JP7423663B2 - エマルジョン組成物、ポリスチレンナノファイバー、ポリスチレンナノファイバー製品及び製造方法並びに応用 - Google Patents
エマルジョン組成物、ポリスチレンナノファイバー、ポリスチレンナノファイバー製品及び製造方法並びに応用 Download PDFInfo
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- 239000004793 Polystyrene Substances 0.000 title claims description 114
- 229920002223 polystyrene Polymers 0.000 title claims description 114
- 239000002121 nanofiber Substances 0.000 title claims description 94
- 239000000203 mixture Substances 0.000 title claims description 57
- 239000000839 emulsion Substances 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000011148 porous material Substances 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 36
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000001523 electrospinning Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- D—TEXTILES; PAPER
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Artificial Filaments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Removal Of Floating Material (AREA)
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Description
前記第1細孔の細孔径は0.1~5nmであり、好ましくは0.2~4nmであり、より好ましくは0.3~2nmであり、
前記第2細孔の細孔径は6~800nmであり、好ましくは10~600nmであり、より好ましくは15~300nmであり、
前記第3細孔の細孔径は0.1~200μmであり、好ましくは0.5~100μmであり、より好ましくは0.5~50μmであり、さらに好ましくは0.5~20μmである。
実施例1で製造された同じ質量のサンプル1、3A分子篩及び活性炭の16ppmのジクロロエタンを含有する汚染空気に対する浄化能力についてそれぞれ比較し、熱重量分析で吸着量を分析すると、サンプル1の吸着量がそれぞれ分子篩及び活性炭より高いことが見出され、且つ低い温度で基本的な脱着を実現することができ、エネルギーの節約に役立ち、具体的には、図5を参照することができ、本発明のポリスチレンナノファイバー製品の複数レベルの細孔構造及び大きな比表面積により吸着能力及び脱着速度を大幅に向上させることが示される。
実施例1~3で製造されたサンプル1~3に対応して取得したポリスチレンナノファイバー製品をそれぞれ異なる有機溶剤及び油料に浸漬し、秤量法によりサンプルの吸油量を取得し、ポリスチレンナノファイバー製品のある有機溶剤に対する吸油量が50倍の自身重量に達することができることが見出され、具体的には、図6を参照することができ、本発明のポリスチレンナノファイバー製品が様々な有機溶剤に対して高い吸収能力を有することが示される。
前述から分かるように、本発明のポリスチレンナノファイバー及びポリスチレンナノファイバー製品は、超疎水性及び親油性を有し、油性液体をよく通過させることができ、同時に水の通過を阻止し、それによって油水分離に用いることができる。
前述から分かるように、本発明のポリスチレンナノファイバー製品の内部構造は複数レベルで、連通するものであり、物質の輸送を大幅に加速することができる。同時に、各ファイバー間の距離及び細孔はナノレベルに過ぎず、大きいサイズの固体粒子をよく保持することができるため、PM 2.5及びPM10の濾過に用いることができる。
Claims (18)
- 分散相及び連続相を含む、ポリスチレンナノファイバーを製造するエマルジョン組成物であって、前記分散相は、可溶性塩及び第1溶媒を含み、前記連続相は、ポリスチレン、第2溶媒及びスルホン化ポリスチレンを含み、前記ポリスチレンは、シンジオタクチックポリスチレン、アイソタクチックポリスチレン又は両者の組み合わせであり、
前記第1溶媒は、水、グリセリン、プロピレングリコール及びエチレングリコールから選択される1つ又は複数の組み合わせであり、
前記第2溶媒は1,2,4-トリクロロベンゼンであり、
前記可溶性塩は、塩化ナトリウム、塩化カリウム、塩化バリウム、塩化カルシウム、炭酸ナトリウム、炭酸水素ナトリウム、硫酸ナトリウム、硫酸カリウム、硝酸ナトリウム、硝酸カリウム及び硝酸カルシウムから選択される1つ又は複数の組み合わせである
ことを特徴とするポリスチレンナノファイバーを製造するためのエマルジョン組成物。 - 前記エマルジョン組成物は、前記分散相と前記連続相とが混合して構成され、前記分散相の投入体積は前記連続相の投入体積以上であることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 前記エマルジョン組成物は前記分散相と前記連続相とが混合して構成され、前記分散相の投入体積は、前記連続相の体積の1.5倍以上であることを特徴とする請求項2に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 前記可溶性塩と前記第1溶媒との投入質量比は0.004~0.080:1であり、好ましくは0.006~0.070:1であることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 前記スルホン化ポリスチレンのスルホン化度は0.5~3.5mol%であることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 前記スルホン化ポリスチレン、前記ポリスチレン及び前記第2溶媒の投入質量比は、0.005~0.025:0.03~0.08:1であることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 質量百分率で、前記エマルジョン組成物において、可溶性塩が0.1~6%、第1溶媒が60~85%、ポリスチレンが0.5~10%、第2溶媒が14~30%、スルホン化ポリスチレンが0.05~3%を占めることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 前記ポリスチレンの平均分子量は、1万~200万であり、好ましくは5万~50万であることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 前記エマルジョン組成物は、前記分散相と前記連続相とが混合して構成され、前記分散相の投入体積は、前記連続相の体積の1.5倍以上であり、前記可溶性塩と前記第1溶媒との投入質量比は、0.004~0.080:1であり、前記スルホン化ポリスチレンのスルホン化度は、0.5~3.5mol%であり、前記スルホン化ポリスチレン、前記ポリスチレン及び前記第2溶媒の投入質量比は、0.005~0.025:0.03~0.08:1であり、質量百分率で、前記エマルジョン組成物において、可溶性塩が0.1~6%、第1溶媒が60~85%、ポリスチレンが0.5~10%、第2溶媒が14~30%、スルホン化ポリスチレンが0.05~3%を占め、前記ポリスチレンの平均分子量は1~200万であることを特徴とする請求項1に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物。
- 加熱及び撹拌の条件で、前記分散相を前記連続相に滴下し、前記エマルジョン組成物を製造するステップを含むことを特徴とする請求項1~9のいずれか一項に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物の製造方法。
- 請求項1~9のいずれか一項に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物で製造されたポリスチレンナノファイバー又はポリスチレンナノファイバー製品。
- 前記製品は複数レベル及び/又は互いに連通する細孔構造を有することを特徴とする請求項11に記載のポリスチレンナノファイバー製品。
- 前記複数レベルの細孔構造は第1細孔、第2細孔及び第3細孔を含み、前記第2細孔の細孔径は、前記第1細孔の細孔径より大きく、かつ前記第3細孔の細孔径より小さく、
前記第1細孔の細孔径は0.1~5nmであり、好ましくは0.2~4nmであり、より好ましくは0.3~2nmであり、
前記第2細孔の細孔径は6~800nmであり、好ましくは10~600nmであり、より好ましくは15~300nmであり、
前記第3細孔の細孔径は800nmより大きく、且つ200μm以下であることを特徴とする請求項12に記載のポリスチレンナノファイバー製品。 - 請求項1~9のいずれか一項に記載のポリスチレンナノファイバーを製造するためのエマルジョン組成物を金型に加えて結晶化を行うことを特徴とする請求項11~13のいずれか一項に記載のポリスチレンナノファイバー製品の製造方法。
- 前記製造方法は、さらに
加熱及び撹拌の条件で、前記分散相を前記連続相に滴下し、前記ポリスチレンナノファイバーを製造するためのエマルジョン組成物を製造することと、
そして、取得された前記エマルジョン組成物を設定時間内に金型に入れて、静置して結晶化し、分離、洗浄、凍結乾燥させ、前記ポリスチレンナノファイバー製品を取得することとを含むことを特徴とする請求項14に記載のポリスチレンナノファイバー製品の製造方法。 - 前記設定時間は、0より大きく10分以下であり、好ましくは0より大きく5分以下であることを特徴とする請求項15に記載のポリスチレンナノファイバー製品の製造方法。
- 前記結晶化時間は、1時間より大きく、好ましくは3時間より大きいことを特徴とする請求項14又は15に記載のポリスチレンナノファイバー製品の製造方法。
- 前記結晶化温度は5~90℃であり、好ましくは10~80℃であり、より好ましくは15~45℃であることを特徴とする請求項14又は15に記載のポリスチレンナノファイバー製品の製造方法。
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