JPH03221501A - Synthesis of cyclodextrin polymer and production of cyclodextrin film - Google Patents
Synthesis of cyclodextrin polymer and production of cyclodextrin filmInfo
- Publication number
- JPH03221501A JPH03221501A JP1870290A JP1870290A JPH03221501A JP H03221501 A JPH03221501 A JP H03221501A JP 1870290 A JP1870290 A JP 1870290A JP 1870290 A JP1870290 A JP 1870290A JP H03221501 A JPH03221501 A JP H03221501A
- Authority
- JP
- Japan
- Prior art keywords
- cyclodextrin
- polymer
- film
- reaction
- pva
- 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.)
- Pending
Links
- 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 abstract description 58
- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 41
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000012528 membrane Substances 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 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 1
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 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 1
- 229940080345 gamma-cyclodextrin Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はシクロデキストリンポリマーの合成方法及びシ
クロデキストリン膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for synthesizing a cyclodextrin polymer and a method for producing a cyclodextrin membrane.
［従来の技術］
シクロデキストリンは水溶液中で種々のゲスト化合物と
構造特異的な包接化合物を形成する。したがって、シク
ロデキストリンを含む固体膜には、特異的な分離能と透
過能などが期待され、またシクロデキストリンが高分子
に担持されることにより単体として成し得なかった種々
の物性を期待することができ、利用面も広がるため、シ
クロデキストリンを含む躾を自由に作成しうる方法が望
まれていた。[Prior Art] Cyclodextrins form structure-specific inclusion compounds with various guest compounds in aqueous solutions. Therefore, solid membranes containing cyclodextrin are expected to have specific separation ability and permeability, and by supporting cyclodextrin on polymers, various physical properties that could not be achieved as a single substance are expected. , and the scope of its use will be expanded.Therefore, a method that would allow for the free creation of cyclodextrin-containing curds was desired.
このようなシクロデキストリン膜の作成に関して、例え
ば特開昭６０−２３２２１０号公報には、シクロデキス
トリンの包接化合物の結晶とイソシアネート基を有する
化合物からなる高分子を市販の限外濾過股上にキャスト
する方法が開示されており、また、特開昭６２−２５８
７０２号公報にはシクロデキストリンと各種モノマーを
反応させた後アクリロニトリル誘導体と共重合して得ら
れた高分子を公知の方法を用いて製！！する方法が開示
されている。Regarding the preparation of such a cyclodextrin membrane, for example, Japanese Patent Application Laid-Open No. 60-232210 discloses that a polymer consisting of crystals of a cyclodextrin clathrate compound and a compound having an isocyanate group is cast onto a commercially available ultrafiltration crotch. A method is disclosed and also disclosed in Japanese Patent Application Laid-Open No. 62-258
No. 702 discloses that a polymer obtained by reacting cyclodextrin with various monomers and then copolymerizing it with an acrylonitrile derivative is produced using a known method! ! A method is disclosed.
［発明が解決しようとする課題］
しかしながら、前記特開昭６０−２３２２１０号開示の
方法はシクロデキストリン膜を高分子自体の膜として使
用しうるちのではなく、また、特開昭６２−２５８７０
２舅開示の方法は、得られる高分子膜中のシクロデキス
トリンの導入率が３〜４％と低く十分なものではなかっ
た。[Problems to be Solved by the Invention] However, the method disclosed in JP-A No. 60-232210 does not use a cyclodextrin membrane as the membrane of the polymer itself;
The method disclosed by the authors was unsatisfactory since the introduction rate of cyclodextrin into the obtained polymer film was as low as 3 to 4%.
従って本発明の目的は、シクロデキストリンを高い導入
率で含有することのできるシクロデキストリンポリマー
の合成方法を提供することにある。Therefore, an object of the present invention is to provide a method for synthesizing a cyclodextrin polymer that can contain cyclodextrin at a high introduction rate.
また、本発明の目的は、シクロデキストリンを高い導入
率で含有し、かつ単体の膜として使用しうるシクロデキ
ストリン膜の製造方法を提供することにある。Another object of the present invention is to provide a method for producing a cyclodextrin membrane that contains cyclodextrin at a high introduction rate and can be used as a single membrane.
［課題を解決するための手段］
本発明者等は前記問題点に鑑みて鋭意研究の結果、本発
明の上記目的は、ポリビニルアルコールにシクロデキス
トリンの誘導体をグラフト重合させることを特徴とする
シクロデキストリンポリマーの合成方法及び該シクロデ
キストリンポリマーを用いたシクロデキストリン膜の製
造方法により達成されることを見出した。[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to provide a cyclodextrin, which is characterized in that a cyclodextrin derivative is graft-polymerized to polyvinyl alcohol. It has been found that this can be achieved by a method for synthesizing a polymer and a method for producing a cyclodextrin membrane using the cyclodextrin polymer.
以下に、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明においては、％１！ｌ！特性に優れ、膜強度及び
連続操作性にも優れているポリビニルアルコール（ＰＶ
Ａ）の水酸基にシクロデキストリン誘導体をグラフト重
合し、化学結合させることによってシフロブ・キストリ
ンユニットを導入し、優れた製膜特性を有するＰＶＡ−
シクロデキストリンポリマー〈以下、シクロデキストリ
ンポリマーと称す）を得ることができる。In the present invention, %1! l! Polyvinyl alcohol (PV) has excellent properties, film strength, and continuous operability.
By graft polymerizing a cyclodextrin derivative to the hydroxyl group of A) and chemically bonding it, a siphlob-kistrin unit is introduced, and PVA- has excellent film-forming properties.
A cyclodextrin polymer (hereinafter referred to as cyclodextrin polymer) can be obtained.
本発明においてシクロデキストリンの誘導体を形成する
シクロデキストリンとしては、例えばαシクロデキスト
リン、β−シクロデキストリン及びγ−シクロデキスト
リンが挙げられる。また、本発明に用いられるシクロデ
キストリンの誘導体としては、好ましくはシクロデキス
トリン残基を有するアクリル酸アミドあるいはメタクリ
ル酸アミド、又はシクロデキストリン残基を有するアク
リル酸エステルあるいはメタクリル酸エステルが挙げら
れ、特に下記のようなものが挙げられる。Examples of the cyclodextrin forming the cyclodextrin derivative in the present invention include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Further, the cyclodextrin derivatives used in the present invention preferably include acrylic acid amide or methacrylic acid amide having a cyclodextrin residue, or acrylic acid ester or methacrylic acid ester having a cyclodextrin residue, and in particular, the following: Examples include things like.
以下】獣；
！２．− フ
１）
アクリル酸型
）
メタクリル酸型
また、本発明において使用しうるＰＶＡとしては製膜性
の点から分子量が１万以上のものが好ましく、また、他
のＰＶＡ分子又はシクロデキストリン誘導体等と各々の
水酸基で部分架橋したものも使用しうる。Below] Beast; ! 2. - F1) Acrylic acid type) Methacrylic acid type In addition, the PVA that can be used in the present invention preferably has a molecular weight of 10,000 or more from the viewpoint of film-forming properties, and can also be used with other PVA molecules or cyclodextrin derivatives, etc. Those partially crosslinked with each hydroxyl group may also be used.
本発明においてＰＶＡにアクリル酸型のシクロデキスト
リン誘導体をグラフト重合させる反応は、例えば、ラジ
カルグラフト重合を用い、硝酸セリウムアンモニウムを
触媒として下記のように行な１１＋ムｔ１：ゴ
（Ａ）
ＰＶＡとシクロデキストリン残基を有するアクリル酸ア
ミ
ドとの反応
（Ｂ）
ＰＶＡとシクロデキストリン残基を有するアクリル酸エ
ステルとの反応
（１ヒしへ
ＣＤ１よシクロデキストリンを表わす。In the present invention, the reaction of graft polymerizing an acrylic acid type cyclodextrin derivative onto PVA is carried out as follows using, for example, radical graft polymerization using cerium ammonium nitrate as a catalyst. Reaction with acrylic acid amide having a dextrin residue (B) Reaction of PVA with an acrylic ester having a cyclodextrin residue (1 and CD1 represent cyclodextrin.
）
上記グラフト重合は例えば硝酸、硝酸セリウムアンモニ
ウムを含む溶液中で行なわれ、その反応条件はシクロデ
キストリン誘導体の種類又は目的により種々選択しうる
が、好ましくはＰＶＡとシクロデキストリン誘導体比を
１：１０〜１：ｉｏ。) The above-mentioned graft polymerization is carried out in a solution containing, for example, nitric acid and cerium ammonium nitrate, and the reaction conditions can be variously selected depending on the type or purpose of the cyclodextrin derivative, but preferably the ratio of PVA and cyclodextrin derivative is 1:10 to 1:10. 1:io.
とし、複反応を防止するため反応虐度２０〜１００℃、
好ましくは２０〜５０℃にて２０分〜６時間、好ましく
は２０分〜３時間で行なわれ、その際、反応雰囲気とし
ては窒素雰囲気下又は窒素置換してもよい減圧下が好ま
しいが、大気中で反応を行ってもよい。例えば上記反応
温度においては前記シクロデキストリン誘導体（１）及
び（３）の場合は２０分〜３時間、（２）の場合は２０
分〜６時間、（４〉の場合は２０分〜１時間で反応が行
なわれる。To prevent double reactions, the reaction temperature was 20-100°C,
Preferably, the reaction is carried out at 20 to 50°C for 20 minutes to 6 hours, preferably 20 minutes to 3 hours. At this time, the reaction atmosphere is preferably a nitrogen atmosphere or a reduced pressure that may be replaced with nitrogen. The reaction may be carried out with For example, at the above reaction temperature, the cyclodextrin derivatives (1) and (3) are used for 20 minutes to 3 hours, and the cyclodextrin derivatives (2) are used for 20 minutes to 3 hours.
The reaction is carried out in minutes to 6 hours, and in the case of (4>) 20 minutes to 1 hour.
以下に上記（Ａ）の反応の具体的反応例を示す。Specific reaction examples of the above reaction (A) are shown below.
（反応例）
１Ｎ硝Ｍ（口Ｎ０３）に硝酸セリウムアンモラム（（Ｎ
Ｈ４）２ Ｃｅ （ＮＯ３）ｓ ）を溶解シ０．１モ
ル／１溶液とする。また、水１００−にＰＶＡ （分子
量；１万）１ｇ、アクリル酸アミド−ＣＤ５ａを溶解し
、これに上記の溶液２５１２を加え、窒素雰囲気下２０
℃で１時間重合反応を行なう。反応液を約２，０００−
のアセトン中に注ぎ、再沈澱した後、濾過し、繰り返し
水洗した後減圧乾燥を行ないＰＶＡ−アクリル酸アミド
ＣＤのグラフト共重合体の沈澱物が得られる。(Reaction example) Cerium ammorum nitrate ((N
H4)2Ce(NO3)s) is dissolved in a solution of 0.1 mol/1. In addition, 1 g of PVA (molecular weight: 10,000) and acrylic acid amide-CD5a were dissolved in 100% of water, and the above solution 2512 was added thereto for 20% under a nitrogen atmosphere.
The polymerization reaction is carried out at ℃ for 1 hour. About 2,000-
The mixture is poured into acetone, reprecipitated, filtered, repeatedly washed with water, and dried under reduced pressure to obtain a precipitate of a graft copolymer of PVA-acrylic acid amide CD.
また、メタクリル酸型のシクロデキストリン誘導体をグ
ラフト重合させる反応も反応触媒としてベルオキソニ＠
酸カリウム（Ｋ２ Ｓ２０ａ ）を用いる以外は前記の
（Ａ＞又は（Ｂ）の反応と同様に、また同様の条件で行
なわれる。但し反応時間に関しては１〜４８１１間、好
ましくは６〜２ＪＦＲ間で行なわれる。In addition, belloxoni@
The reaction is carried out in the same manner and under the same conditions as the reaction (A> or (B)) except that potassium acid (K2 S20a ) is used. However, the reaction time is between 1 and 4811, preferably between 6 and 2 JFR. It is done.
以下に、メタクリル酸型シクロデキストリン誘導体を用
いた場合の具体的反応例を示す。Specific reaction examples using methacrylic acid type cyclodextrin derivatives are shown below.
（反応例）
ＰＶＡ （分子量約１万）２（］をＤ Ｍ Ｓ ０５０
１（１に溶＠後、ベルオキソニ硫酸カリウム（Ｋ２８２
０８ン５１１ｇとメタクリル酸型β−ＣＤ （５）６ｑ
を加え、冷却して釣管する。これを４０℃で２４時間反
応させる。(Reaction example) PVA (molecular weight approximately 10,000) 2(] is D M S 050
1 (after dissolving in 1, potassium beroxonisulfate (K282
08 511g and methacrylic acid type β-CD (5) 6q
Add, cool and pipette. This is reacted at 40°C for 24 hours.
反応終了後、反応液を２０００ｉＲのアセトン中に注ぎ
再沈澱した後濾過し、沈澱物をよく水洗し、減圧乾燥し
てグラフト共重合体を得る。（重合率：約４０％）
元素分析及びＮＭＲの結果、得られた共重合体のＣＤ１
人率は約４０％であった。After the reaction is completed, the reaction solution is poured into 2000 iR acetone to precipitate again, and then filtered, and the precipitate is thoroughly washed with water and dried under reduced pressure to obtain a graft copolymer. (Polymerization rate: approximately 40%) As a result of elemental analysis and NMR, CD1 of the obtained copolymer
The attendance rate was approximately 40%.
尚、本発明においてはＣＤ導入率はＰＶＡの水酸基（−
０口）の反応率で定義されるものである。In addition, in the present invention, the CD introduction rate is determined by the hydroxyl group (-
It is defined by the reaction rate of 0 mouth).
本発明のシクロデキストリンポリマーは、例えば膜とし
て透過又は吸着分離膜等に、粉体あるいはビーズ状にし
てガスクロマトグラフィー又は液体クロマトグラフィー
の分離カラム用充填剤に、更にビーズ状あるいはベレッ
ト状にして吸着剤、捕集剤等に用いられる。The cyclodextrin polymer of the present invention can be adsorbed, for example, on a permeation or adsorption separation membrane as a membrane, as a powder or beads on a packing material for a gas chromatography or liquid chromatography separation column, and further as a bead or pellet. Used as agents, collectors, etc.
本発明においては上記得られたポリマーを用いて製膜を
行なう。製膜には種々の公知の方法が用いられるが、例
えば具体的には以下の方法で行なわれる。In the present invention, film formation is performed using the polymer obtained above. Various known methods are used for film formation, and specifically, for example, the following method is used.
すなわち、本発明のシクロデキストリンポリマーを溶媒
に溶解して得られた溶液を支持体上に展延した後、溶媒
を除去して製膜するキャスト方法。That is, a casting method in which a solution obtained by dissolving the cyclodextrin polymer of the present invention in a solvent is spread on a support, and then the solvent is removed to form a film.
例えば、得られたポリマーをジメチルホルムアミド（Ｄ
ＭＦ）またはジメチルスルホキシド（ＤＭＳＯ）に溶解
した溶液をテフロン板、ガラス板、金属板などの支持体
の上に展延した後溶媒を除去（例えば蒸発〉させ膜を形
成する。この１９ＡＤＭＦ。For example, the resulting polymer can be mixed with dimethylformamide (D
MF) or dimethyl sulfoxide (DMSO) is spread on a support such as a Teflon plate, a glass plate, or a metal plate, and then the solvent is removed (e.g., evaporated) to form a film.This 19ADMF.
ＤＭＳＯとも沸点が高く蒸発しにくいため、４０〜６０
℃の熱をかけ、ある程度蒸発した時点で水中に入れて膜
を剥離し、水洗、乾燥してシクロデキストリン膜を得る
方法をとることが出来る。DMSO also has a high boiling point and is difficult to evaporate, so it is 40 to 60%
It is possible to obtain a cyclodextrin film by applying heat to a temperature of °C, and when it evaporates to some extent, placing it in water to peel off the film, washing with water, and drying.
また、別の方法として、本発明のシクロデキストリンポ
リマーを加熱して溶融し、押出し、延伸してフィルムに
成型する押出し法をとることもできる。Alternatively, an extrusion method may be used in which the cyclodextrin polymer of the present invention is heated and melted, extruded, and stretched to form a film.
［発明の効果］
以上諜報に説明したように、本発明により得られるシク
ロデキストリンポリマーは高い導入率でシクロデキスト
リンを含有することがでさ、また、本発明のシクロデキ
ストリンポリマーを用いて得られるシクロデキストリン
膜は、ポリマー自身が製膜性を有しているので他の支持
膜を使用する必要がなく、またポリビニルアルコールが
非常に膜強度が強いため連続操作にも耐えうる。[Effects of the Invention] As explained above, the cyclodextrin polymer obtained by the present invention can contain cyclodextrin at a high introduction rate, and the cyclodextrin polymer obtained by using the cyclodextrin polymer of the present invention can contain cyclodextrin at a high introduction rate. Since the dextrin membrane itself has film-forming properties, there is no need to use another support membrane, and since polyvinyl alcohol has a very strong membrane strength, it can withstand continuous operation.
Claims (2)
導体をグラフト重合させることを特徴とするシクロデキ
ストリンポリマーの合成方法。(1) A method for synthesizing a cyclodextrin polymer, which comprises graft polymerizing a cyclodextrin derivative to polyvinyl alcohol.
導体をグラフト重合させて得られるポリマーを用いて製
膜することを特徴とするシクロデキストリン膜の製造方
法。(2) A method for producing a cyclodextrin membrane, which comprises forming the membrane using a polymer obtained by graft polymerizing a cyclodextrin derivative to polyvinyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1870290A JPH03221501A (en) | 1990-01-29 | 1990-01-29 | Synthesis of cyclodextrin polymer and production of cyclodextrin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1870290A JPH03221501A (en) | 1990-01-29 | 1990-01-29 | Synthesis of cyclodextrin polymer and production of cyclodextrin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03221501A true JPH03221501A (en) | 1991-09-30 |
Family
ID=11978974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1870290A Pending JPH03221501A (en) | 1990-01-29 | 1990-01-29 | Synthesis of cyclodextrin polymer and production of cyclodextrin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03221501A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603974A (en) * | 1994-06-23 | 1997-02-18 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
| US6613703B1 (en) | 2000-04-27 | 2003-09-02 | Kimberly-Clark Worldwide, Inc. | Thermoplastic nonwoven web chemically reacted with a cyclodextrin compound |
| JP2017145320A (en) * | 2016-02-17 | 2017-08-24 | 公立大学法人 富山県立大学 | Template-forming polymerizable compound and curable composition thereof, and cured product thereof |
| CN108598531A (en) * | 2018-01-24 | 2018-09-28 | 辽宁石油化工大学 | A kind of dibenzo 18 is preced with the preparation method of 6 grafting polyvinyl alcohol microporous barriers |
| JP2019157038A (en) * | 2018-03-15 | 2019-09-19 | 古河電気工業株式会社 | Novel polymer compound |
-
1990
- 1990-01-29 JP JP1870290A patent/JPH03221501A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603974A (en) * | 1994-06-23 | 1997-02-18 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
| US6613703B1 (en) | 2000-04-27 | 2003-09-02 | Kimberly-Clark Worldwide, Inc. | Thermoplastic nonwoven web chemically reacted with a cyclodextrin compound |
| JP2017145320A (en) * | 2016-02-17 | 2017-08-24 | 公立大学法人 富山県立大学 | Template-forming polymerizable compound and curable composition thereof, and cured product thereof |
| CN108598531A (en) * | 2018-01-24 | 2018-09-28 | 辽宁石油化工大学 | A kind of dibenzo 18 is preced with the preparation method of 6 grafting polyvinyl alcohol microporous barriers |
| CN108598531B (en) * | 2018-01-24 | 2020-09-08 | 辽宁石油化工大学 | Preparation method of dibenzo 18 crown 6 grafted polyvinyl alcohol microporous membrane |
| JP2019157038A (en) * | 2018-03-15 | 2019-09-19 | 古河電気工業株式会社 | Novel polymer compound |
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