JPS6143601A - Preparation of carboxymethyl starch having high etherification degree - Google Patents
Preparation of carboxymethyl starch having high etherification degreeInfo
- Publication number
- JPS6143601A JPS6143601A JP16620984A JP16620984A JPS6143601A JP S6143601 A JPS6143601 A JP S6143601A JP 16620984 A JP16620984 A JP 16620984A JP 16620984 A JP16620984 A JP 16620984A JP S6143601 A JPS6143601 A JP S6143601A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- etherification
- water
- sodium monochloroacetate
- amount
- 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
- 229920002472 Starch Polymers 0.000 title claims abstract description 36
- 239000008107 starch Substances 0.000 title claims abstract description 36
- 235000019698 starch Nutrition 0.000 title claims abstract description 36
- 238000006266 etherification reaction Methods 0.000 title claims abstract description 14
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 3
- 239000008103 glucose Substances 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 2
- 239000001632 sodium acetate Substances 0.000 claims 2
- 235000017281 sodium acetate Nutrition 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229920000881 Modified starch Polymers 0.000 claims 1
- 239000004368 Modified starch Substances 0.000 claims 1
- RUZXGXFZSOFFKG-UHFFFAOYSA-L [Na+].[Cl+].CC([O-])=O.CC([O-])=O Chemical compound [Na+].[Cl+].CC([O-])=O.CC([O-])=O RUZXGXFZSOFFKG-UHFFFAOYSA-L 0.000 claims 1
- 235000019426 modified starch Nutrition 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002562 thickening agent Substances 0.000 abstract description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 abstract 4
- 238000005517 mercerization Methods 0.000 abstract 1
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- VRYGRLBNIVQXMY-UHFFFAOYSA-M sodium;acetic acid;chloride Chemical compound [Na+].[Cl-].CC(O)=O VRYGRLBNIVQXMY-UHFFFAOYSA-M 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002230 Pectic acid Polymers 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LCLHHZYHLXDRQG-ZNKJPWOQSA-N pectic acid Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)O[C@H](C(O)=O)[C@@H]1OC1[C@H](O)[C@@H](O)[C@@H](OC2[C@@H]([C@@H](O)[C@@H](O)[C@H](O2)C(O)=O)O)[C@@H](C(O)=O)O1 LCLHHZYHLXDRQG-ZNKJPWOQSA-N 0.000 description 1
- 239000010318 polygalacturonic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は高エーテル化度カルボキシメチル化澱粉の製造
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carboxymethylated starch with a high degree of etherification.
カルボキシル基を有する多糖類には合成物では、カルボ
キシメチルセルローズ（ＣＭＣ）、カルボキシメチル化
澱粉（ＣＭＳ）等が有り、ｌａＭｔ工業、食品工業、医
薬工業１紙・パルプ工業、農薬工業等で糊剤、増粘剤、
粘結剤として使用されている。しかし、天然物であるア
ルギン酪、ペクチン酸は高価であること、価格の変動が
大きく、また高価であるため、さらにカルボキシル基を
導入することは、さらに不利である。Synthetic polysaccharides with carboxyl groups include carboxymethyl cellulose (CMC) and carboxymethylated starch (CMS), which are used as thickeners in laMt industry, food industry, pharmaceutical industry, paper/pulp industry, agrochemical industry, etc. , thickener,
Used as a binding agent. However, since natural products such as alginic acid and pectic acid are expensive, their prices fluctuate widely, and they are expensive, it is even more disadvantageous to further introduce carboxyl groups.
合成物の場合でも、天然のセルロース、澱粉を使用して
いるものの、現在のところ供給が安定していること、安
価なモノクロール酢酸ソーダと反応させることにより、
見掛けの価格を下げることが可能であること、また用途
によりエーテル化度を変化させることができる利点を有
している。Even in the case of synthetic products, although natural cellulose and starch are used, the supply is currently stable, and by reacting with inexpensive monochlorosodium acetate,
It has the advantage that the apparent price can be lowered and the degree of etherification can be changed depending on the application.
但し、近年無計画な森林伐採が大きな社会問題となって
きており、セルロースの安定供給も楽観できない状況に
なりつつある。However, in recent years, unplanned deforestation has become a major social problem, and the situation is becoming less optimistic about the stable supply of cellulose.
そこで、澱粉に対する期待が高まりつつあるが澱粉はセ
ルロースに比較して、カルボキシメチル基が入り難く、
エーテル化度はせいぜい０．７〜０．８までで、これ以
上の高エーテル化カルボキシメチル化澱粉の製造は極め
て困難とする考えが、常識となっている。従って、カル
ボキシメチル化Ｃ粉の用途も、おのずと制限されたもの
になる。０．７〜０．８以上のエーテル化度のカルボキ
シメチル化澱粉の製造が極めて困難とする原因として次
のことが考えられる。Therefore, expectations for starch are increasing, but compared to cellulose, starch is difficult to incorporate carboxymethyl groups,
It is common knowledge that the degree of etherification is at most 0.7 to 0.8, and that it is extremely difficult to produce carboxymethylated starch with a higher degree of etherification. Therefore, the uses of carboxymethylated C powder are naturally limited. The following may be considered to be the reason why it is extremely difficult to produce carboxymethylated starch having a degree of etherification of 0.7 to 0.8 or more.
１）［粉はセルロースと異なり、５５℃以上の温水で糊
化し、取り扱い難く、また糊化温度以下であっても、ア
ルカリによって糊化することにより取り扱い難い。1) Unlike cellulose, powder gelatinizes with hot water above 55°C and is difficult to handle, and even at temperatures below the gelatinization temperature, it gelatinizes with alkali and is difficult to handle.
２）上記ｌ）のごとく、澱粉はセルロースと異なる性質
を有するにもかかわらず、カルボキシメチルセルロース
と同じニーグ一方式で検討されていた傾向にある。2) As mentioned in l) above, although starch has different properties from cellulose, it has tended to be studied using the same Nigue method as carboxymethyl cellulose.
３）水−溶剤系で反応する場合でも、澱粉が糊化し易い
ため、溶剤の種類と澱粉に対する割合、澱粉に対する木
の割合等について、十分な検討がされていなかった。3) Even when reacting in a water-solvent system, starch tends to gelatinize, so sufficient consideration has not been given to the type of solvent and its ratio to starch, the ratio of wood to starch, etc.
未発ｒ！Ａ者は、これらの問題点を解消すべく、鋭意研
究の結果、高エーテル化カルボキシメチル化澱粉の製造
法を見い出し、本発明を完成したものである。即ち、
澱粉に対して０．８〜２重量倍の水および７〜１５重量
倍のイソピルアルコールを加え、ｉｉｉ粉の糊化温度以
下で、苛性ソーダをモノクロール酢酸ソーダに対するモ
ル比１．２以上、モノクロール酢酸ソーダを澱粉に対す
るモル比（モノクロール酢酸ソーダ／グルコース）２．
０以上使用してマルセル化およびエーテル化を行なうこ
とを特徴とするエーテル化度が１．０以上である高エー
テル化度カルボキシメチル化澱粉の製造法を提供するも
のである。Unreleased! In order to solve these problems, as a result of intensive research, Person A discovered a method for producing highly etherified carboxymethylated starch, and completed the present invention. That is, 0.8 to 2 times the weight of water and 7 to 15 times the weight of isopyl alcohol are added to the starch, and at a temperature below the gelatinization temperature of the iii flour, the molar ratio of caustic soda to monochlorosodium acetate is 1.2 or more. , molar ratio of monochlorosodium acetate to starch (monochlorosodium acetate/glucose)2.
The present invention provides a method for producing carboxymethylated starch having a high degree of etherification of 1.0 or more, characterized in that marcellization and etherification are carried out using 0 or more.
本発明では、澱粉に対して、０．８〜２重量倍の水およ
び、７〜１５重ｉ倍のイソピルアルコールを使用するの
で、アルカリを添加しても澱粉が糊化することなく、か
つ適度に膨潤する。このことにより、高エーテル化度カ
ルボキシメチル化澱粉が得られるものである。In the present invention, water is used in an amount of 0.8 to 2 times the weight of starch, and isopyl alcohol is used in an amount of 7 to 15 times the weight of starch, so that the starch does not gelatinize even when alkali is added. Appropriate swelling. By this, carboxymethylated starch with a high degree of etherification can be obtained.
次に本発明を実施例により具体的に説明する。Next, the present invention will be specifically explained using examples.
実施例
表−１に示す所定量のバレイショ諏粉、水およびイソプ
ロピルアルコールを４ツロセパラブルフラスコに入れ撹
拌する。３０℃以下を保持しながらタブレット状の苛性
ソーダを加え、１時間撹拌し澱粉のマルセル化を行なう
０次いで、３０〜４０℃の温度範囲で所定量のモノクロ
ール酢酸ソーダを添加後、３時間撹拌し、酢酸を加え反
応を終了する０反応物は２５９６含水メタノールで洗浄
し、乾燥することによりＣＭＳの白色粉末を得る。Example Predetermined amounts of potato powder shown in Table 1, water and isopropyl alcohol are placed in a 4-piece separable flask and stirred. Tablets of caustic soda were added while maintaining the temperature below 30°C, and the mixture was stirred for 1 hour to marcelize the starch.Next, a predetermined amount of monochlorosodium acetate was added at a temperature range of 30 to 40°C, and the mixture was stirred for 3 hours. The reaction product is washed with 2596 aqueous methanol and dried to obtain a white powder of CMS.
表−１の結果より、明らかなように澱粉に対する水およ
びイソプロピルアルコールの適当な使用割合が有り、水
の割合が少なくなるとエーテル化度は上るものの、水お
よび加温しても溶解しないミクロ状物の発生が見られた
。また、水が多すぎても、反応系がゲル状になり合成反
応ができなかった。From the results in Table 1, it is clear that there is an appropriate ratio of water and isopropyl alcohol to starch, and as the ratio of water decreases, the degree of etherification increases, but water and microscopic particles that do not dissolve even when heated occurrence was observed. Furthermore, if there was too much water, the reaction system became gel-like and the synthesis reaction could not be carried out.
Claims (1)
倍のイソピルアルコールを加え、澱粉の糊化温度以下で
、苛性ソーダをモノクロール酢酸ソーダに対するモル比
１．２以上、モノクロール酢酸ソーダを澱粉に対するモ
ル比（モノクロール酢酸ソーダ／グルコース）２．０以
上使用してマルセル化およびエーテル化を行なうことを
特徴とするエーテル化度が１．０以上である高エーテル
化度カルボキシメチル化澱粉の製造法。Add 0.8 to 2 times the weight of water and 7 to 15 times the weight of isopyl alcohol to the starch, add caustic soda at a molar ratio of 1.2 or more to monochlor sodium acetate at a temperature below the gelatinization temperature of starch, and add monochlor High degree of etherification carboxymethyl having a degree of etherification of 1.0 or more, characterized in that marcerization and etherification are carried out using sodium acetate at a molar ratio of 2.0 or more (monochloric sodium acetate/glucose) to starch. Method for producing modified starch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16620984A JPS6143601A (en) | 1984-08-07 | 1984-08-07 | Preparation of carboxymethyl starch having high etherification degree |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16620984A JPS6143601A (en) | 1984-08-07 | 1984-08-07 | Preparation of carboxymethyl starch having high etherification degree |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6143601A true JPS6143601A (en) | 1986-03-03 |
| JPH0543721B2 JPH0543721B2 (en) | 1993-07-02 |
Family
ID=15827118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16620984A Granted JPS6143601A (en) | 1984-08-07 | 1984-08-07 | Preparation of carboxymethyl starch having high etherification degree |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6143601A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046592A1 (en) * | 1996-06-06 | 1997-12-11 | Chp Carbohydrate Pirna Gmbh & Co. Kg | Substantially uncrosslinked carboxymethyl starch, process for the preparation thereof, use as a retarding agent and a retarding drug |
| CN1075516C (en) * | 1998-03-04 | 2001-11-28 | 中国科学院广州化学研究所 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
| KR100468432B1 (en) * | 2002-09-04 | 2005-01-27 | 원영산업 주식회사 | Manufacturing method of textile printing polysaccharide |
| CN102153664A (en) * | 2011-01-17 | 2011-08-17 | 温州大学 | Method for preparing nanometer lamellar sodium carboxymethyl starch |
| CN102229675A (en) * | 2011-05-19 | 2011-11-02 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN103509126A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for high-substitution degree carboxymethyl starch used for drilling fluid |
| CN106749712A (en) * | 2017-01-16 | 2017-05-31 | 无锡市善源生物科技有限公司 | A kind of method that semidry method prepares CMS |
-
1984
- 1984-08-07 JP JP16620984A patent/JPS6143601A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046592A1 (en) * | 1996-06-06 | 1997-12-11 | Chp Carbohydrate Pirna Gmbh & Co. Kg | Substantially uncrosslinked carboxymethyl starch, process for the preparation thereof, use as a retarding agent and a retarding drug |
| CN1075516C (en) * | 1998-03-04 | 2001-11-28 | 中国科学院广州化学研究所 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
| KR100468432B1 (en) * | 2002-09-04 | 2005-01-27 | 원영산업 주식회사 | Manufacturing method of textile printing polysaccharide |
| CN102153664A (en) * | 2011-01-17 | 2011-08-17 | 温州大学 | Method for preparing nanometer lamellar sodium carboxymethyl starch |
| CN102229675A (en) * | 2011-05-19 | 2011-11-02 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN103509126A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for high-substitution degree carboxymethyl starch used for drilling fluid |
| CN106749712A (en) * | 2017-01-16 | 2017-05-31 | 无锡市善源生物科技有限公司 | A kind of method that semidry method prepares CMS |
| CN106749712B (en) * | 2017-01-16 | 2019-04-09 | 无锡市善源生物科技有限公司 | A kind of method of semidry method preparation carboxymethyl starch |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0543721B2 (en) | 1993-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Properties of granular cold-water-soluble starches prepared by alcoholic-alkaline treatments | |
| US2733238A (en) | Reaction of starch and alkylene oxides | |
| US2599620A (en) | Carboxymethyl ethers | |
| EP0109776A1 (en) | Granular starch ethers having reduced pasting temperatures | |
| US4634596A (en) | Cold water swelling starch composition | |
| WO2000059947A1 (en) | Enhanced gel strength methylcellulose | |
| US3751410A (en) | Starch derivatives | |
| US20180273646A1 (en) | Process for preparing an ester of a cellulose ether in the presence of acetic acid and a reaction catalyst | |
| JPS6143601A (en) | Preparation of carboxymethyl starch having high etherification degree | |
| US3236792A (en) | Water-dispersible form of dialdehyde polysaccharides and process therefor | |
| US3033852A (en) | Preparation of propionamide ethers of starch | |
| US2660577A (en) | Derivatization of starch witch lactones | |
| EP1093466A1 (en) | Method for preparing hydroxyalkyl starch | |
| US2451686A (en) | Starch compositions capable of forming water-soluble derivatives | |
| JP3572213B2 (en) | Low substituted hydroxypropylcellulose | |
| CN108164609B (en) | Carboxymethyl acetyl ether esterification synergistic composite modified starch and preparation method thereof | |
| JP3448402B2 (en) | Modified starch for food and pasty food using the same | |
| JPH05117301A (en) | Production of cellulose mixed ether | |
| US3014901A (en) | Process for preparing ungelatinized starch ethers | |
| JPS5834802A (en) | Microcrystalline cellulose derivative and its production | |
| US3746699A (en) | Dextrin and starch ethers | |
| JPH08183805A (en) | Powdering material for liquid substance | |
| Gönül et al. | Synthesis and characterization of hydroxypropyl acorn starch (HPAS) from Oak acorn | |
| US3271387A (en) | High viscosity starch derivatives | |
| US3878196A (en) | Process for modifying starch to obtain a thixotropic starch |