WO2009123073A1 - Cyclodextrin composite material and process for production thereof - Google Patents
Cyclodextrin composite material and process for production thereof Download PDFInfo
- Publication number
- WO2009123073A1 WO2009123073A1 PCT/JP2009/056402 JP2009056402W WO2009123073A1 WO 2009123073 A1 WO2009123073 A1 WO 2009123073A1 JP 2009056402 W JP2009056402 W JP 2009056402W WO 2009123073 A1 WO2009123073 A1 WO 2009123073A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- cyclodextrin
- composite material
- medium
- containing composite
- 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.)
- Ceased
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
Definitions
- the present invention relates to a composite material containing a cyclodextrin polymer that can be provided in any size and shape, and a method for producing the same.
- Cyclodextrin is a water-soluble substance in which 6 to 8 glucopyranoses are linked in a ring.
- the molecule has a hydrophobic space, and an organic compound such as dioxins, an inorganic compound such as carbon dioxide, and ions such as iodine enter the space to form an inclusion compound.
- a technology for removing environmental pollutants using a water-insoluble polymerized cyclodextrin utilizing such properties is already known.
- a microorganism-immobilized carrier utilizing the microbial growth action of cyclodextrin has also been proposed (Patent Document 1).
- a method for producing a granular epoxy compound crosslinked cyclodextrin polymer of about several tens of ⁇ m to 1300 ⁇ m a method of dropping a mixed solution of a crosslinking agent and an alkaline aqueous solution of a cyclodextrin compound onto a hydrophobic liquid substance such as liquid paraffin (Patent Document) 2) or a method of dropping an alkaline aqueous solution of a cyclodextrin compound into an epoxy compound as a crosslinking agent (Patent Document 3) has been reported. According to them, the operation
- Non-patent Document 1 a method for producing cyclodextrin-bound chitosan by chemically bonding cyclodextrin to the surface of chitosan beads has been proposed.
- the water-insolubilized cyclodextrin compound is effective as an agent for removing environmental pollutants such as dioxins, and as an activation material for microorganisms used in microorganism tanks in water treatment facilities and waste treatment facilities.
- the water-insolubilized cyclodextrin compound is required to have a certain size and shape, simplification of the manufacturing process, and reduction of waste.
- Patent Documents 2 and 3 only a material having a size of about 1300 ⁇ m at maximum can be generated, and a large amount of cleaning organic waste liquid is discharged in the manufacturing process.
- the manufacturing method of Non-Patent Document 1 requires a plurality of manufacturing steps.
- the problem to be solved by the present invention is to provide a composite material containing a cyclodextrin polymer, which can be provided in any size and shape, and a method for producing the same, except for the problems of the above-described technology. .
- the inventor of the present invention added amorphous silicic acid to cyclodextrin under alkaline conditions, added a monoepoxy, diepoxy, triepoxy or polyepoxy compound to the epoxy compound by crosslinking reaction of the epoxy compound.
- a wood component derived wood, an industrial material, a cellulose compound or an industrial plastic is added to produce a multi-component material containing a water-insoluble epoxy compound-crosslinked cyclodextrin polymer.
- a cyclodextrin polymer-containing composite material comprising an epoxy-based compound-crosslinked cyclodextrin polymer and a medium on which it is supported, and having a shape, size and porosity according to the properties of the medium.
- the cyclodextrin polymer-containing composite material according to (1), wherein the medium is a porous polymer.
- the medium is any one of a styrene polymer, a tetrafluoroethylene polymer, a nylon polymer, a propylene polymer, an ethylene polymer, or an acetal polymer. Polymer-containing composite material.
- Amorphous silicic acid is added to cyclodextrin under alkaline conditions, and a monoepoxy compound, diepoxy compound, triepoxy compound or polyepoxy compound is added to the epoxy compound to crosslink the epoxy compound by a crosslinking reaction of the epoxy compound.
- a method for producing a cyclodextrin polymer-containing composite material, wherein a medium in which the cyclodextrin polymer is finally supported is added in the step of producing a cyclodextrin polymer.
- the medium is any one of a melamine polymer, a urethane polymer, a styrene polymer, a tetrafluoroethylene polymer, a nylon polymer, a propylene polymer, an ethylene polymer, or an acetal polymer, (11)
- the term “supported” means that the cyclodextrin polymer is contained in a cellulosic product, a piece of wood, or a medium composed of various polymers, and in particular, is necessarily contained on the surface.
- the composite material carrying the cyclodextrin polymer can be provided in any size and shape. it can.
- toxic substances such as dioxins and useful substances such as catechin are industrially separated from water, or when microorganisms in microbial tanks in water treatment facilities and waste treatment facilities are activated, efficient microbial treatment is performed.
- the composite material of the present invention is very convenient for these treatments.
- the treatment is efficient by floating in a medium (gas, liquid) by a water flow or rising bubbles in addition to the shape of a filler (such as a shape or a cylinder). There is something to become.
- a filler such as a shape or a cylinder.
- the same can be said for the batch type and the continuous type. Therefore, when used for the microorganism fixing layer, it is necessary to devise the shape and increase the size (including the weight of the particles), and the present invention can meet such a demand.
- the non-porous material When packing in a column, etc., the non-porous material must have the same particle size in order to design the column efficiently and without increasing the pressure with the medium (gas, liquid) in which the substance requiring separation exists.
- Spherical fillers are optimal. Therefore, the present invention capable of selecting and controlling the shape as a composite material can meet such a demand.
- the filler is porous, the contact area with the medium (gas, liquid) is large, so that the processing of the medium (gas, liquid) containing substances that require efficient separation is efficient. Can often be implemented. Therefore, the composite material of the present invention having porosity can meet such a demand.
- fillers of various shapes such as a square shape, a cylindrical shape, a semi-cylindrical shape
- the present invention capable of selecting and controlling the shape as a composite material can meet such a demand.
- Cyclodextrin 2 Amorphous silicic acid 3: Epoxy compound 4: Material used as a medium 10: Composite material containing an epoxy compound-crosslinked cyclodextrin polymer P1: Addition process to alkaline aqueous solution P2: Amorphous silicic acid addition process P3: Epoxy compound addition process
- FIG. 1 is a flow diagram showing the structure of a method for producing a composite material containing an epoxy compound-crosslinked cyclodextrin polymer of the present invention.
- cyclodextrin 1 is added to an alkaline aqueous solution (P1), amorphous silicic acid 2 is added thereto (P2), and epichlorohydrin, ethylene glycol diglycidyl ether, butane is further added thereto.
- step (P3) of adding an epoxy-based compound 3 such as diol diglycidyl ether (P3) the material 4 as a medium on which the cyclodextrin polymer is supported in the composite material such as wood chip, cellulose compound or plastic is added before the P3 step or epoxy
- An epoxy compound-crosslinked cyclodextrin polymer-containing composite material (multi-component material) 10 is obtained by adopting a configuration in which the compound is added simultaneously with the system compound 3 or during the process P3.
- the material added with a spherical plastic material is a non-porous CDP-plastic material (“CDP” is a cyclodextrin polymer. The same applies hereinafter), and the ratio of plastic compared to CDP Because of its high material strength, it is suitable for applications such as columns where pressure is applied.
- CDP non-porous CDP-plastic material
- sponge-like plastic materials and materials added with cellulose or cellulose spheres are suitable for use in batch-type devices, bioreactors and the like because they are porous and can be controlled in shape.
- the composite material to which cellulose spheres are added is also suitable for use in columns and the like.
- the cyclodextrin polymer-containing composite material of the present invention can be used as a material for separation / extraction.
- epichlorohydrin which is a monoepoxy compound
- epichlorohydrin which is a monoepoxy compound
- the present invention can be implemented even if an epoxy compound other than a monoepoxy compound such as ethylene glycol diglycidyl ether is used instead. We have confirmed that we can do it.
- ⁇ -cyclodextrin is used as the cyclodextrin, but it has also been confirmed that the present invention can be carried out by using ⁇ -cyclodextrin or ⁇ -cyclodextrin instead.
- ⁇ -cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) Impregnating 45.6 g (492.9 mmol) of epichlorohydrin into 14 g of fibrem (registered trademark) which is a sponge sponge cellulose of about 2 mm square while rotating a stirring rod with blades at 150 rpm. After stirring at 60 ° C.
- aqueous sodium hydroxide solution NaOH 80.0 g / H 2 O 200.0 g
- Teflon Impregnating 45.6 g (492.9 mmol) of epichlorohydrin into 14 g of fibrem (registered trademark) which is a sponge sponge cellulose of about 2 mm square while rotating a stirring rod with blades at 150 rpm.
- ⁇ -cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) While rotating a stirring rod with blades at 150 rpm, 5 g of sponge sponge cellulose having a size of about 4 to 8 mm square was impregnated with 45.6 g (492.9 mmol) of epichlorohydrin. After stirring at 120 ° C.
- ⁇ -cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) While stirring a stirring rod with blades at 150 revolutions per minute, 5.5 g of porous cellulose having a particle size of 4 mm and impregnated with 45.6 g (492.9 mmol) of epichlorohydrin were added, After stirring for 80 minutes, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a particle size of about 4 mm containing 53% by weight of epichlorohydrin crosslinked ⁇ -cyclodextrin polymer.
- ⁇ -cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) While stirring a stirring rod with blades at 150 rpm, a mixture of 15.0 g of a piece of wood having a size of about 2.4 mm to 10 mm and 45.6 g (492.9 mmol) of epichlorohydrin was added, After stirring at 60 ° C.
- an aqueous sodium hydroxide solution NaOH 80.0 g / H 2 O 200.0 g
- Teflon (Registered trademark) While stirring a stirring rod with blades at 150 rpm, a mixture of 15.0 g of a piece of wood having a size of about 2.4 mm to 10 mm and 45.6 g (492.9 mmol) of
- ⁇ -cyclodextrin 60.0 g (52.9 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1.0 mol) was dissolved, What impregnated 45.6 g (492.9 mmol) of epichlorohydrin into 1.0 g of a cubic porous melamine polymer of about 1 cm square while rotating a stirring rod with a Teflon (registered trademark) blade at 150 rpm. In addition, after stirring at 60 ° C.
- ⁇ -cyclodextrin 60.0 g (52.9 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1.0 mol) was dissolved, What impregnated 45.6 g (492.9 mmol) of epichlorohydrin into 1.0 g of a cubic porous urethane polymer of about 1 cm square while rotating a stirring rod with a Teflon (registered trademark) blade at 150 rpm. In addition, after stirring at 60 ° C.
- ⁇ -cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stir bar equipped with a Teflon (registered trademark) blade at 150 revolutions per minute, 20 styrene polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin were added, After stirring for 180 minutes at °C, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked ⁇ -cyclodextrin polymer An epichlorohydrin crosslinked ⁇ -cyclodextrin polymer-styrene polymer having a diameter of
- ⁇ -cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stirring bar with a Teflon (registered trademark) blade at 150 revolutions per minute, an impregnation with 20 tetrafluoroethylene polymers having a spherical diameter of 2.4 mm and epichlorohydrin 4.56 g (49.3 mmol) was added. After stirring at 60 ° C.
- ⁇ -cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stirring bar with a Teflon (registered trademark) blade at 150 revolutions per minute, 20 nylon polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin were added.
- ⁇ -cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While impregnating 20 propylene polymers with a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin while rotating a stirring bar with a Teflon (registered trademark) blade at 150 revolutions per minute, After stirring for 180 minutes at °C, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked ⁇ -cyclodextrin polymer An epichlorohydrin crosslinked ⁇ -cyclodextrin polymer-nylon polymer having a diameter of about 3.2 mm
- ⁇ -cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stir bar equipped with a Teflon (registered trademark) blade at 150 revolutions per minute, an impregnation with 20 ethylene polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin was added.
- ⁇ -cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stir bar equipped with a Teflon (registered trademark) blade at 150 revolutions per minute, 20 acetal polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin were added.
- the epoxy compound-crosslinked cyclodextrin polymer-containing composite material of the present invention can be made into any shape and size, so that it can be used in various industrial fields such as separation / purification, concentration, removal and microbial activation material. It is. In addition, the manufacturing method is simple and the amount of organic solvent used is small. Therefore, industrial applicability is high.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
本発明は、任意の大きさと形状にて提供することが可能な、シクロデキストリンポリマーを含む複合材料、およびその製造方法に関するものである。 The present invention relates to a composite material containing a cyclodextrin polymer that can be provided in any size and shape, and a method for producing the same.
シクロデキストリンは、グルコピラノースが６～８個環状に連なった水溶性物質である。分子内部に疎水性の空間を有しており、この空間にダイオキシン類などの有機化合物、二酸化炭素などの無機化合物、ヨウ素などのイオンが入り込み、包接化合物を形成する。このような性質を利用した水不溶性ポリマー化シクロデキストリンによる環境汚染物質除去技術などが、既に知られている。また、シクロデキストリンの微生物増殖作用を利用した微生物固定化担体も提案されている（特許文献１）。 Cyclodextrin is a water-soluble substance in which 6 to 8 glucopyranoses are linked in a ring. The molecule has a hydrophobic space, and an organic compound such as dioxins, an inorganic compound such as carbon dioxide, and ions such as iodine enter the space to form an inclusion compound. A technology for removing environmental pollutants using a water-insoluble polymerized cyclodextrin utilizing such properties is already known. In addition, a microorganism-immobilized carrier utilizing the microbial growth action of cyclodextrin has also been proposed (Patent Document 1).
従来、数十μｍ～１３００μｍ程度の粒状エポキシ化合物架橋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の疎水性液状物質に架橋剤とシクロデキストリン化合物のアルカリ水溶液の混合液を滴下する方法（特許文献２）、または架橋剤であるエポキシ化合物にシクロデキストリン化合物のアルカリ水溶液を滴下する方法（特許文献３）が報告されている。それらによれば、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。なおまた、キトサンのビーズ表面にシクロデキストリンを化学結合させてシクロデキストリン結合キトサンを製造する方法も提案されている（非特許文献１）。 Conventionally, as a method for producing a granular epoxy compound crosslinked cyclodextrin polymer of about several tens of μm to 1300 μm, a method of dropping a mixed solution of a crosslinking agent and an alkaline aqueous solution of a cyclodextrin compound onto a hydrophobic liquid substance such as liquid paraffin (Patent Document) 2) or a method of dropping an alkaline aqueous solution of a cyclodextrin compound into an epoxy compound as a crosslinking agent (Patent Document 3) has been reported. According to them, the operation | work which wash | cleans a hydrophobic liquid substance with an organic solvent etc. was required, and it was necessary to discard a washing | cleaning liquid after the fact. In addition, a method for producing cyclodextrin-bound chitosan by chemically bonding cyclodextrin to the surface of chitosan beads has been proposed (Non-patent Document 1).
水不溶化したシクロデキストリン化合物は、ダイオキシン類などの環境汚染物質の除去材や、水処理施設・廃棄物処理施設における微生物槽で用いる微生物の活性化材として有効である。このように工業的材料として利用する場合、多くの場合において、水不溶化シクロデキストリン化合物には、ある程度の大きさと形状、そして、製造工程の簡略化および廃棄物の低減などが求められる。しかし、特許文献２および３に開示されている製造方法では、最大１３００μｍ程度の大きさの材料しか生成できず、さらに製造工程において多量の洗浄有機廃液が排出される。また、非特許文献１の製造方法では、複数の製造工程が必要である。
The water-insolubilized cyclodextrin compound is effective as an agent for removing environmental pollutants such as dioxins, and as an activation material for microorganisms used in microorganism tanks in water treatment facilities and waste treatment facilities. Thus, when used as an industrial material, in many cases, the water-insolubilized cyclodextrin compound is required to have a certain size and shape, simplification of the manufacturing process, and reduction of waste. However, in the manufacturing methods disclosed in
本発明が解決しようとする課題は、上記技術の問題点を除き、任意の大きさと形状にて提供することが可能な、シクロデキストリンポリマーを含む複合材料、およびその製造方法を提供することにある。 The problem to be solved by the present invention is to provide a composite material containing a cyclodextrin polymer, which can be provided in any size and shape, and a method for producing the same, except for the problems of the above-described technology. .
本願発明者は上記課題に関して検討した結果、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添加し、これにモノエポキシ、ジエポキシ、トリエポキシまたはポリエポキシ化合物を加えてエポキシ化合物の架橋反応によりエポキシ化合物架橋シクロデキストリンポリマーを製造する工程において、木材由来の木片、工業材料であるセルロース化合物または工業プラスチックのいずれかを添加して、水不溶性エポキシ化合物架橋シクロデキストリンポリマーを含む複成分系材料を製造すること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もしくは少なくとも開示される発明は以下の通りである。 As a result of studying the above problems, the inventor of the present invention added amorphous silicic acid to cyclodextrin under alkaline conditions, added a monoepoxy, diepoxy, triepoxy or polyepoxy compound to the epoxy compound by crosslinking reaction of the epoxy compound. In the step of producing a compound-crosslinked cyclodextrin polymer, a wood component derived wood, an industrial material, a cellulose compound or an industrial plastic is added to produce a multi-component material containing a water-insoluble epoxy compound-crosslinked cyclodextrin polymer. As a result, the present inventors have found that the above problem can be solved, and have reached the present invention. That is, the invention claimed or at least disclosed in the present application as means for solving the above problems is as follows.
（１） エポキシ系化合物架橋シクロデキストリンポリマーと、これが担持される媒体とからなり、該媒体の性状に従った形状、大きさおよび多孔性を有する、シクロデキストリンポリマー含有複合材料。
（２） 前記媒体がセルロース系化合物であることを特徴とする、（１）に記載のシクロデキストリンポリマー含有複合材料。
（３） 前記媒体が木片であることを特徴とする、（１）に記載のシクロデキストリンポリマー含有複合材料。
（４） 前記媒体がポリマーであることを特徴とする、（１）に記載のシクロデキストリンポリマー含有複合材料。
（５） 前記媒体が多孔性ポリマーであることを特徴とする、（１）に記載のシクロデキストリンポリマー含有複合材料。
（６） 前記多孔性ポリマーがメラミン系ポリマーまたはウレタン系ポリマーであることを特徴とする、（５）に記載のシクロデキストリンポリマー含有複合材料。
(1) A cyclodextrin polymer-containing composite material comprising an epoxy-based compound-crosslinked cyclodextrin polymer and a medium on which it is supported, and having a shape, size and porosity according to the properties of the medium.
(2) The cyclodextrin polymer-containing composite material according to (1), wherein the medium is a cellulose compound.
(3) The cyclodextrin polymer-containing composite material according to (1), wherein the medium is a piece of wood.
(4) The cyclodextrin polymer-containing composite material according to (1), wherein the medium is a polymer.
(5) The cyclodextrin polymer-containing composite material according to (1), wherein the medium is a porous polymer.
(6) The cyclodextrin polymer-containing composite material according to (5), wherein the porous polymer is a melamine polymer or a urethane polymer.
（７） 前記媒体が球状またはその他の形状のプラスチック材料であることを特徴とする、（１）に記載のシクロデキストリンポリマー含有複合材料。
（８） 前記媒体がスチレン系ポリマー、テトラフルオロエチレン系ポリマー、ナイロン系ポリマー、プロピレン系ポリマー、エチレン系ポリマーまたはアセタール系ポリマーのいずれかであることを特徴とする、（１）に記載のシクロデキストリンポリマー含有複合材料。
（９） エポキシ系化合物がエピクロロヒドリン、エチレングリコールジグリシジルエーテルまたはブタンジオールジグリシジルエーテルのいずれかであることを特徴とする、（１）ないし（８）のいずれかに記載のシクロデキストリンポリマー含有複合材料。
（１０） 水中の有機化合物の分離材もしくは抽出材として使用されることを特徴とする、（１）ないし（９）のいずれかに記載のシクロデキストリンポリマー含有複合材料。
(7) The cyclodextrin polymer-containing composite material according to (1), wherein the medium is a plastic material having a spherical shape or other shapes.
(8) The cyclodextrin according to (1), wherein the medium is any one of a styrene polymer, a tetrafluoroethylene polymer, a nylon polymer, a propylene polymer, an ethylene polymer, or an acetal polymer. Polymer-containing composite material.
(9) The cyclodextrin polymer according to any one of (1) to (8), wherein the epoxy compound is any one of epichlorohydrin, ethylene glycol diglycidyl ether or butanediol diglycidyl ether Containing composite material.
(10) The cyclodextrin polymer-containing composite material according to any one of (1) to (9), wherein the composite material is used as a separator or extractant for an organic compound in water.
（１１） 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添加し、これにモノエポキシ化合物、ジエポキシ化合物、トリエポキシ化合物またはポリエポキシ化合物のいずれかを加えてエポキシ化合物の架橋反応によりエポキシ化合物架橋シクロデキストリンポリマーを製造する工程において、最終的にシクロデキストリンポリマーが担持されることになる媒体を添加する、シクロデキストリンポリマー含有複合材料の製造方法。
（１２） 前記媒体がセルロース化合物であることを特徴とする、（１１）に記載のシクロデキストリンポリマー含有複合材料の製造方法。
（１３） 前記媒体が木片であることを特徴とする、（１１）に記載のシクロデキストリンポリマー含有複合材料の製造方法。
（１４） 前記媒体がメラミン系ポリマー、ウレタン系ポリマー、スチレン系ポリマー、テトラフルオロエチレン系ポリマー、ナイロン系ポリマー、プロピレン系ポリマー、エチレン系ポリマーまたはアセタール系ポリマーのいずれかであることを特徴とする、（１１）に記載のシクロデキストリンポリマー含有複合材料の製造方法。
(11) Amorphous silicic acid is added to cyclodextrin under alkaline conditions, and a monoepoxy compound, diepoxy compound, triepoxy compound or polyepoxy compound is added to the epoxy compound to crosslink the epoxy compound by a crosslinking reaction of the epoxy compound. A method for producing a cyclodextrin polymer-containing composite material, wherein a medium in which the cyclodextrin polymer is finally supported is added in the step of producing a cyclodextrin polymer.
(12) The method for producing a cyclodextrin polymer-containing composite material according to (11), wherein the medium is a cellulose compound.
(13) The method for producing a cyclodextrin polymer-containing composite material according to (11), wherein the medium is a piece of wood.
(14) The medium is any one of a melamine polymer, a urethane polymer, a styrene polymer, a tetrafluoroethylene polymer, a nylon polymer, a propylene polymer, an ethylene polymer, or an acetal polymer, (11) The manufacturing method of the cyclodextrin polymer containing composite material as described in (11).
なお本発明において「担持」とは、シクロデキストリンポリマーが、セルロース加工物、木片あるいは各種ポリマーからなる媒体に含まれていること、特に表面には必ず含まれていることをいう。 In the present invention, the term “supported” means that the cyclodextrin polymer is contained in a cellulosic product, a piece of wood, or a medium composed of various polymers, and in particular, is necessarily contained on the surface.
本発明のシクロデキストリンポリマーを含む複合材料およびその製造方法は上述のように構成されるため、これによれば、シクロデキストリンポリマーが担持された複合材料を任意の大きさと形状にて提供することができる。たとえば、ダイオキシン類等の有害物質やカテキン等の有用物質を工業的に水から分離する場合や、また、水処理施設や廃棄物処理施設における微生物槽の微生物を活性化し効率的な微生物処理を行う場合などにおいて、本発明の複合材料はこれらの処理用として大変便利である。 Since the composite material containing the cyclodextrin polymer of the present invention and the manufacturing method thereof are configured as described above, according to this, the composite material carrying the cyclodextrin polymer can be provided in any size and shape. it can. For example, when toxic substances such as dioxins and useful substances such as catechin are industrially separated from water, or when microorganisms in microbial tanks in water treatment facilities and waste treatment facilities are activated, efficient microbial treatment is performed. In some cases, the composite material of the present invention is very convenient for these treatments.
本発明のシクロデキストリンポリマー含有複合材料は、任意の大きさと形状にて提供することが大きな利点であるが、これについて、さらに説明する。
〈１〉大粒径化や粒径制御が可能であること
たとえば上述の水処理において、回分式の場合、小さな粒径の粒子では媒体（気体、液体）中に容易に拡散するため、これを沈殿させるためには相当の時間が必要となる。また、充填剤と媒体の分離時において、粒径が小さいと網目の開きを小さくする必要があるため、これも相当の時間が必要となる。したがって、ある程度の大粒径化は必要であり、本発明はかかる要請に応えることができる。
It is a great advantage to provide the composite material containing cyclodextrin polymer of the present invention in an arbitrary size and shape, which will be further described.
<1> Capable of increasing particle size and controlling particle size
For example, in the above-described water treatment, in the case of a batch system, a particle having a small particle diameter easily diffuses into a medium (gas, liquid), so that it takes a considerable time to precipitate it. In addition, when separating the filler and the medium, if the particle size is small, it is necessary to reduce the opening of the mesh, which also requires considerable time. Therefore, it is necessary to increase the particle size to some extent, and the present invention can meet such a demand.
また連続式（並流、向流とも）の場合、充填剤の大きさと媒体にかける圧力との間には逆の関係がある。工業的に大量の媒体を処理するためには、媒体にかける圧力を抑える必要があることから、ある一定の大きさ、特に理想的には粒径の揃った球形であることが必要である。また、充填剤の粒径が小さいと、オーバーフロー型では媒体と一緒に流れ出てしまい、回分容器下部に媒体出口があるものは媒体と固形材料を分離するためのメッシュに詰まってしまう。したがって、ある程度の大粒径化や粒径を制御できることは必要であり、本発明はかかる要請に応えることができる。 In the case of continuous type (both parallel and countercurrent), there is an inverse relationship between the size of the filler and the pressure applied to the medium. In order to process a large amount of medium industrially, it is necessary to suppress the pressure applied to the medium, and therefore it is necessary to have a certain size, particularly ideally a spherical shape with uniform particle diameter. In addition, when the particle size of the filler is small, the overflow type flows out together with the medium, and the medium outlet at the bottom of the batch container is clogged with a mesh for separating the medium and the solid material. Therefore, it is necessary to control the particle size and particle size to some extent, and the present invention can meet such a demand.
さらに、バイオリアクター等の微生物固定層に用いる場合、充填剤の形状（くら型や円筒状など）の他、水流または上昇する気泡により媒体（気体、液体）中に浮遊させることによって処理が効率的になるものがある。その他、上記回分式や連続式と同様のことがいえる。したがって微生物固定層に用いる場合も、形状を工夫するとともに大きさ（粒子の重量も含めて）を大きくする必要があり、本発明はかかる要請に応えることができる。 Furthermore, when it is used for a microorganism fixed layer such as a bioreactor, the treatment is efficient by floating in a medium (gas, liquid) by a water flow or rising bubbles in addition to the shape of a filler (such as a shape or a cylinder). There is something to become. In addition, the same can be said for the batch type and the continuous type. Therefore, when used for the microorganism fixing layer, it is necessary to devise the shape and increase the size (including the weight of the particles), and the present invention can meet such a demand.
〈２〉形状を選択、制御できること
カラム等に充填する場合、非多孔性の材料では、分離を要する物質が存在する媒体（気体、液体）と効率的、かつ圧力を上げないようにカラムを設計するためには、粒度の揃った球形の充填剤が最適である。したがって、複合材料としての形状を選択、制御できる本発明はかかる要請に応えることができる。
すべての使用方法において、充填剤が多孔質であると媒体（気体、液体）との接触面積が大きいことから、効率的な分離を要する物質含有の媒体（気体、液体）の処理が効率的に実施できることが多い。したがって、多孔性を有する本発明の複合材料はかかる要請に応えることができる。
媒体（気体、液体）中を浮遊させるためや、媒体（気体、液体）と効率的に接触させるために、様々な形（くら型、円筒状、半円筒状など）の充填材が必要とされる。したがって、複合材料としての形状を選択、制御できる本発明はかかる要請に応えることができる。
<2> Able to select and control the shape
When packing in a column, etc., the non-porous material must have the same particle size in order to design the column efficiently and without increasing the pressure with the medium (gas, liquid) in which the substance requiring separation exists. Spherical fillers are optimal. Therefore, the present invention capable of selecting and controlling the shape as a composite material can meet such a demand.
In all methods of use, if the filler is porous, the contact area with the medium (gas, liquid) is large, so that the processing of the medium (gas, liquid) containing substances that require efficient separation is efficient. Can often be implemented. Therefore, the composite material of the present invention having porosity can meet such a demand.
In order to float in the medium (gas, liquid) and to make efficient contact with the medium (gas, liquid), fillers of various shapes (such as a square shape, a cylindrical shape, a semi-cylindrical shape) are required. The Therefore, the present invention capable of selecting and controlling the shape as a composite material can meet such a demand.
１：シクロデキストリン
２：非晶質ケイ酸
３：エポキシ系化合物
４：媒体となる材料
１０：エポキシ化合物架橋シクロデキストリンポリマー含有複合材料
Ｐ１：アルカリ水溶液への添加過程
Ｐ２：非晶質ケイ酸等添加過程
Ｐ３：エポキシ系化合物添加過程
1: Cyclodextrin
2: Amorphous silicic acid
3: Epoxy compound
4: Material used as a medium
10: Composite material containing an epoxy compound-crosslinked cyclodextrin polymer
P1: Addition process to alkaline aqueous solution
P2: Amorphous silicic acid addition process
P3: Epoxy compound addition process
以下、本発明について詳細に説明する。
図１は、本発明のエポキシ化合物架橋シクロデキストリンポリマーを含む複合材料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をアルカリ水溶液に加え（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、エチレングリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル等のエポキシ系化合物３を加える（Ｐ３）工程において、木片・セルロース化合物またはプラスチックといった複合材料においてシクロデキストリンポリマーの担持される媒体となる材料４を、Ｐ３工程の前に、もしくはエポキシ系化合物３と同時に、もしくはＰ３工程中に加えるという構成をとることによって、エポキシ化合物架橋シクロデキストリンポリマー含有複合材料（複成分系材料）１０が得られる。
Hereinafter, the present invention will be described in detail.
FIG. 1 is a flow diagram showing the structure of a method for producing a composite material containing an epoxy compound-crosslinked cyclodextrin polymer of the present invention. As shown in the figure, in this method,
本発明の複合材料のうち、球状のプラスチック材料を添加したものは、非多孔性のＣＤＰ－プラスチック材料（「ＣＤＰ」はシクロデキストリンポリマー。以下も同じ。）であり、ＣＤＰと比べてプラスチックの比率が高いことから、材料強度が高く、圧力をかけるカラム等への用途に適している。 Among the composite materials of the present invention, the material added with a spherical plastic material is a non-porous CDP-plastic material (“CDP” is a cyclodextrin polymer. The same applies hereinafter), and the ratio of plastic compared to CDP Because of its high material strength, it is suitable for applications such as columns where pressure is applied.
また、スポンジ状のプラスチック材料やセルロースまたはセルロース球を添加した材料は、多孔性かつ形状が制御できるため、回分式装置やバイオリアクター等への用途に適している。なおセルロース球を添加した複合材料は、カラム等への用途にも適している。 In addition, sponge-like plastic materials and materials added with cellulose or cellulose spheres are suitable for use in batch-type devices, bioreactors and the like because they are porous and can be controlled in shape. The composite material to which cellulose spheres are added is also suitable for use in columns and the like.
また、スポンジ状の材料の添加では、立方体状、平板状を始めとして、種々の形状の複合材料とすることができる。最終的な複合材料の形状や大きさは、媒体として添加するスポンジ状材料の形状に依存する。また、球状セルロースを用いた場合も同様である。したがって、本複合材料の形状、大きさは、ＣＤＰ原料以外の添加物に依存するといえる。 In addition, by adding a sponge-like material, composite materials having various shapes such as a cubic shape and a flat plate shape can be obtained. The shape and size of the final composite material depend on the shape of the sponge material added as a medium. The same applies when spherical cellulose is used. Therefore, it can be said that the shape and size of the composite material depend on additives other than the CDP raw material.
シクロデキストリンモノマーとしては、たとえば下記のようなものを包接することが明らかになっているので、本発明のシクロデキストリンポリマー含有複合材料は、これらを分離・抽出対象とした材料として用いることができる。
天然ペプチド、脂肪酸、脂溶性ビタミン類、辛み成分、テルペン類、天然色素、カテキン類、スチルベノイド類、フラボノイド類、有機塩素化合物（ビスフェノールＡやダイオキシン類）、ヨウ素、光学活性物質（カルボン酸エステル等を分別沈殿する）。
As the cyclodextrin monomer, for example, it has been clarified that the following are included, and therefore the cyclodextrin polymer-containing composite material of the present invention can be used as a material for separation / extraction.
Natural peptides, fatty acids, fat-soluble vitamins, spicy ingredients, terpenes, natural pigments, catechins, stilbenoids, flavonoids, organochlorine compounds (bisphenol A and dioxins), iodine, optically active substances (carboxylic acid esters, etc.) Fractional precipitation).
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下説明する実施例ではエポキシ化合物としてモノエポキシ化合物であるエピクロロヒドリンを用いているが、エチレングリコールジグリシジルエーテル等、モノエポキシ化合物以外のエポキシ化合物を代わりに用いても本発明を実施できることは、確認済みである。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples described below, epichlorohydrin, which is a monoepoxy compound, is used as an epoxy compound, but the present invention can be implemented even if an epoxy compound other than a monoepoxy compound such as ethylene glycol diglycidyl ether is used instead. We have confirmed that we can do it.
多孔質セルロース、木片等のセルロース系化合物や、メラミン樹脂、ポリウレタン樹脂、ポリスチレン樹脂、ポリテトラフルオロエチレン樹脂、ナイロン樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ポリアセタール樹脂等の樹脂をシクロデキストリンと非晶質ケイ酸のアルカリ水溶液に添加する時期は、エポキシ化合物を添加する前でも、同時でも、あるいはポリマーの析出前である限りはエポキシ化合物を添加後でも、さらにまた、ポリマーの析出前である限りはエポキシ化合物を含浸させた状態でも、本発明を実施できることは確認済みである。 Cellulose compounds such as porous cellulose and wood chips, and resins such as melamine resin, polyurethane resin, polystyrene resin, polytetrafluoroethylene resin, nylon resin, polypropylene resin, polyethylene resin, polyacetal resin, cyclodextrin and amorphous silicic acid The timing of addition to the alkaline aqueous solution is before or after the epoxy compound is added, or after the addition of the epoxy compound as long as it is before the precipitation of the polymer, and as long as it is before the precipitation of the polymer. It has been confirmed that the present invention can be carried out even in the impregnated state.
また、各実施例ではシクロデキストリンとしてβ－シクロデキストリンを用いているが、α－シクロデキストリン、あるいはγ－シクロデキストリンを代わりに用いても本発明を実施できることもまた、確認済みである。 In each example, β-cyclodextrin is used as the cyclodextrin, but it has also been confirmed that the present invention can be carried out by using α-cyclodextrin or γ-cyclodextrin instead.
＜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（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、２ｍｍ角程度の立方体のスポンジ状セルロースであるファイバーム（登録商標）１４ｇにエピクロロヒドリン４５．６ｇ（４９２．９ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを８３重量％含む２ｍｍ角程度の多孔かつ立方体状のエピクロロヒドリン架橋β－シクロデキストリンポリマー－ファイバーム（登録商標）を得た。
<Example 1>
Β-cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) Impregnating 45.6 g (492.9 mmol) of epichlorohydrin into 14 g of fibrem (registered trademark) which is a sponge sponge cellulose of about 2 mm square while rotating a stirring rod with blades at 150 rpm. After stirring at 60 ° C. for 180 minutes, the solution was suction filtered using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and epichlorohydrin cross-linked β-cyclodextrin polymer 83 Porous and cubic epichlorohydrin cross-linked β-cyclodextrin polymer-fibrium (weight%) containing 2% by weight To obtain a recording trademark).
＜実施例２＞
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（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、４－８ｍｍ角程度の立方体のスポンジ状セルロース５ｇにエピクロロヒドリン４５．６ｇ（４９２．９ｍｍｏｌ）を含浸させたものを加え、６０℃で１２０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを７９重量％含む４－８ｍｍ角程度の多孔かつ立方体状のエピクロロヒドリン架橋β－シクロデキストリンポリマー－セルロースを得た。
<Example 2>
Β-cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) While rotating a stirring rod with blades at 150 rpm, 5 g of sponge sponge cellulose having a size of about 4 to 8 mm square was impregnated with 45.6 g (492.9 mmol) of epichlorohydrin. After stirring at 120 ° C. for 120 minutes, suction filtration was performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and 4-8 mm containing 79% by weight of epichlorohydrin crosslinked β-cyclodextrin polymer. A porous and cubic epichlorohydrin-crosslinked β-cyclodextrin polymer-cellulose having an angular degree was obtained.
＜実施例３＞
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（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、多孔性の粒径４ｍｍ球状セルロース５．５ｇにエピクロロヒドリン４５．６ｇ（４９２．９ｍｍｏｌ）を含浸させたものを加え、６０℃で８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを５３重量％含む粒径４ｍｍ程度の多孔かつ球状のエピクロロヒドリン架橋β－シクロデキストリンポリマー－球状セルロースを得た。
<Example 3>
Β-cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) While stirring a stirring rod with blades at 150 revolutions per minute, 5.5 g of porous cellulose having a particle size of 4 mm and impregnated with 45.6 g (492.9 mmol) of epichlorohydrin were added, After stirring for 80 minutes, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a particle size of about 4 mm containing 53% by weight of epichlorohydrin crosslinked β-cyclodextrin polymer. A porous and spherical epichlorohydrin crosslinked β-cyclodextrin polymer-spherical cellulose was obtained.
＜実施例４＞
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（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、２．４ｍｍ～１０ｍｍ程度の大きさの木片１５．０ｇとエピクロロヒドリン４５．６ｇ（４９２．９ｍｍｏｌ）を混合したものを加え、６０℃で１２０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーが木片表面を面または点状に覆った形態で５０重量％含まれるエピクロロヒドリン架橋β－シクロデキストリンポリマー－木片を得た。
<Example 4>
Β-cyclodextrin 60.0 g (52.86 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1 mol) was dissolved, and Teflon ( (Registered trademark) While stirring a stirring rod with blades at 150 rpm, a mixture of 15.0 g of a piece of wood having a size of about 2.4 mm to 10 mm and 45.6 g (492.9 mmol) of epichlorohydrin was added, After stirring at 60 ° C. for 120 minutes, suction filtration is performed using a Buchner funnel, washed with water until neutral, and then dried under reduced pressure. The epichlorohydrin-crosslinked β-cyclodextrin polymer faces the surface of the wood chip. An epichlorohydrin-crosslinked β-cyclodextrin polymer-wood piece containing 50% by weight in a covered form was obtained.
＜実施例５＞
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（５２．９ｍｍｏｌ）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（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、１ｃｍ角程度の立方体の多孔性メラミンポリマー１．０ｇにエピクロロヒドリン４５．６ｇ（４９２．９ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを９６重量％含む１ｃｍ角程度の多孔かつ立方体状のエピクロロヒドリン架橋β－シクロデキストリンポリマー－メラミンポリマーを得た。
<Example 5>
Β-cyclodextrin 60.0 g (52.9 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1.0 mol) was dissolved, What impregnated 45.6 g (492.9 mmol) of epichlorohydrin into 1.0 g of a cubic porous melamine polymer of about 1 cm square while rotating a stirring rod with a Teflon (registered trademark) blade at 150 rpm. In addition, after stirring at 60 ° C. for 180 minutes, suction filtration is performed using a Buchner funnel, washed with water until neutral, and then dried under reduced pressure, containing 96 wt% of epichlorohydrin crosslinked β-cyclodextrin polymer. A porous and cubic epichlorohydrin crosslinked β-cyclodextrin polymer-melamine polymer of about 1 cm square was obtained.
＜実施例６＞
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（５２．９ｍｍｏｌ）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（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、１ｃｍ角程度の立方体の多孔性ウレタンポリマー１．０ｇにエピクロロヒドリン４５．６ｇ（４９２．９ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを９６重量％含む１～１．３ｃｍ角程度の多孔性かつ立方体状のエピクロロヒドリン架橋β－シクロデキストリンポリマー－ウレタンポリマーを得た。
<Example 6>
Β-cyclodextrin 60.0 g (52.9 mmol) was dissolved in an aqueous sodium hydroxide solution (NaOH 80.0 g / H 2 O 200.0 g), then amorphous silicic acid 60.0 g (1.0 mol) was dissolved, What impregnated 45.6 g (492.9 mmol) of epichlorohydrin into 1.0 g of a cubic porous urethane polymer of about 1 cm square while rotating a stirring rod with a Teflon (registered trademark) blade at 150 rpm. In addition, after stirring at 60 ° C. for 180 minutes, suction filtration is performed using a Buchner funnel, washed with water until neutral, and then dried under reduced pressure, containing 96 wt% of epichlorohydrin crosslinked β-cyclodextrin polymer. A porous and cubic epichlorohydrin crosslinked β-cyclodextrin polymer-urethane polymer having a size of about 1 to 1.3 cm square was obtained.
＜実施例７＞
水酸化ナトリウム水溶液（ＮａＯＨ８．０ｇ／Ｈ２Ｏ２０．０ｇ）にβ－シクロデキストリン６．０ｇ（５．３ｍｍｏｌ）を溶解させ、次に、非晶質ケイ酸６．０ｇ（０．１ｍｏｌ）を溶解し、テフロン（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、球径３．２ｍｍのスチレンポリマー２０個とエピクロロヒドリン４．５６ｇ（４９．３ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを０．０１重量％含む球径３．２ｍｍ程度のエピクロロヒドリン架橋β－シクロデキストリンポリマー－スチレンポリマーを得た。
<Example 7>
Β-cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stir bar equipped with a Teflon (registered trademark) blade at 150 revolutions per minute, 20 styrene polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin were added, After stirring for 180 minutes at ℃, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked β-cyclodextrin polymer An epichlorohydrin crosslinked β-cyclodextrin polymer-styrene polymer having a diameter of about 3.2 mm was obtained.
＜実施例８＞
水酸化ナトリウム水溶液（ＮａＯＨ８．０ｇ／Ｈ２Ｏ２０．０ｇ）にβ－シクロデキストリン６．０ｇ（５．３ｍｍｏｌ）を溶解させ、次に、非晶質ケイ酸６．０ｇ（０．１ｍｏｌ）を溶解し、テフロン（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、球径２．４ｍｍのテトラフルオロエチレンポリマー２０個とエピクロロヒドリン４．５６ｇ（４９．３ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを０．０１重量％含む球径２．４ｍｍ程度のエピクロロヒドリン架橋β－シクロデキストリンポリマー－テトラフルオロエチレンポリマーを得た。
<Example 8>
Β-cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stirring bar with a Teflon (registered trademark) blade at 150 revolutions per minute, an impregnation with 20 tetrafluoroethylene polymers having a spherical diameter of 2.4 mm and epichlorohydrin 4.56 g (49.3 mmol) was added. After stirring at 60 ° C. for 180 minutes, suction filtration is performed using a Buchner funnel, washed with water until neutral, and then dried under reduced pressure to give 0.01% by weight of epichlorohydrin crosslinked β-cyclodextrin polymer. An epichlorohydrin crosslinked β-cyclodextrin polymer-tetrafluoroethylene polymer having a spherical diameter of about 2.4 mm was obtained.
＜実施例９＞
水酸化ナトリウム水溶液（ＮａＯＨ８．０ｇ／Ｈ２Ｏ２０．０ｇ）にβ－シクロデキストリン６．０ｇ（５．３ｍｍｏｌ）を溶解させ、次に、非晶質ケイ酸６．０ｇ（０．１ｍｏｌ）を溶解し、テフロン（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、球径３．２ｍｍのナイロンポリマー２０個とエピクロロヒドリン４．５６ｇ（４９．３ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを０．０１重量％含む球径３．２ｍｍ程度のエピクロロヒドリン架橋β－シクロデキストリンポリマー－ナイロンポリマーを得た。
<Example 9>
Β-cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stirring bar with a Teflon (registered trademark) blade at 150 revolutions per minute, 20 nylon polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin were added. After stirring for 180 minutes at ℃, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked β-cyclodextrin polymer An epichlorohydrin crosslinked β-cyclodextrin polymer-nylon polymer having a diameter of about 3.2 mm was obtained.
＜実施例１０＞
水酸化ナトリウム水溶液（ＮａＯＨ８．０ｇ／Ｈ２Ｏ２０．０ｇ）にβ－シクロデキストリン６．０ｇ（５．３ｍｍｏｌ）を溶解させ、次に、非晶質ケイ酸６．０ｇ（０．１ｍｏｌ）を溶解し、テフロン（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、球径３．２ｍｍのプロピレンポリマー２０個とエピクロロヒドリン４．５６ｇ（４９．３ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを０．０１重量％含む球径３．２ｍｍ程度のエピクロロヒドリン架橋β－シクロデキストリンポリマー－ナイロンポリマーを得た。
<Example 10>
Β-cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While impregnating 20 propylene polymers with a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin while rotating a stirring bar with a Teflon (registered trademark) blade at 150 revolutions per minute, After stirring for 180 minutes at ℃, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked β-cyclodextrin polymer An epichlorohydrin crosslinked β-cyclodextrin polymer-nylon polymer having a diameter of about 3.2 mm was obtained.
＜実施例１１＞
水酸化ナトリウム水溶液（ＮａＯＨ８．０ｇ／Ｈ２Ｏ２０．０ｇ）にβ－シクロデキストリン６．０ｇ（５．３ｍｍｏｌ）を溶解させ、次に、非晶質ケイ酸６．０ｇ（０．１ｍｏｌ）を溶解し、テフロン（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、球径３．２ｍｍのエチレンポリマー２０個とエピクロロヒドリン４．５６ｇ（４９．３ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを０．０１重量％含む球径３．２ｍｍ程度のエピクロロヒドリン架橋β－シクロデキストリンポリマー－ナイロンポリマーを得た。
<Example 11>
Β-cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stir bar equipped with a Teflon (registered trademark) blade at 150 revolutions per minute, an impregnation with 20 ethylene polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin was added. After stirring for 180 minutes at ℃, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked β-cyclodextrin polymer An epichlorohydrin crosslinked β-cyclodextrin polymer-nylon polymer having a diameter of about 3.2 mm was obtained.
＜実施例１２＞
水酸化ナトリウム水溶液（ＮａＯＨ８．０ｇ／Ｈ２Ｏ２０．０ｇ）にβ－シクロデキストリン６．０ｇ（５．３ｍｍｏｌ）を溶解させ、次に、非晶質ケイ酸６．０ｇ（０．１ｍｏｌ）を溶解し、テフロン（登録商標）羽根付きの撹拌棒を毎分１５０回転させながら、球径３．２ｍｍのアセタールポリマー２０個とエピクロロヒドリン４．５６ｇ（４９．３ｍｍｏｌ）を含浸させたものを加え、６０℃で１８０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後、減圧乾燥し、エピクロロヒドリン架橋β－シクロデキストリンポリマーを０．０１重量％含む球径３．２ｍｍ程度のエピクロロヒドリン架橋β－シクロデキストリンポリマー－ナイロンポリマーを得た。
<Example 12>
Β-cyclodextrin 6.0 g (5.3 mmol) was dissolved in sodium hydroxide aqueous solution (NaOH 8.0 g / H 2 O 20.0 g), then amorphous silicic acid 6.0 g (0.1 mol) was dissolved, While stirring a stir bar equipped with a Teflon (registered trademark) blade at 150 revolutions per minute, 20 acetal polymers having a spherical diameter of 3.2 mm and 4.56 g (49.3 mmol) of epichlorohydrin were added. After stirring for 180 minutes at ℃, suction filtration is performed using a Buchner funnel, washed with water until neutral, dried under reduced pressure, and a sphere containing 0.01% by weight of epichlorohydrin cross-linked β-cyclodextrin polymer An epichlorohydrin crosslinked β-cyclodextrin polymer-nylon polymer having a diameter of about 3.2 mm was obtained.
本発明のエポキシ化合物架橋シクロデキストリンポリマー含有複合材料は、任意の形状、大きさにすることができるため、分離・精製、濃縮、除去および微生物活性化材等の様々な工業分野での使用が可能である。また、製造方法も簡易、かつ有機溶媒使用量が少ないなどの環境保護志向である。したがって、産業上利用性が高い。
The epoxy compound-crosslinked cyclodextrin polymer-containing composite material of the present invention can be made into any shape and size, so that it can be used in various industrial fields such as separation / purification, concentration, removal and microbial activation material. It is. In addition, the manufacturing method is simple and the amount of organic solvent used is small. Therefore, industrial applicability is high.
Claims (14)
12. The medium according to claim 11, wherein the medium is any one of a melamine polymer, a urethane polymer, a styrene polymer, a tetrafluoroethylene polymer, a nylon polymer, a propylene polymer, an ethylene polymer, or an acetal polymer. The manufacturing method of the cyclodextrin polymer containing composite material as described in any one of.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-090442 | 2008-03-31 | ||
| JP2008090442A JP5467217B2 (en) | 2008-03-31 | 2008-03-31 | Cyclodextrin composite material and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009123073A1 true WO2009123073A1 (en) | 2009-10-08 |
Family
ID=41135451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2009/056402 Ceased WO2009123073A1 (en) | 2008-03-31 | 2009-03-29 | Cyclodextrin composite material and process for production thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5467217B2 (en) |
| WO (1) | WO2009123073A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756260A (en) * | 2014-01-23 | 2014-04-30 | 苏州大学 | Biomass modified thermosetting resin and preparation method thereof |
| CN106336680A (en) * | 2016-09-05 | 2017-01-18 | 台州五麦香生物科技有限公司 | A kind of plastic masterbatch containing biomass, its preparation method and application |
| CN109231406A (en) * | 2018-10-15 | 2019-01-18 | 滨州学院 | The recovery method of surfactant in surfactant flooding sewage |
| CN109865529A (en) * | 2019-03-29 | 2019-06-11 | 中国石油大学(北京) | A kind of N doping stratiform nanocarbon catalyst and its preparation and application |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5590289B2 (en) * | 2008-10-22 | 2014-09-17 | 三菱マテリアル株式会社 | Method for producing silver paste |
| JP5493123B2 (en) * | 2008-10-24 | 2014-05-14 | 関西ペイント株式会社 | Carrier for immobilizing microorganisms |
| JP2011207917A (en) * | 2010-03-26 | 2011-10-20 | Aomori Prefectural Industrial Technology Research Center | Cyclodextrin polymer-containing composite material and method for producing the same |
| US8337967B2 (en) | 2010-09-22 | 2012-12-25 | Empire Technology Development Llc | Can with bisphenol A capture system |
| JP5759772B2 (en) * | 2011-03-31 | 2015-08-05 | シーシーアイ株式会社 | Nanocarbon material with excellent dispersibility |
| JP5759770B2 (en) * | 2011-03-31 | 2015-08-05 | シーシーアイ株式会社 | Nanocarbon dispersant and nanocarbon dispersion |
| JP5759771B2 (en) * | 2011-03-31 | 2015-08-05 | シーシーアイ株式会社 | Nanocarbon dispersant and nanocarbon dispersion |
| JP5836797B2 (en) * | 2011-12-28 | 2015-12-24 | シーシーアイ株式会社 | Nanocarbon dispersant and nanocarbon dispersion |
| 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 |
| JP5892847B2 (en) * | 2012-04-27 | 2016-03-23 | Ｄｏｗａホールディングス株式会社 | Composite material of cyclodextrin and silica-containing substance, method for producing the same, and gas adsorbent |
| JP2014176802A (en) * | 2013-03-14 | 2014-09-25 | Toshiba Corp | Water treatment column and pretreatment device |
| JP6819955B2 (en) * | 2016-09-06 | 2021-01-27 | 日本化学工業株式会社 | Composite particles, their manufacturing methods, oil-water separators using them, and organic compound adsorbents using them. |
| CN110117054B (en) * | 2019-05-20 | 2022-01-25 | 湖南科技大学 | Chelating decolorizing flocculant and preparation method thereof |
| CN113209943B (en) * | 2021-04-16 | 2022-02-01 | 武汉大学 | Cyclodextrin microporous organic net material and preparation method and application thereof |
| CN120248581A (en) * | 2025-04-03 | 2025-07-04 | 临邑大正特纤新材料有限公司 | Preparation and application of biodegradable waterborne polyurethane cross-linked carboxymethyl chitosan-cyclodextrin biomass porous materials |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539399A (en) * | 1984-07-27 | 1985-09-03 | Advanced Separation Technologies Inc. | Bonded phase material for chromatographic separations |
| JPH02228558A (en) * | 1989-03-01 | 1990-09-11 | Showa Denko Kk | Adsorption carrier for chromatography and manufacture thereof |
| JPH04230852A (en) * | 1990-03-06 | 1992-08-19 | Merck Patent Gmbh | Separating material for chromatography |
| JPH07113797A (en) * | 1993-10-13 | 1995-05-02 | Kaken Pharmaceut Co Ltd | Packing agent for separation and purification of heparin affinity substances |
| JPH07225225A (en) * | 1994-02-15 | 1995-08-22 | Showa Denko Kk | Adsorption carrier for chromatography |
| JP2003080225A (en) * | 2001-09-12 | 2003-03-18 | Sekisui Chem Co Ltd | Soil cleaning method by cyclodextrins immobilizing adsorbent |
| JP2003226737A (en) * | 2002-02-04 | 2003-08-12 | Maeda Seikan Kk | Cross-linked cyclodextrin and endocrine disrupter remover using the same |
| JP2005281372A (en) * | 2004-03-29 | 2005-10-13 | Kanagawa Prefecture | Method for producing insoluble cyclodextrin-supported polymer molding |
| JP2007111630A (en) * | 2005-10-20 | 2007-05-10 | Aomori Prefecture | Collecting method and recovery method of dioxins in solution |
| JP2008246287A (en) * | 2007-03-29 | 2008-10-16 | Aomori Prefecture | Method for removing surfactant |
-
2008
- 2008-03-31 JP JP2008090442A patent/JP5467217B2/en not_active Expired - Fee Related
-
2009
- 2009-03-29 WO PCT/JP2009/056402 patent/WO2009123073A1/en not_active Ceased
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539399A (en) * | 1984-07-27 | 1985-09-03 | Advanced Separation Technologies Inc. | Bonded phase material for chromatographic separations |
| JPH02228558A (en) * | 1989-03-01 | 1990-09-11 | Showa Denko Kk | Adsorption carrier for chromatography and manufacture thereof |
| JPH04230852A (en) * | 1990-03-06 | 1992-08-19 | Merck Patent Gmbh | Separating material for chromatography |
| JPH07113797A (en) * | 1993-10-13 | 1995-05-02 | Kaken Pharmaceut Co Ltd | Packing agent for separation and purification of heparin affinity substances |
| JPH07225225A (en) * | 1994-02-15 | 1995-08-22 | Showa Denko Kk | Adsorption carrier for chromatography |
| JP2003080225A (en) * | 2001-09-12 | 2003-03-18 | Sekisui Chem Co Ltd | Soil cleaning method by cyclodextrins immobilizing adsorbent |
| JP2003226737A (en) * | 2002-02-04 | 2003-08-12 | Maeda Seikan Kk | Cross-linked cyclodextrin and endocrine disrupter remover using the same |
| JP2005281372A (en) * | 2004-03-29 | 2005-10-13 | Kanagawa Prefecture | Method for producing insoluble cyclodextrin-supported polymer molding |
| JP2007111630A (en) * | 2005-10-20 | 2007-05-10 | Aomori Prefecture | Collecting method and recovery method of dioxins in solution |
| JP2008246287A (en) * | 2007-03-29 | 2008-10-16 | Aomori Prefecture | Method for removing surfactant |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756260A (en) * | 2014-01-23 | 2014-04-30 | 苏州大学 | Biomass modified thermosetting resin and preparation method thereof |
| CN106336680A (en) * | 2016-09-05 | 2017-01-18 | 台州五麦香生物科技有限公司 | A kind of plastic masterbatch containing biomass, its preparation method and application |
| CN106336680B (en) * | 2016-09-05 | 2018-09-14 | 台州五麦香生物科技有限公司 | A kind of plastic masterbatch containing biomass, its preparation method and application |
| CN109231406A (en) * | 2018-10-15 | 2019-01-18 | 滨州学院 | The recovery method of surfactant in surfactant flooding sewage |
| CN109865529A (en) * | 2019-03-29 | 2019-06-11 | 中国石油大学(北京) | A kind of N doping stratiform nanocarbon catalyst and its preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009242556A (en) | 2009-10-22 |
| JP5467217B2 (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5467217B2 (en) | Cyclodextrin composite material and production method thereof | |
| Aragaw et al. | Biomass-based adsorbents for removal of dyes from wastewater: a review | |
| Islam et al. | Cellulose acetate-based membrane for wastewater treatment—A state-of-the-art review | |
| Li et al. | Novel composite adsorbent consisting of dissolved cellulose fiber/microfibrillated cellulose for dye removal from aqueous solution | |
| Alzate-Sánchez et al. | β-Cyclodextrin polymers on microcrystalline cellulose as a granular media for organic micropollutant removal from water | |
| Modrzejewska et al. | Separation of Cr (VI) on chitosan membranes | |
| Sultan | Polyurethane for removal of organic dyes from textile wastewater | |
| Liu et al. | Review on the aerogel-type oil sorbents derived from nanocellulose | |
| Ghiorghita et al. | Polysaccharide-based composite hydrogels as sustainable materials for removal of pollutants from wastewater | |
| Peng et al. | Nanoporous magnetic cellulose–chitosan composite microspheres: preparation, characterization, and application for Cu (II) adsorption | |
| Liu et al. | Adsorptive removal of copper ions with highly porous chitosan/cellulose acetate blend hollow fiber membranes | |
| Chatterjee et al. | Supersorption capacity of anionic dye by newer chitosan hydrogel capsules via green surfactant exchange method | |
| Cao et al. | Bioinspired multifunctional membrane for aquatic micropollutants removal | |
| JP2019218535A (en) | Novel cyclodextrin polymer which rapidly adsorbs organic contaminants dissolved in water | |
| WO2017026453A1 (en) | Separating agent and liquid-chromatography column | |
| Urbano et al. | Polymer supports for the removal and degradation of hazardous organic pollutants: an overview | |
| Zhu et al. | Aerogels fabricated from wood-derived functional cellulose nanofibrils for highly efficient separation of microplastics | |
| Wang et al. | Fast microwave-assisted hydrolysis of unsaturated polyester resin into column packing for rapid purifying of dye wastewater | |
| Liu et al. | Cellulose/chitosan composite sponge for efficient protein adsorption | |
| Wang et al. | Facile preparation of cyclodextrin polymer materials with rigid spherical structure and flexible network for sorption of organic contaminants in water | |
| Sobolciak et al. | Materials and technologies for the tertiary treatment of produced water contaminated by oil impurities through nonfibrous deep-bed media: A review | |
| Liu et al. | Tentacle-type poly (hydroxamic acid)-modified macroporous cellulose beads: Synthesis, characterization, and application for heavy metal ions adsorption | |
| Crini et al. | Sorption of 4-n-nonylphenol, 4-n-octylphenol, and 4-tert-octyphenol on cyclodextrin polymers | |
| JP2009061429A (en) | Method for separating hydrophobic substance using polyvalent anionic cyclodextrin compound, and selective adsorbent for hydrophobic substance | |
| Han et al. | Encapsulating TiO 2 into polyvinyl alcohol coated polyacrylonitrile composite beads for the effective removal of methylene blue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09727132 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 09727132 Country of ref document: EP Kind code of ref document: A1 |