JPH0655765B2 - Cellulose derivative - Google Patents
Cellulose derivativeInfo
- Publication number
- JPH0655765B2 JPH0655765B2 JP59079634A JP7963484A JPH0655765B2 JP H0655765 B2 JPH0655765 B2 JP H0655765B2 JP 59079634 A JP59079634 A JP 59079634A JP 7963484 A JP7963484 A JP 7963484A JP H0655765 B2 JPH0655765 B2 JP H0655765B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- acid
- product
- cellulose derivative
- ester
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 本発明は新規なセルロース誘導体に関するものであり、
詳しくは、環員数３〜８のシクロアルカンカルボン酸の
セルロースエステルに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel cellulose derivative,
Specifically, it relates to a cellulose ester of a cycloalkanecarboxylic acid having 3 to 8 ring members.
セルロースのカルボン酸エステルは種々の化合物が知ら
れているが、カルボン酸がシクロアルカン環に直結した
カルボキシル基を有するものである場合は殆んど知られ
ていない。セルロースのシクロアルカンカルボン酸エス
テルは、特にそれがセルロース分子中の水酸基の５０％
以上が置換された高置換度エステルの場合は、一般に有
機溶剤に可溶性であり、吸着剤、酵素担体、クロマトグ
ラフイー用担体、光学異性体分離剤、液晶物質等として
利用できる可能性が高い。Various compounds of carboxylic acid esters of cellulose are known, but little is known when the carboxylic acid has a carboxyl group directly linked to a cycloalkane ring. The cycloalkanecarboxylic acid ester of cellulose is particularly composed of 50% of the hydroxyl groups in the cellulose molecule.
In the case of the above substituted highly substituted ester, it is generally soluble in an organic solvent and is highly likely to be usable as an adsorbent, an enzyme carrier, a chromatographic carrier, an optical isomer separating agent, a liquid crystal substance and the like.
即ち本発明はセルロース分子中の水酸基が次式 （式中Ｒは環員数３〜８のシクロアルカンを表わす） で表わされる基で置換されているセルロース誘導体に係
わるものである。That is, in the present invention, the hydroxyl group in the cellulose molecule has the following formula (Wherein R represents a cycloalkane having 3 to 8 ring members) and is related to a cellulose derivative substituted with a group.
本発明の誘導体を得る出発物質としてのシクロアルカン
カルボン酸は、例えばシクロプロパンカルボン酸、シク
ロブタンカルボン酸、シクロペンタンカルボン酸、シク
ロヘキサンカルボン酸、菊酸 のように、シクロアルカンが無置換のもの及び他の置換
基を有するものも包含される。Examples of the cycloalkanecarboxylic acid as a starting material for obtaining the derivative of the present invention include cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid and chrysanthemic acid. Such as those in which the cycloalkane is unsubstituted and those having other substituents are also included.
セルロースをエステル化し、本発明の誘導体に導くため
の反応試薬は、対応するシクロアルカンカルボン酸無水
物又はシクロアルカンカルボン酸ハライドを用いれば良
く、反応触媒としては硫酸、過塩素酸のようなブレンス
テツド酸、塩化亜鉛のようなルイス酸、ピリジン、トリ
エチルアミン、４−ジメチルアミノピリジン等の塩基が
適宜使用できる。As a reaction reagent for esterifying cellulose and leading to the derivative of the present invention, a corresponding cycloalkanecarboxylic acid anhydride or cycloalkanecarboxylic acid halide may be used, and as a reaction catalyst, sulfuric acid, or Brlensted acid such as perchloric acid. Lewis acids such as zinc chloride, bases such as pyridine, triethylamine, and 4-dimethylaminopyridine can be appropriately used.
本発明のセルロース誘導体の合成にあたり、原料セルロ
ースは一旦水或いは蟻酸などの溶媒に溶解させたものを
別種の溶媒中に沈澱させて乾燥したもの、水溶液を直接
凍結乾燥したもの、あるいは酢酸エステルのような多糖
類エステルを加水分解して得たものなどを原料とする
と、反応に対する活性が大きく有利に使用できる。In synthesizing the cellulose derivative of the present invention, the raw material cellulose is once dissolved in a solvent such as water or formic acid and then precipitated in another solvent and dried, an aqueous solution is directly freeze-dried, or an acetate ester is used. When a material obtained by hydrolyzing a different polysaccharide ester is used as a raw material, it has a large activity for the reaction and can be advantageously used.
セルロースの種類、重合度によつて反応性は異なるが、
反応条件の選択により誘導体の置換度は調節が可能であ
る。The reactivity varies depending on the type of cellulose and the degree of polymerization,
The degree of substitution of the derivative can be adjusted by selecting the reaction conditions.
本発明のセルロース誘導体は種々の形態で利用できる。
例えば、フイルム状、繊維状、粒子状などに成型して使
用する。この場合には重合度は比較的高いもの、例えば
６０以上のものが、成型品の物理的強度などの点で好ま
しい。また、微小シリカゲルに担持して使用するような
場合には重合度の比較的低いもの、例えば１０〜８０程
度のものの方が、コーテイング性などの点で有利であ
る。The cellulose derivative of the present invention can be used in various forms.
For example, it is used after being formed into a film shape, a fiber shape, a particle shape, or the like. In this case, a polymer having a relatively high degree of polymerization, for example, a polymer having a degree of polymerization of 60 or more is preferable in terms of physical strength of the molded product. Further, in the case of being used by being supported on fine silica gel, those having a relatively low degree of polymerization, for example, those having a degree of polymerization of about 10 to 80 are more advantageous in terms of coating properties and the like.
本発明のセルロース誘導体は、分子中の水酸基の５０％
以上がカルボン酸エステル化しており、好ましくは水酸
基の全部が置換した三置換体であり、有機溶剤溶解性に
すぐれ、吸着剤、光学異性体分離剤等の用途に利用し得
る。The cellulose derivative of the present invention contains 50% of hydroxyl groups in the molecule.
The above is a carboxylic ester, preferably a tri-substituted product in which all the hydroxyl groups are substituted, has excellent solubility in organic solvents, and can be used for applications such as adsorbents and optical isomer separating agents.
以下に実施例をあげて本発明を説明するが、本発明はこ
れに限定されるものではない。The present invention is described below with reference to examples, but the present invention is not limited thereto.
実施例１ 酢酸セルロースをヒドラジンでケン化し、洗浄後アセト
ン置換し、乾燥し、セルロースとした。このセルロース
３ｇに脱水したピリジン９０ml、脱水したトリエチルア
ミン15.4ml、４−ジメチルアミノピリジン１００mgを加
え、攪拌しながらシクロプロパンカルボン酸クロリド1
7.4ｇを添加し、１００℃で５時間攪拌反応した。冷却
後エタノール５００mlに生成物を攪拌しながら加えて沈
殿させ、グラスフイルターで過後、エタノールで良く
洗浄した。真空乾燥した後、塩化メチレン３０mlに溶解
し、不溶物を除いた後４００mlのエタノールに再沈殿し
た。沈殿を過後、エタノールで洗浄し、脱液、乾燥し
た。生成物の精製収量は4.2ｇであつた。生成物の塩化
メラレン溶液を食塩に塗布し、乾燥した後赤外吸収スペ
クトル測定に付した。得られた赤外吸収スペクトルは第
１図の通りであり、特徴的な吸収帯は次の通りである。Example 1 Cellulose acetate was saponified with hydrazine, washed, replaced with acetone, and dried to obtain cellulose. 90 ml of dehydrated pyridine, 15.4 ml of dehydrated triethylamine and 100 mg of 4-dimethylaminopyridine were added to 3 g of this cellulose, and cyclopropanecarboxylic acid chloride 1 was added with stirring.
7.4 g was added, and the mixture was reacted at 100 ° C. for 5 hours with stirring. After cooling, the product was added to 500 ml of ethanol with stirring to cause precipitation, which was filtered through a glass filter and thoroughly washed with ethanol. After vacuum drying, it was dissolved in 30 ml of methylene chloride, the insoluble material was removed, and the precipitate was reprecipitated in 400 ml of ethanol. After passing through the precipitate, it was washed with ethanol, drained and dried. The purified yield of the product was 4.2 g. A melalene chloride solution of the product was applied to sodium chloride, dried and subjected to infrared absorption spectrum measurement. The obtained infrared absorption spectrum is as shown in FIG. 1, and the characteristic absorption bands are as follows.
2900〜3100cm-1 シクロプロパン環Ｃ−Ｈ伸縮振動 1740cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1450cm-1 シクロプロパン環Ｃ−Ｈ変角振動 1260cm-1 エステルのＣ−Ｏ伸縮振動 1060〜1160cm-1 セルロースのＣ−Ｏ−Ｃの伸縮振動 セルロースのOHに基づく3450cm-1付近の吸収はほとんど
認められず、ほぼ三置換体であると認められる。またCD
Cl3中で測定したプロトンＭＭＲスペクトルの特徴的な
吸収は次の通りである。2900～3100Cm -1 cyclopropane ring C-H stretching vibration 1740 cm -1 C-O stretching vibration 1060~1160cm of C = O stretching vibration 1450 cm -1 cyclopropane ring C-H deformation vibration 1260 cm -1 esters of carboxylic acid ester -1 Cellulose C-O-C stretching vibration of cellulose Almost no absorption around 3450 cm -1 based on OH of cellulose is recognized, and it is recognized that it is almost a tri-substituted product. Also CD
The characteristic absorption of the proton MMR spectrum measured in Cl 3 is as follows.
0.6〜1.2ppm シクロプロパン環メチレンプロトン 1.4〜1.9ppm シクロプロパン環メチンプロトン 3.4〜5.4ppm セルロース環および６位のメチレンのプ
ロトン それぞれの吸収の強度比は１２：３：７であり、ほぼ三
置換体と認められる。0.6-1.2ppm Cyclopropane ring methylene proton 1.4-1.9ppm Cyclopropane ring methine proton 3.4-5.4ppm The absorption intensity ratio of each of the cellulose ring and the methylene proton at the 6-position is 12: 3: 7, which is almost a tri-substituted product. Is recognized.
従つて生成物は置換度約3.0のセルロースシクロプロパ
ンカルボン酸エステルであると推定される。Therefore, the product is presumed to be a cellulose cyclopropanecarboxylic acid ester having a degree of substitution of about 3.0.
実施例２ 酢酸セルロースをヒドラジンでケン化し、洗浄後アセト
ン置換し乾燥してセルロースとした。このセルロース2.
4ｇに脱水したピリジン９０ml、脱水したトリエチルア
ミン12.3ml、４−ジメチルアミノピリジン８０mgを加
え、攪拌しながら、シクロヘキサンカルボニルクロリド
12.2ｇを添加し、１００℃で５時間反応した。冷却後エ
タノール５００mlに生成物を攪拌しながら加えて沈殿さ
せ、グラスフイルターで過後、エタノールでよく洗浄
した。真空乾燥した後、塩化メチレン３０mlに溶解し、
不溶物を除いた後、４００mlのエタノールに再沈殿し
た。沈殿をろ過後、エタノールで洗浄し、脱液、乾燥し
た。生成物の精製収量は4.0ｇであつた。この生成物の
塩化メチレン溶液を食塩に塗布し、乾燥した後赤外吸収
スペクトル分析に付した。得られた赤外吸収スペクトル
は第２図の通りであり、特徴的な吸収帯は次の通りであ
る。Example 2 Cellulose acetate was saponified with hydrazine, washed, substituted with acetone and dried to obtain cellulose. This cellulose 2.
To 4 g, 90 ml of dehydrated pyridine, 12.3 ml of dehydrated triethylamine, and 80 mg of 4-dimethylaminopyridine were added, and cyclohexanecarbonyl chloride was added while stirring.
12.2 g was added, and the mixture was reacted at 100 ° C. for 5 hours. After cooling, the product was added to 500 ml of ethanol with stirring to cause precipitation, which was filtered with a glass filter and thoroughly washed with ethanol. After vacuum drying, dissolve in 30 ml of methylene chloride,
After removing the insoluble matter, it was reprecipitated in 400 ml of ethanol. The precipitate was filtered, washed with ethanol, drained and dried. The purified yield of the product was 4.0 g. A methylene chloride solution of this product was applied to sodium chloride, dried and subjected to infrared absorption spectrum analysis. The obtained infrared absorption spectrum is as shown in FIG. 2, and the characteristic absorption bands are as follows.
2870〜3000cm-1 シクロヘキサン環Ｃ−Ｈ伸縮振動 1740〜1760cm-1 カルボン酸エステルのＣ＝Ｏ伸縮振動 1460cm-1 メチレン基はさみ振動 1250cm-1 エステルのＣ−Ｏ伸縮振動 1060〜1170cm-1 セルロースのＣ−Ｏ−Ｃ伸縮振動 セルロースのOHに基づく3450cm-1付近の吸収はほとんど
認められず、ほぼ三置換体であると認められる。またCD
Cl3中で測定したプロトンＮＭＲスペクトルの特徴的な
吸収は次の通りである。2870～3000Cm -1 cyclohexane ring C-H stretching vibration 1740～1760Cm -1 carboxylic acid ester C = O stretching vibration 1460 cm -1 methylene scissor vibration 1250 cm -1 ester C-O stretching vibration 1060～1170Cm -1 of cellulose C—O—C stretching vibrations Absorption at around 3450 cm −1 based on OH of cellulose was hardly recognized, and it was recognized that it was almost a tri-substituted product. Also CD
The characteristic absorptions of the proton NMR spectrum measured in Cl 3 are:
0.4ppm〜3ppm シクロヘキサン環のプロトン 〜6ppm セルロースの環および６位のメチレンの
プロトン 以上より生成物は置換度約3.0のセルロースシクロヘキ
サンカルボン酸エステルであると推定される。0.4 ppm to 3 ppm Cyclohexane ring proton to 6 ppm Cellulose ring and methylene proton at 6-position As described above, the product is presumed to be a cellulose cyclohexanecarboxylic acid ester having a degree of substitution of about 3.0.
第１図及び第２図は夫々実施例で得られた本発明のセル
ロース誘導体の赤外吸収スペクトルである。1 and 2 are infrared absorption spectra of the cellulose derivative of the present invention obtained in Examples, respectively.
Claims (2)
式 （式中Ｒは環員数３〜８のシクロアルカンを表わす） で表わされる基で置換されているセルロース誘導体。1. 50% or more of the hydroxyl groups in the cellulose molecule have the following formula: (In the formula, R represents a cycloalkane having 3 to 8 ring members) A cellulose derivative substituted with a group represented by.
記載のセルロース誘導体。2. The cellulose derivative according to claim 1, wherein the degree of substitution is about 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59079634A JPH0655765B2 (en) | 1984-04-20 | 1984-04-20 | Cellulose derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59079634A JPH0655765B2 (en) | 1984-04-20 | 1984-04-20 | Cellulose derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60223802A JPS60223802A (en) | 1985-11-08 |
| JPH0655765B2 true JPH0655765B2 (en) | 1994-07-27 |
Family
ID=13695515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59079634A Expired - Fee Related JPH0655765B2 (en) | 1984-04-20 | 1984-04-20 | Cellulose derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655765B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2648516B2 (en) * | 1989-07-27 | 1997-09-03 | ダイセル化学工業株式会社 | Separation of stereoisomers |
| JP6120590B2 (en) * | 2013-02-01 | 2017-04-26 | 国立大学法人京都大学 | Modified nanocellulose and resin composition containing modified nanocellulose |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5315113A (en) * | 1976-07-26 | 1978-02-10 | Hokuryo Denko | Method of producing magnetic video tape and recording video signal processor |
| JPS5390384A (en) * | 1977-01-21 | 1978-08-09 | Nat Starch Chem Corp | Process for preparing starch ester |
-
1984
- 1984-04-20 JP JP59079634A patent/JPH0655765B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60223802A (en) | 1985-11-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |