JPS59152901A - Carboxyalkyl acetyl cellulose, its salt and its preparation - Google Patents
Carboxyalkyl acetyl cellulose, its salt and its preparationInfo
- Publication number
- JPS59152901A JPS59152901A JP2798383A JP2798383A JPS59152901A JP S59152901 A JPS59152901 A JP S59152901A JP 2798383 A JP2798383 A JP 2798383A JP 2798383 A JP2798383 A JP 2798383A JP S59152901 A JPS59152901 A JP S59152901A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- carboxyalkyl
- cellulose
- acetyl
- substitution
- 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.)
- Granted
Links
- -1 Carboxyalkyl acetyl cellulose Chemical compound 0.000 title claims abstract description 24
- 229940081735 acetylcellulose Drugs 0.000 title claims abstract description 23
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 23
- 150000003839 salts Chemical class 0.000 title claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006467 substitution reaction Methods 0.000 claims abstract description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 26
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 21
- 229920002678 cellulose Polymers 0.000 claims abstract description 13
- 239000001913 cellulose Substances 0.000 claims abstract description 13
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000006640 acetylation reaction Methods 0.000 abstract description 7
- 230000021736 acetylation Effects 0.000 abstract description 4
- 230000000397 acetylating effect Effects 0.000 abstract description 3
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 abstract 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 abstract 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012345 acetylating agent Substances 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002702 enteric coating Substances 0.000 description 2
- 238000009505 enteric coating Methods 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
この発明はカルボキシメチル基とアセチル基による置換
度（ＤＢ）の高い新規なカルボキシアルキル・アセチル
・セルロースとその塩およびその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel carboxyalkyl acetyl cellulose having a high degree of substitution (DB) by carboxymethyl groups and acetyl groups, salts thereof, and a method for producing the same.
カルボキシアルキル・アセチル・セルロースに関する報
告は少なく、カルボキシアルキル基が酸型のものについ
てはその有機溶媒に対する溶解性２−
と腸溶性により腸溶性コーティング剤としての使用が記
載されている（特公昭４６−８５８９８号公報）。
しかしそのカルボキシアルキル・アセチル・セルロース
のカルボキシメチル基ｗｍｉｕ０８〜１．２と開示され
ているが、そのアセチル基による置換度および製造法に
ついては全く開示されていない。 捷だカルボキシメチ
ル・セルロースをアセチル化する方法（英国特許第１，
１２６，２４４号）や、アルカリセルロースにモノクロ
ル酢酸全反応させた後、触媒の存在下で大量の無水酢酸
を使用してアセチル化する例が知られている（ソ連発明
者証第６１２９８８号明細書）。 しかしこれらは反応
中にアセチル基が脱離したり大量の無水酢酸を必要とす
るなどの欠点を有するものであった。 また前者の方法
によるカルボキシアルキル・アセチル壷セルロースはカ
ルボキシアルキル基首極度が著しく低く、後者の方法に
よって得られたものけアセチル基置換度が著しく低いも
のであり、カルボキシアルキル基とアセチル基との両者
の置換度の高いカルボキシアルキル、アセチル・セルロ
ースは知られていない。There are few reports on carboxyalkyl acetyl cellulose, and for those with acid-type carboxyalkyl groups, their use as enteric coating agents has been described due to their solubility in organic solvents and enteric properties (Japanese Patent Publication No. 1972- 85898).
However, although the carboxymethyl group wmiu08-1.2 of the carboxyalkyl acetyl cellulose is disclosed, the degree of substitution by the acetyl group and the manufacturing method are not disclosed at all. Method for acetylating crushed carboxymethyl cellulose (British Patent No. 1,
126,244) and acetylation using a large amount of acetic anhydride in the presence of a catalyst after subjecting alkali cellulose to a complete reaction with monochloroacetic acid (USSR Inventor's Certificate No. 612,988). ). However, these have drawbacks such as the acetyl group being eliminated during the reaction and the need for a large amount of acetic anhydride. In addition, the carboxyalkyl/acetyl cellulose obtained by the former method has a significantly low carboxyalkyl radical, and the monomer cellulose obtained by the latter method has a significantly low degree of acetyl group substitution. Carboxyalkyl and acetyl cellulose with a high degree of substitution are not known.
この発明の発明者は、カルボキシアルキル・アセチル・
セルロースの製造法につき鋭意検討した結果、前記ふた
つの置換基の＠極度の高い新規なカルボキシアルキル・
アセチル・セルロースを製造することができたのである
。The inventor of this invention is a carboxyalkyl acetyl
As a result of intensive studies on cellulose production methods, we discovered a novel carboxyalkyl group with extremely high levels of the above two substituents.
It was possible to produce acetyl cellulose.
かくしてこの発明はカルボキシアルキル基の置換度（Ｄ
Ｓ）が０．２〜２．５で、アセチル基の置換度（：ＯＳ
）が０゜５〜２．８であるカルボキシアルキル−アセチ
ル・セルロースおよびその塩を提供するものである。Thus, the present invention provides a method for determining the degree of substitution of carboxyalkyl groups (D
S) is 0.2 to 2.5, and the degree of substitution of acetyl group (:OS
) is 0°5 to 2.8, and provides carboxyalkyl-acetyl cellulose and salts thereof.
この発明のカルボキシアルキル・アセチル・セルロース
のカルボキシアルキル基のアルキル基としてはｃｌ−３
程度の低級アルキル基が挙げられる。The alkyl group of the carboxyalkyl group of the carboxyalkyl acetyl cellulose of this invention is cl-3
and lower alkyl groups.
またこの発明のカルボキシアルキル・アセチル−セルロ
ースの塩としては、ナトリウム塩、カリウム塩、カルシ
ウム塩およびアンモニウム塩が挙げられる。Further, the carboxyalkyl acetyl cellulose salts of the present invention include sodium salts, potassium salts, calcium salts, and ammonium salts.
そして、特に硫酸を触媒として無水酢酸によってアセチ
ル化して得られたカルボキシアルキル・アセチル・セル
ロース（酸型）は水や水含有量の多い含水低級アルキル
アルコールに不溶であり、アセトンや、メチレンクロリ
ド／メタノールには均一溶解する。 一方そのす） Ｉ
Ｊウム塩は水、水含有量の多い含水低級アルキルアルコ
ール、および水含有量の多い含水アセトンには均一に溶
解するがメチレンクロリド／メタノール混合液には不溶
である。 従って特に上記酸型のものは有機溶媒に対す
る熔解性により腸溶性コーティング剤として使用するこ
とができ名。In particular, carboxyalkyl acetyl cellulose (acid type) obtained by acetylation with acetic anhydride using sulfuric acid as a catalyst is insoluble in water and water-containing lower alkyl alcohols with a high water content, and is insoluble in acetone, methylene chloride/methanol, etc. It dissolves uniformly. On the other hand) I
Jium salt is uniformly soluble in water, aqueous lower alkyl alcohol containing a large amount of water, and aqueous acetone containing a large amount of water, but is insoluble in a methylene chloride/methanol mixture. Therefore, in particular, the above acid type can be used as an enteric coating agent due to its solubility in organic solvents.
この発明の方法に用いる出発原料のカルボキシアルキル
・セルロースのアルカリ金属塩としてはナトリウム塩と
カリウム塩が挙げられ、そのカルボキシアルキル基の置
換度は、本願の目的物質であるカルボキシアルキル・ア
セチル・セルロースのカルボキシアルキル基の置換度の
範囲のものが５−
使用できる。 例えば市販されているカルボキシメチル
セルロースナトリウム（ｃＭｅナトリウム）のような粉
末状のものはもちろん、繊維状のものも使用できる。The alkali metal salts of the starting material carboxyalkyl cellulose used in the method of this invention include sodium salts and potassium salts, and the degree of substitution of the carboxyalkyl group is determined by the carboxyalkyl acetyl cellulose, which is the target substance of the present application. A range of degrees of substitution of carboxyalkyl groups can be used. For example, not only powdered materials such as commercially available sodium carboxymethylcellulose (cMe sodium) but also fibrous materials can be used.
カルボキシアルキル・セルロースヲ酸型、！：スルため
に使用する酸としては、硫酸、塩酸、硝酸等の鉱酸また
は酢酸等の有機酸の水溶液が使用される。 この酸型に
する反応は通常、室温で行われる。Carboxyalkyl cellulose wo acid type! : As the acid used for cleaning, an aqueous solution of a mineral acid such as sulfuric acid, hydrochloric acid, or nitric acid or an organic acid such as acetic acid is used. This reaction to form the acid form is usually carried out at room temperature.
無水酢酸等のアセチル化剤の効率を高めるためＫは、！
［化したカルボキシアルキルセルロースを酢酸等ででき
るだけ脱水することが望ましい。To increase the efficiency of acetylating agents such as acetic anhydride, K is!
It is desirable to dehydrate the converted carboxyalkylcellulose with acetic acid or the like as much as possible.
また鉱酸が残っていても酢化反応に影響しない限りは問
題ではない。Further, even if mineral acid remains, it is not a problem as long as it does not affect the acetylation reaction.
アセチル化剤としては無水酢酸が主として使用される。Acetic anhydride is mainly used as the acetylating agent.
アセチル化反応の触媒としては硫酸、スルホ酢酸、過塩
素酸、塩化亜鉛等が使用できる。 このアセチル化反応
は若干高められた温度４０〜６０℃で行われる。Sulfuric acid, sulfoacetic acid, perchloric acid, zinc chloride, etc. can be used as a catalyst for the acetylation reaction. This acetylation reaction is carried out at a slightly elevated temperature of 40-60°C.
また塩（例えば、ナトリウム塩もしくはアンモニウム塩
）を得たいときけ、酸型のカルボキシアルキル了セチル
・セルロースの有機溶媒の溶液に対応するアルカリ（例
えば水酸化ナトリウムもしくけ水酸化アンモニウムの水
溶液）を反応させて簡便に製造することができる。Alternatively, if you want to obtain a salt (e.g., sodium salt or ammonium salt), react a solution of the acid form of carboxyalkyl cellulose in an organic solvent with a corresponding alkali (e.g., an aqueous solution of sodium hydroxide or ammonium hydroxide). It can be easily manufactured by
次に実際の実施態様について述べるが、これに限定され
るものではない。Next, actual embodiments will be described, but the present invention is not limited thereto.
実施例１
置換Ｉｆ （ＤＢ） ０．６８ノＯＭ Ｏす） ！Ｊウ
ム５０ｒを２０係硫酸１．５ ｋｇに２時間常温で浸漬
し水洗後、酢酸でよく置換した。 よく脱液した後、小
型ニーダ−に投入し酢酸２５Ｏｒ、硫酸５．６Ｖ、無水
酢酸１５０ｒを加え、４８〜５０℃で４時間反応した。Example 1 Replacement If (DB) 0.68 OM Osu)! Jum 50r was immersed in 1.5 kg of 20% sulfuric acid for 2 hours at room temperature, washed with water, and thoroughly replaced with acetic acid. After thoroughly removing the liquid, the mixture was placed in a small kneader, and 25 Or of acetic acid, 5.6 V of sulfuric acid, and 150 R of acetic anhydride were added, and the mixture was reacted at 48 to 50°C for 4 hours.
反応が進むにつれＣＭＣナトリウムは溶解した。 反
応液を水に沈澱し、沈澱をよく水洗し、真空乾燥した。CMC sodium dissolved as the reaction proceeded. The reaction solution was precipitated in water, and the precipitate was thoroughly washed with water and dried in vacuum.
試料の１部をアセトンに溶解し、０．５Ｎ水酸ナトリ
ウム液を滴下して中和し、ロータリーエバポレーターで
吸引乾燥してナトリウム塩にした。A portion of the sample was dissolved in acetone, neutralized by dropwise addition of 0.5N sodium hydroxide solution, and dried by suction on a rotary evaporator to give the sodium salt.
生成したカルボキシメチル・アセチル・セルロース・ナ
トリウムのカルボキシメチル及びアセチルの置換度を灰
化後滴定する方法及びケン化法により測定したところそ
れぞれＤ Ｂ ０．６８及び２．８４であった。 その
溶媒に対する溶解性は次の通りであった。The degree of substitution of carboxymethyl and acetyl in the produced sodium carboxymethyl acetyl cellulose was measured by a titration method after ashing and a saponification method, and the D B was 0.68 and 2.84, respectively. Its solubility in solvents was as follows.
ナトリウム塩型 酸型
水 均一溶解 不溶メタノール
水を５チ以上含むと均一溶解 不溶エタノール
水を２０チ以上含むと均一熔解 不溶アセトン
水を２０％以上含むと溶解 均一溶解メチレンク
ロリドン／、−、／ −７＋／” ／１ 不溶
均−溶解本実施例で得た酸型のカルボキシメチル拳アセ
チル・セルロースの赤外吸収スペクトルを第１図に示す
。Sodium salt type Acid type water Uniformly soluble Insoluble methanol Uniformly soluble when containing 5 ml or more of water Insoluble ethanol Uniformly soluble when containing 20% or more of water Insoluble acetone Dissolved when containing 20% or more of water Uniformly soluble Methylene chloridone /, -, / −7+/”/1 Insoluble
The infrared absorption spectrum of the acid type carboxymethyl acetyl cellulose obtained in this example is shown in FIG.
比較例１
置換度（ＤＢ） ０．６８のＣＭＣナトリウム５０ｆを
酢酸１ｋｇに常温で２時間浸漬しよく脱液した後小型ニ
ーダ−に入れ、酢酸２５０？、硫酸１５．８Ｆ、無水酢
酸１５ｆを加え４８〜５０℃で４時間反応した。 時間
が経過してもＣＭＣナトリウムは酢酸に溶解しなかった
。 時間経過後ｐ過し、よく水洗した後真空乾燥した。Comparative Example 1 50f of CMC sodium with a degree of substitution (DB) of 0.68 was immersed in 1 kg of acetic acid at room temperature for 2 hours, thoroughly drained, and then placed in a small kneader and immersed in 1 kg of acetic acid at 250 ml of acetic acid. , 15.8F of sulfuric acid, and 15F of acetic anhydride were added and reacted at 48 to 50°C for 4 hours. CMC sodium did not dissolve in acetic acid over time. After a period of time, it was filtered, thoroughly washed with water, and then dried in vacuum.
この試料の赤外スペクトルは酸型ＯＭＯと同じであり、
ナトリウム塩とした後ケン化法によりアセチル化置換度
を求めたが０．１以下であった。The infrared spectrum of this sample is the same as that of acid form OMO,
After converting into a sodium salt, the degree of acetylation substitution was determined by a saponification method and was found to be 0.1 or less.
実施例２
ＴｆｌＪｌ［（ＤＢ） ０．６５ｔｖａＭｃｔ−トｖつ
Ａ５（１’を２０チ硫酸１．５ ｋｇに常温で２時間浸
漬した。Example 2 TflJl [(DB) 0.65tvaMct-A5 (1') was immersed in 1.5 kg of 20 sulfuric acid at room temperature for 2 hours.
水洗後節酸でよく置換し、脱液した後、小型ニーダ−に
投入し、酢酸８４ｔ、塩化メチレン８１６ｆ、無水酢酸
２１Ｏｆ、硫酸１．５ｔを加え、４８〜５０℃で６時間
反応した。 反応が進むにつれＣＭＣナトリウムは溶解
した。 反応液を水に沈澱し、沈澱は水でよく水洗した
後、真空乾燥した。After washing with water, the mixture was thoroughly substituted with acid, and after deliquing, it was placed in a small kneader, and 84 tons of acetic acid, 816 grams of methylene chloride, 21 tons of acetic anhydride, and 1.5 tons of sulfuric acid were added, and the mixture was reacted at 48 to 50° C. for 6 hours. CMC sodium dissolved as the reaction proceeded. The reaction solution was precipitated in water, and the precipitate was thoroughly washed with water and then dried in vacuum.
試料の１部をアセトンに溶解し、Ｏ，ｌＮ水酸化ナトリ
ウム溶液で中和した後、ロータリーエバポレーターで減
圧乾燥してナトリウム塩トシタ。A portion of the sample was dissolved in acetone, neutralized with O, IN sodium hydroxide solution, and dried under reduced pressure on a rotary evaporator to obtain the sodium salt.
生成したカルボキシメチル拳アセチル・セルロース・ナ
トリウムの置換度はカルボキシメチルＤＳ０．５ｇ、ア
セチルＤ８２．１９であった。The degree of substitution of the produced carboxymethyl acetyl cellulose sodium was 0.5 g for carboxymethyl DS and 82.19 g for acetyl D.
溶媒に対する溶解性は次の通りである。The solubility in solvents is as follows.
ナトリウム塩型 酸型
水 均一に溶解 不溶メタノ
ール 水を２０−以上含むと均一溶解 ηエタノール
水を５０％以上含むと均一溶解 〃工Ｐム
アセトン 水を２５％以上含むと均一溶解均一溶解メ
チレンクロリド人、）ゆ＝４ 不溶Ｉｌ実施例８
置換度（ＤＢ） ｏ、 ｅ ４のＣＭＣナトリウム１６
．７りを２０％硫酸６００ｆに常温で２時間浸漬した。Sodium salt type Acid type water Dissolves uniformly Insoluble methanol Dissolves uniformly when containing 20% or more of water. η Ethanol Dissolves uniformly when containing 50% or more of water. ) Yu = 4 Insoluble Il Example 8 CMC sodium 16 with degree of substitution (DB) o, e 4
．． The sample was immersed in 600f of 20% sulfuric acid for 2 hours at room temperature.
脱液水洗後、酢酸でよく置換し脱液した後、トルエン
８５０ｆと混合した。 一方、無水酢酸６（１’に硫酸
１．２７ ｆを加え、７０’ＣでＩＪ１１分加熱して硫
酸をスルホ酢酸とした後、ＣＭ（３とトルエンとの前記
混合物と混合して５゜℃で６．５時間反応した。After removing liquid and washing with water, the mixture was thoroughly replaced with acetic acid to remove liquid, and then mixed with 850 f of toluene. On the other hand, 1.27 f of sulfuric acid was added to acetic anhydride 6 (1') and heated at 70'C for 11 minutes in an IJ to convert the sulfuric acid into sulfoacetic acid. The reaction was carried out for 6.5 hours.
反応物は脱液した後メタノールでよく置換し、水洗、乾
燥した。After the reaction product was dehydrated, it was thoroughly replaced with methanol, washed with water, and dried.
実施例１と同様に置換度を測定したところカルボキシメ
チルＤＢ０，６４．アセチルＤ８１．７８であり、酸型
のものはアセトンに溶解しなかった。The degree of substitution was measured in the same manner as in Example 1 and found to be carboxymethyl DB0.64. Acetyl D was 81.78, and the acid form was not soluble in acetone.
実施例４
置換度（ＤＢ） ０．６５のＯＭＯナトリウム１７Ｆを
２０チ硫酸６００ｆに常温で２時間浸漬した。Example 4 OMO sodium 17F having a degree of substitution (DB) of 0.65 was immersed in 600f of 20-thiosulfuric acid at room temperature for 2 hours.
脱液水洗後、酢酸でよく置換し脱液した後、酢酸２５（
１，無水酢酸８９ｆ、塩化並塩１４２を加え、６０℃で
７時間反応した。 ５％食塩水１０ＧＯｆに沈澱後水洗
、乾燥した。 実施例１と同様にして置換度を測定した
ところカルボキシメチルＤ Ｓ ０．６８アセチルＤＢ
２．２８であり、酸型のものけアセトンに均一に溶解し
なかった。After removing liquid and washing with water, thoroughly replacing with acetic acid and removing liquid, add acetic acid 25 (
1. 89 f of acetic anhydride and 142 g of common salt chloride were added, and the mixture was reacted at 60°C for 7 hours. It was precipitated in 10 GO of 5% saline, washed with water, and dried. The degree of substitution was measured in the same manner as in Example 1 and found that carboxymethyl DS 0.68 acetyl DB
2.28, and it was not uniformly dissolved in acid type Mononoke acetone.
なお上記実施例におけるカルボキシメチル・アセチル・
セルロースのカルボキシメチルＷｍＷ（ｎｓ）とアセチ
ル置換度（ＤＢ）は下記の方法で測定した。In addition, carboxymethyl acetyl in the above examples
Carboxymethyl WmW (ns) and degree of acetyl substitution (DB) of cellulose were measured by the following methods.
（１） 酸Ｗカルボキシメチル・アセチル・セルロー
スの置換度
酸型カルボキシメチル・アセチル・セルロース約ｌｔを
精秤（純分ｍ＋ｆ）Ｌ、、アセトン７０ｄと水ａｏＷｄ
！に加え、−！−Ｎ ＮａＯＨでフェノール０
フタレンを指示薬としてすげやく滴定する。(1) Substitution degree of acid W carboxymethyl acetyl cellulose Accurately weigh about lt of acid type carboxymethyl acetyl cellulose (purity m + f) L, 70 d of acetone and ao W d of water
! In addition to -! Quickly titrate with -N NaOH using phenol 0 phthalene as an indicator.
１”ＯＮ Ｎａ ＯＨの使用量をＶｔｇ／、そのファク
ターをｆｌ＋カルボキシメチル置換度り日をｘとしアセ
チル置換度ＤＢをｙとする。 ゛また酸型カルボ
キシメチル・アセチル・セルロース約１２を精秤（純分
ｍ！Ｓ’）ｌ、、−！−Ｎ ＮａＯＨ０
ｔ５０ｓ＋７に溶解し、−昼夜室温で放置し、過剰指示
薬として滴定する。 −！−ＮＨ，ｓｏ４の使用量Ｏ
をＶ！ＩＩｌ、そのファクターをｆ！とする。The amount of 1" ON Na OH used is Vtg/, the factor is fl + the degree of carboxymethyl substitution is x, and the degree of acetyl substitution DB is y. Also, accurately weigh about 12% of acid-form carboxymethyl acetyl cellulose ( Purity m!S')l,, -!-N NaOH0 Dissolved in t50s+7, - left at room temperature day and night, and titrated as an excess indicator. Let be f!
この連立方程式より導いた下記式からＸ（！ニアを算出
する。X(!near is calculated from the following formula derived from this simultaneous equation.
（２）ナトリウム塩型カルボキシメチル・アセチル・セ
ルロースの置換度
ナトリウム塩型カルボキシメチル・アセチル・セルロー
ス約１ｆ！を精秤（純分ｍ１ｆ）Ｌ、磁性ルツボに入れ
て６００℃で灰化し、灰化によつて生成し念酸化ナトリ
ウムを、１）ＮＨ，５Ｏ４１００ｍｌで中和し、次に、
過剰のＨ，８０４を、 ｏ Ｎ Ｎａ ＯＨでフェノー
ルフタレンを指示薬として滴定した。(2) Substitution degree of sodium salt type carboxymethyl acetyl cellulose: Approximately 1f! Precisely weigh (purity m1f) L, put in a magnetic crucible and incinerate at 600°C, and neutralize the sodium peroxide produced by the ashing with 1) NH, 5O4, 100ml, and then:
Excess H,804 was titrated with oN NaOH using phenolphthalene as indicator.
その滴定旨をｖｉ譚ｌとし、ｉＮ Ｎａ ＯＨのファク
タ−を／ｉ ＊ 、、Ｎｎ、ｓｏ４のファクターを１
２とする。Let the titration be 1, the factor of iN NaOH is /i*, ,Nn, and the factor of so4 is 1.
Set it to 2.
カルボキシメチル置換度Ｄ８を！’とし、アセチル置換
一度ＤＢをｙｏとする。Carboxymethyl substitution degree D8! ' and once acetyl substitution DB is yo.
またナトリウム塩型カルボキシメチル・アセチル・セル
ロース約ｌｔを精秤（純分ｍ＊ｒ）ｔ、、八ＮＩＪａＯ
’Ｈ１５０ＭＩに溶解し、−昼夜放置し、過剰のＮａＯ
ＨをｉＮＨ！８０ｒフェノールフタレンを指示薬として
滴定する。 ｉＮＵ、８０４の使用量をｖ２璽ｌとす
る。In addition, approximately lt of sodium salt type carboxymethyl acetyl cellulose was accurately weighed (purity m * r) t, 8 NIJaO
'Dissolved in H150MI, left for day and night, excess NaO
H is iNH! Titrate with 80r phenolphthalene as indicator. The usage amount of iNU, 804 is assumed to be v2.
この連立方程式より導いた下記式からＸ“とｙ。From the following equation derived from this simultaneous equation, X" and y.
を算出する。Calculate.
第１図は実施例１で得られた酸型のカルボキシメチル・
アセチル・セルロースの赤外吸収スペクトルである。
１４−Figure 1 shows the acid form of carboxymethyl obtained in Example 1.
This is an infrared absorption spectrum of acetyl cellulose. 14-
Claims (1)
、 ｚ〜２．５で、アセチル基の置換度（ＤＢ）が０．
５〜２．８であるカルボキシアルキル・アセチルΦセル
ロースおよびその塩。 ４ 塩がナトリウム塩、カリウム塩、カルシウム塩もし
くはアンモニウム塩である特許請求の範囲第１項記載の
化合物。 ８、 カルボキシアルキル基の置換度が０．２〜２．５
のカルボキシアルキル・セルロースのアルカリ金属塩を
酸の水溶液中で処理することによって酸型とした後、触
媒の存在下で無水酢酸を反応させてアセチル化して、カ
ルボキシアルキル基の置換度が０．２〜２．５でアセチ
ル基の置換度が０．５〜２．８であるカルボキシアルキ
ルアセチルセルロースを得ることを特徴とするカルボキ
シアルキル・アセチル・セルロースの製造法。 ４、 カルボキシアルキル・セルロースのアルカリ金属
塩を酸型にするのに、硫酸、塩酸、硝酸などの鉱酸捷た
は酢酸などの有機酸の水溶液を用いる特許請求の範囲第
８項記載の製造法。 ５、触媒が硫酸、スルホ酢酸、過塩素酸または塩化亜鉛
である特許請求の範囲第８項記載の製造法。[Claims] 1. Degree of substitution of carboxyalkyl group (DB) Kao
, z~2.5, and the degree of substitution (DB) of the acetyl group is 0.
5 to 2.8 carboxyalkyl acetyl Φ cellulose and salts thereof. 4. The compound according to claim 1, wherein the salt is a sodium salt, potassium salt, calcium salt or ammonium salt. 8. Degree of substitution of carboxyalkyl group is 0.2 to 2.5
After converting the alkali metal salt of carboxyalkyl cellulose into an acid form by treating it in an aqueous acid solution, it was acetylated by reacting with acetic anhydride in the presence of a catalyst, so that the degree of substitution of the carboxyalkyl group was 0.2. A method for producing carboxyalkyl acetyl cellulose, which comprises obtaining carboxyalkyl acetyl cellulose having a degree of substitution of acetyl groups of 0.5 to 2.8. 4. The production method according to claim 8, in which an aqueous solution of a mineral acid such as sulfuric acid, hydrochloric acid, or nitric acid or an organic acid such as acetic acid is used to convert the alkali metal salt of carboxyalkyl cellulose into an acid form. . 5. The production method according to claim 8, wherein the catalyst is sulfuric acid, sulfoacetic acid, perchloric acid, or zinc chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2798383A JPS59152901A (en) | 1983-02-21 | 1983-02-21 | Carboxyalkyl acetyl cellulose, its salt and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2798383A JPS59152901A (en) | 1983-02-21 | 1983-02-21 | Carboxyalkyl acetyl cellulose, its salt and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59152901A true JPS59152901A (en) | 1984-08-31 |
| JPH0372082B2 JPH0372082B2 (en) | 1991-11-15 |
Family
ID=12236083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2798383A Granted JPS59152901A (en) | 1983-02-21 | 1983-02-21 | Carboxyalkyl acetyl cellulose, its salt and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59152901A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59166503A (en) * | 1983-03-10 | 1984-09-19 | Daicel Chem Ind Ltd | Carboxymethylcellulose derivative and its preparation |
| JPH01261401A (en) * | 1988-02-25 | 1989-10-18 | Akzo Nv | Modified cellulose and production thereof |
| JP2006520420A (en) * | 2003-03-14 | 2006-09-07 | イーストマン ケミカル カンパニー | Low molecular weight carboxyalkyl cellulose esters and their use in coating compositions as low viscosity binders and modifiers |
| JP2014224183A (en) * | 2013-05-15 | 2014-12-04 | 川研ファインケミカル株式会社 | Acylated carboxymethyl cellulose and cosmetic containing acylated carboxymethyl cellulose |
-
1983
- 1983-02-21 JP JP2798383A patent/JPS59152901A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59166503A (en) * | 1983-03-10 | 1984-09-19 | Daicel Chem Ind Ltd | Carboxymethylcellulose derivative and its preparation |
| JPH0372047B2 (en) * | 1983-03-10 | 1991-11-15 | Daicel Chem | |
| JPH01261401A (en) * | 1988-02-25 | 1989-10-18 | Akzo Nv | Modified cellulose and production thereof |
| JP2006520420A (en) * | 2003-03-14 | 2006-09-07 | イーストマン ケミカル カンパニー | Low molecular weight carboxyalkyl cellulose esters and their use in coating compositions as low viscosity binders and modifiers |
| JP2014224183A (en) * | 2013-05-15 | 2014-12-04 | 川研ファインケミカル株式会社 | Acylated carboxymethyl cellulose and cosmetic containing acylated carboxymethyl cellulose |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0372082B2 (en) | 1991-11-15 |
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