JP4888879B2 - Method for producing beaded cyclodextrin polymer - Google Patents
Method for producing beaded cyclodextrin polymer Download PDFInfo
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- JP4888879B2 JP4888879B2 JP2004338716A JP2004338716A JP4888879B2 JP 4888879 B2 JP4888879 B2 JP 4888879B2 JP 2004338716 A JP2004338716 A JP 2004338716A JP 2004338716 A JP2004338716 A JP 2004338716A JP 4888879 B2 JP4888879 B2 JP 4888879B2
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- 229920000858 Cyclodextrin Polymers 0.000 title claims description 42
- 229920000642 polymer Polymers 0.000 title claims description 37
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000001116 FEMA 4028 Substances 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 7
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 7
- 229960004853 betadex Drugs 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 description 6
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 4
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 4
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Description
本発明はビーズ状シクロデキストリンポリマー製造方法に係り、特に、従来よりも製造工程を簡素化することができるとともに、ビーズ状のポリマーを得ることのできる、ビーズ状シクロデキストリンポリマー製造方法に関する。 The present invention relates to a method for producing a bead-shaped cyclodextrin polymer, and more particularly to a method for producing a bead-shaped cyclodextrin polymer, which can simplify the production process as compared with the conventional method and can obtain a bead-shaped polymer.
包接現象を有するシクロデキストリンポリマーは、食品や医薬品をはじめとした広範な分野で、可溶化、消臭、物理・化学的な条件に対する安定化、選択的な分離・抽出、洗浄などの目的で利用されている。従来、ビーズ状シクロデキストリンポリマーの製造方法としては、流動パラフィンなど疎水性液状物質に反応液を滴下し、製造する方法が報告されている。それによれば、疎水性液状物質を有機溶媒等で洗浄する作業が必要であり、洗浄液を事後に処分する必要があった（特許文献１）。 Cyclodextrin polymers with inclusion phenomena are used in a wide range of fields including food and pharmaceuticals for the purposes of solubilization, deodorization, stabilization against physical and chemical conditions, selective separation / extraction, and washing. It's being used. Conventionally, as a method for producing a bead-shaped cyclodextrin polymer, a method for producing a bead-like cyclodextrin polymer by dropping a reaction solution onto a hydrophobic liquid substance such as liquid paraffin has been reported. According to this, the operation | work which wash | cleans a hydrophobic liquid substance with an organic solvent etc. was required, and it was necessary to dispose a washing | cleaning liquid after the fact (patent document 1).
また、非晶質ケイ酸を主成分とするもみ殻灰を添加して、不定形のシクロデキストリンポリマーを調製する方法も提案されている（特許文献２）。 A method for preparing an amorphous cyclodextrin polymer by adding rice husk ash containing amorphous silicic acid as a main component has also been proposed (Patent Document 2).
さて、取り扱い性、各種用途における機能性等の観点から、シクロデキストリンポリマーはビーズ状であることが要求される。しかしながら上記特許文献２の提案では、上述の通り得られる形状は不定形である。一方、特許文献１に示される製法では、製造過程で疎水性液状物質およびその有機溶媒による洗浄過程が必要となり、工程数が多く、そのために製造コストもかかり、さらに有機溶媒洗浄という環境負荷の大きい工程が避けられない。
The cyclodextrin polymer is required to be in the form of beads from the viewpoints of handleability and functionality in various applications. However, in the proposal of
本発明が解決しようとする課題は、上記従来技術の問題点を除き、製造工程を簡素化することができ、かつ環境負荷の大きい工程を排することができるとともに、ビーズ状のポリマーを得ることのできる、ビーズ状シクロデキストリンポリマー製造方法を提供することである。 The problem to be solved by the present invention is to obtain a bead-like polymer while simplifying the production process and eliminating a process with a large environmental load, excluding the above-mentioned problems of the prior art. The present invention provides a method for producing a bead-shaped cyclodextrin polymer.
本願発明者は上記課題について検討した結果、非晶質ケイ酸等を用いた所定条件によって上記課題の解決が可能であることを見出し、本発明に至った。すなわち、上記課題を解決するための手段として本願で特許請求される発明、もしくは少なくとも開示される発明は、以下のとおりである。
As a result of studying the above problems, the present inventor has found that the above problems can be solved by a predetermined condition using amorphous silicic acid or the like, and has reached the present invention. That is, the invention claimed in the present application , or at least the disclosed invention , as means for solving the above-described problems is as follows.
（１） アルカリ条件下でシクロデキストリンに非晶質ケイ酸を溶解し、これにエピクロロヒドリンを加えることによってビーズ状のポリマーが得られる、ビーズ状シクロデキストリンポリマー製造方法。
（２） 非晶質ケイ酸に替えて、ケイ酸ナトリウム、ケイ酸カリウム等のアルカリケイ酸塩、もしくはそれらの水溶液を添加することを特徴とする、（１）に記載のビーズ状シクロデキストリンポリマー製造方法。
（３） 疎水性液状物質の使用およびその有機溶媒による洗浄過程が不要であることを特徴とする、（１）または（２）に記載のビーズ状シクロデキストリンポリマー製造方法。
(1) dissolving the amorphous silicate in the cyclodextrin under alkaline conditions, bead-like polymer is obtained by adding this to the epichlorohydrin, beaded cyclodextrin polymer production process.
(2) The bead-like cyclodextrin polymer according to (1), wherein an alkali silicate such as sodium silicate or potassium silicate or an aqueous solution thereof is added instead of amorphous silicic acid. Production method.
(3) The method for producing a beaded cyclodextrin polymer according to (1) or (2), wherein the use of a hydrophobic liquid substance and the washing process with an organic solvent thereof are unnecessary.
すなわち本発明は、非晶質ケイ酸またはケイ酸塩を反応液に添加して、ビーズ状のシクロデキストリンポリマー製造を行う方法に係るものであり、本発明によれば、従来技術では必要であった有機溶媒等による洗浄工程が省略され、製造工程を簡素化することができるとともに、環境負荷の大きい有機溶媒等廃棄物の排出工程をなくすることができる。そしてなおかつ、取り扱い性・機能性において優れるビーズ状のポリマーを得ることができる。 That is, the present invention relates to a method for producing a bead-shaped cyclodextrin polymer by adding amorphous silicic acid or silicate to a reaction solution, and according to the present invention, it is necessary in the prior art. In addition, the cleaning process using an organic solvent or the like can be omitted, the manufacturing process can be simplified, and the waste discharging process such as an organic solvent having a large environmental load can be eliminated. In addition, a bead-like polymer having excellent handling properties and functionality can be obtained.
以下、本発明を図面も用いつつ詳細に説明する。
図１は、本発明のビーズ状シクロデキストリンポリマー製造方法の構成を示すフロー図である。図示するように本方法では、シクロデキストリン１をアルカリ条件下に加え（Ｐ１）、これに非晶質ケイ酸２を添加し（Ｐ２）、さらにこれにエピクロロヒドリン３を加える（Ｐ３）という構成をとることによって、ビーズ状シクロデキストリンポリマー１０が得られる。シクロデキストリンポリマー１０としては、水不溶性のもの、水溶性のもの、いずれをも得ることができる。
Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a flow diagram showing the configuration of the method for producing a bead-shaped cyclodextrin polymer of the present invention. As shown in the figure, in this method,
図のＰ１において、非晶質ケイ酸２に替えてケイ酸ナトリウム、ケイ酸カリウム等のアルカリケイ酸塩、もしくはそれらの水溶液を添加することとしてもよい。
In P1 of the figure, instead of amorphous
図示されるように、本発明の方法によれば、ビーズ状シクロデキストリンポリマー１０を製造するために、疎水性液状物質の使用や、また、その有機溶媒による洗浄過程が不要である。
As shown in the figure, according to the method of the present invention, it is not necessary to use a hydrophobic liquid substance or a washing process with an organic solvent in order to produce the bead-
以下、本発明の実施例を説明するが、本願はかかる実施例に限定されるものではない。
＜実施例１＞
水酸化ナトリウム水溶液（ＮａＯＨ80.0g/Ｈ２Ｏ200.0g）にβ−シクロデキストリン60.0g（52.86mmol）を溶解させ、次に、非晶質ケイ酸60.0g（1mol）を溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状β−シクロデキストリンポリマーを得た。
Examples of the present invention will be described below, but the present application is not limited to such examples.
<Example 1>
Β-cyclodextrin 60.0 g (52.86 mmol) is dissolved in sodium hydroxide aqueous solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) is dissolved, and a Teflon blade is attached. Add 45.6 g (492.9 mmol) of epichlorohydrin while rotating the stir bar at 400 rpm, and after stirring at 50 ° C. for 420 minutes, perform suction filtration using a Buchner funnel until neutral with water. Washing and finally washing with methanol and drying under reduced pressure gave a colorless or white bead-like β-cyclodextrin polymer.
＜実施例２＞
実施例１と同様に、水酸化ナトリウム水溶液（ＮａＯＨ80.0g/Ｈ２Ｏ200.0g）にα−シクロデキストリン51.5g（52.9mmol）を溶解させ、次に、非晶質ケイ酸60.0g（1.0mol）を溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状α−シクロデキストリンポリマーを得た。
<Example 2>
In the same manner as in Example 1, 51.5 g (52.9 mmol) of α-cyclodextrin was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), and then amorphous silicic acid 60.0 g (1.0 mol) ), Add 45.6 g (492.9 mmol) of epichlorohydrin while rotating a stir bar with a Teflon blade at 400 rpm, stir for 420 minutes at 50 ° C., and perform suction filtration using a Buchner funnel. After washing with water until neutral, and finally with methanol, drying under reduced pressure gave a colorless or white bead-like α-cyclodextrin polymer.
＜実施例３＞
実施例１と同様に、水酸化ナトリウム水溶液（ＮａＯＨ80.0g/Ｈ２Ｏ200.0g）にγ−シクロデキストリン68.6g（52.9mmol）を溶解させ、次に、非晶質ケイ酸60.0g（1.0mol）を溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状γ−シクロデキストリンポリマーを得た。
<Example 3>
In the same manner as in Example 1, 68.6 g (52.9 mmol) of γ-cyclodextrin was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), and then amorphous silicic acid 60.0 g (1.0 mol) ), Add 45.6 g (492.9 mmol) of epichlorohydrin while rotating a stir bar with a Teflon blade at 400 rpm, stir for 420 minutes at 50 ° C., and perform suction filtration using a Buchner funnel. After washing with water until neutral, and finally with methanol, drying under reduced pressure gave a colorless or white bead-like γ-cyclodextrin polymer.
＜実施例４＞
実施例１と同様に、水酸化ナトリウム水溶液（ＮａＯＨ80.0g/Ｈ２Ｏ200.0g）にα−シクロデキストリン25.7g（26.4mmol）およびβ−シクロデキストリン30.0g（26.4mmol）を溶解させ、次に、非晶質ケイ酸60.0g（1.0mol）を溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状α，β−シクロデキストリン混合ポリマーを得た。
<Example 4>
In the same manner as in Example 1, 25.7 g (26.4 mmol) of α-cyclodextrin and 30.0 g (26.4 mmol) of β-cyclodextrin were dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g). Dissolve 60.0 g (1.0 mol) of amorphous silicic acid, add 45.6 g (492.9 mmol) of epichlorohydrin while rotating a stirring rod with a Teflon blade at 400 rpm, and stir for 420 minutes at 50 ° C. The solution was subjected to suction filtration using a Buchner funnel, washed with water until neutral, finally washed with methanol, and then dried under reduced pressure to obtain colorless or white bead-like α, β-cyclodextrin mixed polymer.
＜実施例５＞
実施例４と同様に、水酸化ナトリウム水溶液（ＮａＯＨ80.0g/Ｈ２Ｏ200.0g）にβ−シクロデキストリン30.0g（26.4mmol）およびγ−シクロデキストリン34.3g（26.4mmol）を溶解させ、次に、非晶質ケイ酸60.0g（1.0mol）を溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状β，γ−シクロデキストリン混合ポリマーを得た。
<Example 5>
In the same manner as in Example 4, 30.0 g (26.4 mmol) of β-cyclodextrin and 34.3 g (26.4 mmol) of γ-cyclodextrin were dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g). Dissolve 60.0 g (1.0 mol) of amorphous silicic acid, add 45.6 g (492.9 mmol) of epichlorohydrin while rotating a stirring rod with a Teflon blade at 400 rpm, and stir for 420 minutes at 50 ° C. The solution was subjected to suction filtration using a Buchner funnel, washed with water until neutral, finally washed with methanol, and then dried under reduced pressure to obtain colorless or white bead-like β, γ-cyclodextrin mixed polymer.
＜実施例６＞
実施例４と同様に、水酸化ナトリウム水溶液（ＮａＯＨ80.0g/Ｈ２Ｏ200.0g）にα−シクロデキストリン25.7g（26.4mmol）およびγ−シクロデキストリン34.3g（26.4mmol）を溶解させ、次に、非晶質ケイ酸60.0g（1.0mol）を溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状α，γ−シクロデキストリン混合ポリマーを得た。
<Example 6>
In the same manner as in Example 4, 25.7 g (26.4 mmol) of α-cyclodextrin and 34.3 g (26.4 mmol) of γ-cyclodextrin were dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g). Dissolve 60.0 g (1.0 mol) of amorphous silicic acid, add 45.6 g (492.9 mmol) of epichlorohydrin while rotating a stirring rod with a Teflon blade at 400 rpm, and stir for 420 minutes at 50 ° C. The solution was suction filtered using a Buchner funnel, washed with water until neutral, finally washed with methanol, and then dried under reduced pressure to obtain colorless or white bead-like α, γ-cyclodextrin mixed polymer.
＜実施例７＞
実施例１と同様に、水酸化ナトリウム水溶液（ＮａＯＨ42.4g/Ｈ２Ｏ128.0g）にβ−シクロデキストリン60.0g（52.86mmol）を溶解させ、次に、ケイ酸ナトリウム溶液（Ｎａ２Ｏ含有量17.0-19.0重量%、ＳｉＯ２含有量35.0-38.0重量%）171.4gを溶解し、テフロン羽根付きの撹拌棒を毎分400回転させながら、エピクロロヒドリン45.6g（492.9mmol）を加え、50℃で420分撹拌後、ブフナー漏斗を使用して吸引濾過を行い、水で中性になるまで洗浄、最後にメタノールで洗浄後、減圧乾燥し、無色または白色のビーズ状β−シクロデキストリンポリマーを得た。
<Example 7>
In the same manner as in Example 1, 60.0 g (52.86 mmol) of β-cyclodextrin was dissolved in an aqueous sodium hydroxide solution (NaOH 42.4 g / H 2 O 128.0 g), and then sodium silicate solution (Na 2 O content) 17.0-19.0 wt%, SiO 2 content 35.0-38.0 wt%) 171.4 g was dissolved, and 45.6 g (492.9 mmol) of epichlorohydrin was added while rotating a stir bar equipped with a Teflon blade at 400 rpm. After stirring for 420 minutes at ℃, suction filtration is performed using a Buchner funnel, washed with water until neutral, finally washed with methanol, dried under reduced pressure, and colorless or white bead-like β-cyclodextrin polymer is obtained. Obtained.
本発明のビーズ状シクロデキストリンポリマー製造方法は上述のように構成されているため、分離・精製、濃縮および除去剤等の様々な分野で使用されているビーズ状シクロデキストリンポリマーの有機溶媒使用量が少ない環境にやさしい新規製造法として利用することができる。また、本技術による水不溶性ビーズ状シクロデキストリンポリマーはその製造が簡易かつ環境保護志向であるため、新規分析技術等への応用、実用化研究に広く活用されやすいものであり、新事業創出の活性化が大きく期待できる。 Since the method for producing a beaded cyclodextrin polymer of the present invention is configured as described above, the amount of the organic solvent used for the beaded cyclodextrin polymer used in various fields such as separation / purification, concentration and removal agent is small. It can be used as a new environment-friendly new manufacturing method. In addition, the water-insoluble beaded cyclodextrin polymer produced by this technology is easy to manufacture and environmentally friendly, so it can be widely used for new analytical technologies and practical research. We can expect great progress.
１…シクロデキストリン
２…非晶質ケイ酸
３…エピクロロヒドリン
１０…ビーズ状シクロデキストリンポリマー
Ｐ１…アルカリ条件下への添加過程
Ｐ２…非晶質ケイ酸等添加過程
Ｐ３…エピクロロヒドリン添加過程
DESCRIPTION OF
Claims (3)
The method for producing a beaded cyclodextrin polymer according to claim 1 or 2, characterized in that the use of a hydrophobic liquid substance and the washing process with an organic solvent are unnecessary.
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| JP5892837B2 (en) * | 2012-03-30 | 2016-03-23 | Ｄｏｗａホールディングス株式会社 | Composite material of cyclodextrin and porous silica particles, and production method thereof, metal extractant, cesium extractant, and gas adsorbent |
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