preferable fiber was obtained.
本発明により、ナノポーラス結晶化度が高く、可紡性に優れたシンジオタクチックポリスチレン繊維の製造方法が提供出来る。 INDUSTRIAL APPLICABILITY According to the present invention, a method for producing syndiotactic polystyrene fibers having high nanoporous crystallinity and excellent spinnability can be provided.
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| CN114015154A (en) * | 2021-11-09 | 2022-02-08 | 南方电网科学研究院有限责任公司 | Preparation method of environment-friendly high-voltage cable polypropylene insulating material |
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| JPH0253909A (en) * | 1988-07-22 | 1990-02-22 | Dow Chem Co:The | High-strength fiber of a stereoregular polystyrene |
| JPH0368432A (en) * | 1989-07-14 | 1991-03-25 | Dow Chem Co:The | Isotropic or anisotropic porous syndiotactic polystyrene membrane and manufacture thereof |
| JPH09192653A (en) * | 1996-01-25 | 1997-07-29 | Dainippon Ink & Chem Inc | Absorbing method of chlorine-based organic solvent and water treating apparatus |
| JP2004075733A (en) * | 2002-08-12 | 2004-03-11 | Japan Science & Technology Corp | Method for producing polymer structure having controlled cavity structure |
| WO2008023331A2 (en) * | 2006-08-22 | 2008-02-28 | Gaetano Guerra | New nanoporous crystalline form of syndiotactic polystyrene, processes for its preparation and related molecular-complex crystalline forms |
| JP2014504659A (en) * | 2010-12-30 | 2014-02-24 | ナノ アクティブ フィルム ソチエタ レスポンサビリタ リミテ | Disordered nanoporous crystal form didiotactic polystyrene, process for its preparation and article comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021533282A (en) * | 2018-07-31 | 2021-12-02 | マテリアス・ソチエタ・ア・レスポンサビリタ・リミタータMATERIAS S.r.l. | Active twine and woven fabric for stabilization and controlled release of active compounds |
| JP7391094B2 (en) | 2018-07-31 | 2023-12-04 | マテリアス・ソチエタ・ア・レスポンサビリタ・リミタータ | Active strands and fabrics for stabilization and controlled release of active compounds |
| CN114015154A (en) * | 2021-11-09 | 2022-02-08 | 南方电网科学研究院有限责任公司 | Preparation method of environment-friendly high-voltage cable polypropylene insulating material |
| CN114015154B (en) * | 2021-11-09 | 2023-08-18 | 南方电网科学研究院有限责任公司 | Preparation method of environment-friendly high-voltage cable polypropylene insulating material |
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