JPH0479361B2 - - Google Patents
Info
- Publication number
- JPH0479361B2 JPH0479361B2 JP14610685A JP14610685A JPH0479361B2 JP H0479361 B2 JPH0479361 B2 JP H0479361B2 JP 14610685 A JP14610685 A JP 14610685A JP 14610685 A JP14610685 A JP 14610685A JP H0479361 B2 JPH0479361 B2 JP H0479361B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose acetate
- substitution
- hydroxyl groups
- cellulose
- reaction
- 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
Links
- 229920002301 cellulose acetate Polymers 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 27
- 238000006467 substitution reaction Methods 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 8
- 229920001747 Cellulose diacetate Polymers 0.000 description 7
- 229920002284 Cellulose triacetate Polymers 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
〔産業上の利用分野〕
本発明は、高置換度酢酸セルロースを特定の加
水分解条件で処理することにより、分子中に第２
級水酸基が比較的多量に存在する低置換度酢酸セ
ルロースを製造する方法に関するものである。
〔従来の技術〕
最近分岐多糖には強い生理活性を有するものが
あることが見出されている。例えば松崎らは２酢
酸セルロースに３，４，６−トリ−ｏ−アセチル
−１，２−ｏ−エチルオルトアセチル−α−Ｄ−
グルコピラノースを反応させた後脱アセチル化す
ることにより水溶性分岐多糖を得、このものが高
い抗腫瘍性を有するものであることを見出した。
このものは、セルロース主鎖にグルコースが分岐
付加した構造を有しており、その分岐位置は主鎖
グルコースのC6位、即ち第１級水酸基の位置に
結合しているものである（繊維学会第59回年次大
会研究発表会）。
一方天然には、同様に短い分岐鎖を有する多糖
類、例えばグアガム、ローカストビーンガム、タ
マリンドガムなどがあるが、これらもその分岐の
位置は、主鎖多糖の１級水酸基に結合しているも
のである。
〔発明が解決しようとする問題点〕
酢酸セルロースはそれ自身、繊維やプラスチツ
クの素材として工業的に有用であるが、セルロー
スを主鎖とする種々の誘導体の原料としても有用
である。後者の場合、酢酸エステル基は、水酸基
の保護基としての役割を果させることができる。
反応性の遊離水酸基を有し、汎用の有機溶剤に可
溶の２酢酸セルロースは、工業的には３酢酸セル
ロースを酢酸水溶液中で部分加水分解して得られ
るが、この方法によつて得られる２酢酸セルロー
スの遊離水酸基は無水グルコース単位構造のC2，
C3，C6にあるが、そのうち第１級水酸基である
C6位の水酸基が最も多い。
このような３酢酸セルロースの部分加水分解条
件をかえることにより、２級水酸基であるC2又
はC3位置の水酸基をより多く有する２酢酸セル
ロースを得ることができればそれら２級水酸基か
らの分岐構造を有する新たな多糖類の合成に到る
可能性がある。
〔問題点を解決するための手段〕
発明者らは、高置換度酢酸セルロースの加水分
解条件について鋭意研究した結果、過酸化水素の
存在下アルカリ金属水酸化物を用い、有機溶媒／
水混合溶媒中で反応させることにより、分子中に
C6位水酸基よりもC2，C3位水酸基をより多量に
有する低置換度酢酸セルロースが得られことを見
出して本発明に到つたものである。
即ち本発明は高置換度酢酸セルロースを部分加
水分解して低置換度酢酸セルロースを製造する方
法において、高置換度酢酸セルロースをアルカリ
金属水酸化物と過酸化水素の共存下に処理するこ
とにより、第２級水酸基を優先的に生成しせしめ
ることを特徴とする酢酸セルロースの部分加水分
解法に係わるものである。
本発明に用いられるアルカリ金属水酸化物とし
ては、水酸化ナトリウム、水酸化カリウム及び水
酸化リチウムがあるが、水酸化リチウムが最も適
当である。
アルカリ金属水酸化物の使用量は、高置換度酢
酸セルロースの無水グルコース単位あたり１モル
当量程度とすれば、置換度２程度の酢酸セルロー
スを得るのに好適である。更にアルカリ金属水酸
化物の量を多くすればより低置換度の酢酸セルロ
ースが得られる。
この部分加水分解反応における試薬の活性種は
アルカリ金属バーハイドロオキシド（MOOH）
と考えられるので、過酸化水素はアルカリ金属水
酸化物に対して等モル以上使用するのが好まし
い。
原料とする高置換度酢酸セルロースは一般に塩
化メチレン、クロロホルムなどのハロゲン化炭化
水素に溶解するので、それらに溶解させて反応に
使用する。一方、アルカリ金属水酸化物及び過酸
化水素は水溶液の形で使用する。更に反応に際し
ては、水及びハロゲン化炭化水素に混和性を有す
る溶媒を添加するのが好ましい。この目的で用い
る溶媒としてはテトラヒドロフラン、ジオキサ
ン、ジメトキシエタン、ジメチルホルムアミド、
ジメチルアセトアミド、ジメチルスルホキシド、
ピロリドンなどの中から選択することができる。
〔実施例〕
以下に実施例を挙げて本発明を説明するが、実
施例において、酢酸セルロース試料のアセチル基
置換度及びアセチル基の結合位置に関する分布
は、重水素化ジメチルスルホキシド（C6）溶液
中で測定した13C−NMRスペクトルに基づいて
定量した。
第１図に次式で示される二酢酸セルロースの
13C−NMRスペクトルを示す。
第１図において無水グルコース環の骨格炭素
（Ｃ−１〜Ｃ−６）シグナルが58〜104ppmの領域
に現れているが、そのうちＣ−１，Ｃ−４及びＣ
−６炭素はそれぞれ２本ずつに分裂している。こ
れらの分裂は各炭素に隣接する水酸基に結合した
アセチル基の置換基効果によるものであり、各シ
グナルは次の表１のように帰属される。
[Industrial Field of Application] The present invention is a method of treating highly substituted cellulose acetate under specific hydrolysis conditions to add secondary cells into the molecule.
The present invention relates to a method for producing low-substituted cellulose acetate in which a relatively large amount of grade hydroxyl groups is present. [Prior Art] Recently, it has been discovered that some branched polysaccharides have strong physiological activity. For example, Matsuzaki et al.
They obtained a water-soluble branched polysaccharide by reacting glucopyranose and then deacetylating it, and found that this polysaccharide had high antitumor properties.
This product has a structure in which glucose is branched and added to the cellulose main chain, and the branch position is bonded to the C 6 position of the main chain glucose, that is, the position of the primary hydroxyl group (Fiber Science Society 59th Annual Conference Research Presentation). On the other hand, in nature, there are polysaccharides that similarly have short branched chains, such as guar gum, locust bean gum, and tamarind gum, but the branching positions of these are also bonded to the primary hydroxyl group of the main chain polysaccharide. It is. [Problems to be Solved by the Invention] Cellulose acetate itself is industrially useful as a material for fibers and plastics, but it is also useful as a raw material for various derivatives having cellulose as the main chain. In the latter case, the acetate group can serve as a protecting group for the hydroxyl group.
Cellulose diacetate, which has reactive free hydroxyl groups and is soluble in general-purpose organic solvents, is industrially obtained by partially hydrolyzing cellulose triacetate in an acetic acid aqueous solution; The free hydroxyl group of cellulose diacetate is C 2 of the anhydroglucose unit structure,
Located at C 3 and C 6 , among which is the primary hydroxyl group
The hydroxyl group at the C6 position is the most abundant. By changing the conditions for partial hydrolysis of cellulose triacetate, cellulose diacetate having more hydroxyl groups at the C 2 or C 3 position, which are secondary hydroxyl groups, can be obtained. This may lead to the synthesis of new polysaccharides containing [Means for Solving the Problems] As a result of intensive research on the hydrolysis conditions of highly substituted cellulose acetate, the inventors found that the hydrolysis conditions for highly substituted cellulose acetate were solved using an alkali metal hydroxide in the presence of hydrogen peroxide, an organic solvent/
By reacting in a water mixed solvent,
The present invention was achieved by discovering that low-substituted cellulose acetate having a larger amount of hydroxyl groups at the C2 and C3 positions than hydroxyl groups at the C6 position can be obtained. That is, the present invention provides a method for producing low-substituted cellulose acetate by partially hydrolyzing highly substituted cellulose acetate, by treating highly substituted cellulose acetate in the coexistence of an alkali metal hydroxide and hydrogen peroxide. The present invention relates to a method for partial hydrolysis of cellulose acetate, which is characterized by preferentially producing secondary hydroxyl groups. Alkali metal hydroxides used in the present invention include sodium hydroxide, potassium hydroxide, and lithium hydroxide, with lithium hydroxide being the most suitable. The amount of alkali metal hydroxide to be used is about 1 molar equivalent per anhydroglucose unit of highly substituted cellulose acetate, which is suitable for obtaining cellulose acetate with a degree of substitution of about 2. Furthermore, by increasing the amount of alkali metal hydroxide, cellulose acetate with a lower degree of substitution can be obtained. The active species of the reagent in this partial hydrolysis reaction is alkali metal bar hydroxide (MOOH).
Therefore, it is preferable to use hydrogen peroxide in an amount equivalent to or more than the alkali metal hydroxide. The highly substituted cellulose acetate used as a raw material is generally soluble in halogenated hydrocarbons such as methylene chloride and chloroform, so it is used in the reaction after being dissolved therein. On the other hand, alkali metal hydroxides and hydrogen peroxide are used in the form of aqueous solutions. Furthermore, during the reaction, it is preferable to add a solvent that is miscible with water and the halogenated hydrocarbon. Solvents used for this purpose include tetrahydrofuran, dioxane, dimethoxyethane, dimethylformamide,
dimethylacetamide, dimethyl sulfoxide,
It can be selected from pyrrolidone and the like. [Example] The present invention will be explained below with reference to examples. In the example, the distribution regarding the degree of acetyl group substitution and the bonding position of the acetyl group of a cellulose acetate sample was determined using a deuterated dimethyl sulfoxide (C 6 ) solution. Quantification was performed based on the 13 C-NMR spectrum measured in the inside. Figure 1 shows the cellulose diacetate shown by the following formula:
13C -NMR spectrum is shown. In Figure 1, the skeletal carbon (C-1 to C-6) signals of the anhydroglucose ring appear in the region of 58 to 104 ppm, among which C-1, C-4 and C-1
-6 carbons are each split into two. These splits are due to the substituent effect of the acetyl group bonded to the hydroxyl group adjacent to each carbon, and each signal is assigned as shown in Table 1 below.
【表】
表１に示した帰属に基づき次に示す式〜に
より無水グルコース環内の全置換度ｆ及び各置換
位置における置換度（f2，f3及びf6）が求められ
る。
f2＝〔C1′〕／〔C1〕＋〔C1′〕 −
f3＝１−f2×〔C4〕／〔C1′〕 −
f6＝〔C6′〕／〔C6〕＋〔C6′〕 −
ｆ＝f2＋f3＋f6 −
注 〔Ｃ〕はピークＣのシグナル強度を表わす。
実施例 １
工業的に生産されており、プラスチツクスの製
造に用いられる置換度2.90の３酢酸セルロース
（アルドリツチ製）１ｇを塩化メチレン30mlに溶
解しておき、1N水酸化リチウム３ml、30％過酸
化水素水３ml及びテトラヒドロフラン30mlの混合
液を、室温攪拌下に添加した。混合物は均一な溶
液を形成した。この混合物を室温で１時間攪拌し
て反応させた後、水200mlを加えて反応を停止さ
せた。
本反応において使用した３酢酸セルロース中の
無水グルコース単位対水酸化リチウムのモル比は
略１：１である。
反応液を減圧下濃縮して、低沸点溶媒の一部を
除去すると、白色固体沈殿が生成した。固体を炉
別し水、エタノールで洗浄、乾燥した。収量0.88
ｇであつた。
原料に用いた３酢酸セルロース及び本実施例で
得た部分加水分解試料の置換度分析結果は表２の
とおりであつた。但し表２中の数字は、アセチル
置換度、（ ）内数字は全遊離水酸基に対する当
該炭素位置の遊離水酸基の割合を示す。[Table] Based on the assignments shown in Table 1, the total degree of substitution f in the anhydroglucose ring and the degree of substitution (f 2 , f 3 and f 6 ) at each substitution position are determined by the following formulas. f 2 = [C1′] / [C1] + [C1′] − f 3 = 1 − f 2 × [C4] / [C1′] − f 6 = [C6′] / [C6] + [C6′] − f=f 2 +f 3 +f 6 − Note [C] represents the signal intensity of peak C. Example 1 1 g of cellulose triacetate (manufactured by Aldrich) with a degree of substitution of 2.90, which is industrially produced and used in the production of plastics, was dissolved in 30 ml of methylene chloride, and 3 ml of 1N lithium hydroxide and 30% peroxide were dissolved. A mixed solution of 3 ml of hydrogen water and 30 ml of tetrahydrofuran was added under stirring at room temperature. The mixture formed a homogeneous solution. The mixture was stirred at room temperature for 1 hour to react, and then 200 ml of water was added to stop the reaction. The molar ratio of anhydroglucose units to lithium hydroxide in the cellulose triacetate used in this reaction was approximately 1:1. The reaction solution was concentrated under reduced pressure to remove a portion of the low boiling point solvent, producing a white solid precipitate. The solid was separated in a furnace, washed with water and ethanol, and dried. Yield 0.88
It was hot at g. Table 2 shows the results of substitution degree analysis of the cellulose triacetate used as the raw material and the partially hydrolyzed sample obtained in this example. However, the numbers in Table 2 indicate the degree of acetyl substitution, and the numbers in parentheses indicate the ratio of free hydroxyl groups at the carbon position to all free hydroxyl groups.
【表】
表２からわかる様に本実施例の反応による部分
加水分解生成物は、遊離第２級水酸基を多く含有
するものであつた。
比較例
工業的に生産されており繊維製造に用いられる
置換度2.39の２酢酸セルロース（ダイセル化学工
業製）及び混合セルロースエステル製造に用いら
れる置換度1.72の低置換度酢酸セルロース（ダイ
セル化学工業製）を、実施例１と同様の分析法に
より分析し、置換度分布を求めた。その結果は表
３に示す通りであつた。[Table] As can be seen from Table 2, the partial hydrolysis product obtained by the reaction of this example contained a large amount of free secondary hydroxyl groups. Comparative examples Industrially produced cellulose diacetate with a degree of substitution of 2.39 used in fiber production (manufactured by Daicel Chemical Industries) and cellulose acetate with a low degree of substitution of 1.72 used in the production of mixed cellulose esters (manufactured by Daicel Chemical Industries) was analyzed by the same analytical method as in Example 1 to determine the substitution degree distribution. The results were as shown in Table 3.
【表】
実施例 ２
反応時間を２時間とした以外は、実施例１と同
様にして生成物を得た。収量0.83ｇ。本反応にお
いて酢酸セルロースの無水グルコース単位対水酸
化リチウムのモル比は略１：１である。生成物の
置換度分布は表４にまとめた。
実施例 ３
実施例１と同じ３酢酸セルロース１ｇに対して
実施例１のそれぞれ2.4倍量の水酸化リチウム、
過酸化水素水、テトラヒドロフランを用い、室温
下１時間反応させて反応生成物を得た。収量0.77
ｇ。（無水グルコース単位対水酸化リチウム＝略
１：2.4）生成物の置換度分布を表４に示す。
実施例 ４
実施例１と同じ２酢酸セルロース１ｇに対し
て、実施例１のそれぞれ３倍量の水酸化リチウ
ム、過酸化水素水、テトラヒドロフランを用い、
室温下２時間反応させて反応生成物を得た。収量
0.65ｇ。（無水グルコース単位対水酸化リチウム
＝略１：３）
生成物の置換度分布を表４に示す。[Table] Example 2 A product was obtained in the same manner as in Example 1, except that the reaction time was 2 hours. Yield 0.83g. In this reaction, the molar ratio of anhydroglucose units in cellulose acetate to lithium hydroxide is approximately 1:1. The substitution degree distribution of the products is summarized in Table 4. Example 3 2.4 times the amount of lithium hydroxide as in Example 1 for 1 g of cellulose triacetate, the same as in Example 1,
A reaction product was obtained by reacting at room temperature for 1 hour using hydrogen peroxide and tetrahydrofuran. Yield 0.77
g. (Anhydroglucose unit to lithium hydroxide = approximately 1:2.4) Table 4 shows the substitution degree distribution of the product. Example 4 For 1 g of cellulose diacetate, which is the same as in Example 1, three times the amount of lithium hydroxide, hydrogen peroxide, and tetrahydrofuran as in Example 1 was used,
The reaction was carried out at room temperature for 2 hours to obtain a reaction product. yield
0.65g. (Anhydroglucose unit to lithium hydroxide = approximately 1:3) Table 4 shows the substitution degree distribution of the product.
第１図は二酢酸セルロースの13C−NMRスペ
クトルを示す。
Figure 1 shows the 13 C-NMR spectrum of cellulose diacetate.
Claims (1)
低置換度酢酸セルロースを製造する方法におい
て、高置換度酢酸セルロースをアルカリ金属水酸
化物と過酸化水素の共存下に処理することによ
り、第２級水酸基を優先的に生成せしめることを
特徴とする酢酸セルロースの部分加水分解法。1. In a method for producing low-substituted cellulose acetate by partially hydrolyzing highly substituted cellulose acetate, high-substituted cellulose acetate is treated in the coexistence of an alkali metal hydroxide and hydrogen peroxide to produce A method for partial hydrolysis of cellulose acetate, which is characterized by preferentially generating hydroxyl groups.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14610685A JPS627701A (en) | 1985-07-03 | 1985-07-03 | Process for partial hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14610685A JPS627701A (en) | 1985-07-03 | 1985-07-03 | Process for partial hydrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS627701A JPS627701A (en) | 1987-01-14 |
| JPH0479361B2 true JPH0479361B2 (en) | 1992-12-15 |
Family
ID=15400282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14610685A Granted JPS627701A (en) | 1985-07-03 | 1985-07-03 | Process for partial hydrolysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS627701A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60143658A (en) * | 1984-12-10 | 1985-07-29 | Hitachi Ltd | Complementary insulated gate field effect transistor integrated circuit |
| JPS6410656A (en) * | 1987-07-03 | 1989-01-13 | Hitachi Ltd | Complementary type semiconductor device |
| JP2002265501A (en) * | 2001-03-14 | 2002-09-18 | Fuji Photo Film Co Ltd | Process for preparation of cellulose acylate solution and cellulose acylate film |
| JP4189372B2 (en) * | 2004-10-26 | 2008-12-03 | 富士フイルム株式会社 | Cellulose acetate, cellulose acetate solution and preparation method thereof |
| WO2014142166A1 (en) * | 2013-03-13 | 2014-09-18 | 株式会社ダイセル | Low-substituted cellulose acetate |
| KR102162542B1 (en) * | 2013-12-20 | 2020-10-07 | 주식회사 다이셀 | Nutrient composition having lipid metabolism-improving action |
| JP6283523B2 (en) * | 2014-01-30 | 2018-02-21 | 株式会社ダイセル | Water-soluble cellulose acetate-based resin composition, water-soluble cellulose acetate composite molded article and method for producing the same |
| US10300085B2 (en) | 2014-03-24 | 2019-05-28 | Daicel Corporation | Nutritional composition |
| JP6187653B1 (en) * | 2016-08-12 | 2017-08-30 | 富士ゼロックス株式会社 | Cellulose acylate, resin composition, and resin molded article |
| JP2021008565A (en) * | 2019-07-01 | 2021-01-28 | 株式会社ダイセル | Cellulose acetate and manufacturing method of cellulose acetate |
-
1985
- 1985-07-03 JP JP14610685A patent/JPS627701A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS627701A (en) | 1987-01-14 |
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