CN101407554B - Sodium carboxymethylstarch and preparation thereof - Google Patents
Sodium carboxymethylstarch and preparation thereof Download PDFInfo
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- CN101407554B CN101407554B CN2008103052869A CN200810305286A CN101407554B CN 101407554 B CN101407554 B CN 101407554B CN 2008103052869 A CN2008103052869 A CN 2008103052869A CN 200810305286 A CN200810305286 A CN 200810305286A CN 101407554 B CN101407554 B CN 101407554B
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- alcohol
- carboxymethylstach sodium
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- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 47
- 239000011734 sodium Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 title claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920002472 Starch Polymers 0.000 claims abstract description 22
- 230000007062 hydrolysis Effects 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 239000008107 starch Substances 0.000 claims abstract description 22
- 235000019698 starch Nutrition 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 230000000630 rising effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229940106681 chloroacetic acid Drugs 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 229940079593 drug Drugs 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 5
- 238000005352 clarification Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 206010057190 Respiratory tract infections Diseases 0.000 abstract description 2
- 208000006673 asthma Diseases 0.000 abstract description 2
- 201000010099 disease Diseases 0.000 abstract description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 2
- 208000030603 inherited susceptibility to asthma Diseases 0.000 abstract description 2
- 230000036039 immunity Effects 0.000 abstract 1
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 229940032147 starch Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002955 immunomodulating agent Substances 0.000 description 3
- 229940121354 immunomodulator Drugs 0.000 description 3
- 230000002584 immunomodulator Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940079832 sodium starch glycolate Drugs 0.000 description 1
- 229920003109 sodium starch glycolate Polymers 0.000 description 1
- 239000008109 sodium starch glycolate Substances 0.000 description 1
Landscapes
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention belongs to the pharmaceutical field, which relates to sodium carboxy methyl starch and a preparation method thereof. Products prepared by the existing preparation method of the sodium carboxy methyl starch are poor in clarification, have a plurality of white blocks, are extremely low in degree of substitution and are not in accordance with pharmaceutical standards; the technical problem solved by the invention is the improvement to the existing method, and the obtained products are colorless, transparent, uniform, exquisite and are in accordance with the pharmaceutical standards. The preparation method comprises the following steps: A. starch is hydrolyzed and gelatinized in a water solution with alcohol; B. carboxymethylation is carried out; and C pulpous products are settled, still stood overnight, filtered, alcohol precipitated, disssolved repeatedly, settled so as to obtain the sodium carboxy methyl starch; and the improvement lies in that a method of gradient heating is adopted to heat room temperature to 85 DEG C for carring out heating during the hydrolysis and gelatinization in the step A. The sodium carboxy methyl starch prepared by the preparation method iscompletely in accordance with requirements of the sodium carboxy methyl starch in ministry standards, which can satisfy the demands of the sodium carboxy methyl starch to be applied as immunity regulation medicines and is used for treating diseases, such as child repetitive respiratory infections and the induced bronchial asthma and the llike.
Description
Technical field
The invention belongs to pharmacy field, be specifically related to immunomodulator carboxymethylstach sodium and preparation method thereof.
Background technology
Immunomodulator carboxymethylstach sodium (pulpous state) records in two ones the 6th of Ministry of Health of the People's Republic of China's drug standard promulgated by the ministries or commissions of the Central Government (abbreviation ministerial standard), the carboxymethylstach sodium that it is made after partial hydrolysis for starch, calculate according to dry product, containing sodium carboxymethyl is more than 12.5%, the specific optical rotation of carboxymethylstach sodium is more than+175 °, intrinsic viscosity is 20～45, and muriate must not cross 5 ‰.
Chinese patent CN85103760A, application number 85103760, denomination of invention is sodium starch glycolate and the manufacture method that contains the preparation of this material.Wherein disclose starch and after hydrolysis, carboxymethylation, prepared the Preparation of sodium carboxymethy starch method.When the contriver prepares carboxymethylstach sodium in this method of application, discovery can't prepare the carboxymethylstach sodium that meets the drug standard: its finished product clarity is poor, gelling hydrolysed starch and make its molecular size consistent as far as possible at a certain temperature not, carboxymethylstach sodium according to embodiment 1 production, clarity is poor, a large amount of white pieces are arranged, substitution value is also extremely low, require to differ greatly with ministerial standard, do not meet the regulation of two ones the 6th of Ministry of Health of the People's Republic of China's drug standard promulgated by the ministries or commissions of the Central Government, so need the technology of this patent disclosure is improved.
Summary of the invention
Owing to the product clarity that the preparation method's preparation that has carboxymethylstach sodium now gets is poor, a large amount of white pieces are arranged, substitution value is also extremely low, require to differ greatly with ministerial standard, technical problem solved by the invention is that the carboxymethylstach sodium prior preparation method is improved, the product water white transparency, the uniform and smooth that prepare and get meet the drug standard.
The preparation method of carboxymethylstach sodium provided by the present invention comprises the steps:
A, with starch hydrolysis gelatinization in aqueous solution of alcohol;
B, carboxymethylation;
C, sedimentation pulpous state product, standing over night is filtered, and alcohol precipitation dissolves repeatedly, precipitates, and promptly gets carboxymethylstach sodium;
Its improvement is when steps A hydrolysis gelatinization to adopt the mode of gradient increased temperature to rise to 85 ℃ by room temperature to heat.Starch suspension is when heating to certain temperature gradually, and its particle can expand suddenly, and volume can increase tens of even hundreds of times, and that starch suspension becomes is transparent, the colloidal liquid of the no white heart, claims that traditionally this process is gelatinization.Its essence is that water molecules enters starch granules inside, broken the hydrogen bond structure between starch molecule, destroyed particulate crystalline texture, high degree of hydration claims reticulated structure, continue stirring heating, viscosity degradation, so gradient increased temperature is to gelatinization point slowly, continuing after gelatinization is finished heats up again stirs is to guarantee that intrinsic viscosity is in one of key of expecting scope.Too fast if heat up, the inequality of being heated can form white piece, and this white piece can enter in the finished product always, is not dissolved in water, can not guarantee that promptly finished product is dissolved in the solution that forms water white transparency, uniform and smooth behind the water, influences the quality of carboxymethylstach sodium.Facts have proved, reaction solution gelatinization in the time of about 72 ℃, thinning in the time of about 82 ℃.
The carboxymethylstach sodium that gets by above-mentioned preparation method preparation meets in the ministerial standard requirement to carboxymethylstach sodium fully.Can satisfy carboxymethylstach sodium and use, the diseases such as bronchial asthma that are used for the treatment of infantile respiratory tract infection repeatedly and bring out thus as immunomodulator.
Obviously, according to foregoing of the present invention,,, can also make modification, replacement or the change of other various ways not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite according to the ordinary skill knowledge and the customary means of this area.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
Below by specific description of embodiments of the present invention the explanation but do not limit the present invention.
The prior art for preparing carboxymethylstach sodium: direct temperature reaction during the hydrolysis gelatinization, at 50～100 ℃ of hydrolysis 0.2～3.5h.
Preparation method of the present invention prepares carboxymethylstach sodium: adopt the mode of gradient increased temperature to rise to 85 ℃ by room temperature during the hydrolysis gelatinization and heat.Concrete heating mode is for rising to 60 ℃ by room temperature, 0.5-1 ℃ of per minute intensification earlier; Rise to 85 ℃ by 60 ℃ again, 0.05-0.5 ℃ of per minute intensification.Table 1 is for investigating different the intensification to the result of the deliquescent influence of finished product.
Table 1 is investigated different the intensification to the deliquescent influence of finished product
By investigating heat-up rate to deliquescent influence, rise to 60 ℃ by 30 ℃, the time that every intensification is 1 ℃ white piece can not occur in the product during greater than 1min.From time and cost consideration, preferred 30 ℃ of times that rise to 1 ℃ of 60 ℃ of every intensification are 1min, and then investigate by 60 ℃ and rise to 75 ℃, the time that every intensification is 1 ℃ during greater than 2min product white piece can not appear.From time and cost consideration, preferred 60 ℃ of times that rise to 1 ℃ of 75 ℃ of every intensification are 2min, and then investigate by 75 ℃ and rise to 80 ℃, the time that every intensification is 1 ℃ during greater than 6min product white piece can not appear.From time and cost consideration, preferred 75 ℃ of times that rise to 1 ℃ of 80 ℃ of every intensification are 6min, and then investigate by 80 ℃ and rise to 85 ℃, the time that every intensification is 1 ℃ during greater than 12min product white piece can not appear, from time and cost consideration, the time that preferred every intensification is 1 ℃ is 12min.
After the intensification condition of having investigated the hydrolysis gelatinization, the aqueous solution of alcohol that the contriver has also investigated the hydrolysis gelatinization contains alcohol amount and pure kind, pH value, hydrolysis time; Carboxymethylation material mole ratio, pH value, temperature of reaction and time; Settling conditions etc. influence the factor of carboxymethylstach sodium quality.Determined that finally following preparation method is used to prepare carboxymethylstach sodium:
A, with starch hydrolysis gelatinization in aqueous solution of alcohol.
Wherein, to heat be earlier to rise to 60 ℃ by room temperature, 0.5-1 ℃ of per minute intensification to the mode of above-mentioned gradient increased temperature; Rise to 85 ℃ by 60 ℃ again, 0.05-0.5 ℃ of per minute intensification.
Because of heat-up rate has very big influence to the product solvability, so the contriver has done following screening to heat-up rate: when rising to 60 ℃ for 30 ℃, with the speed intensification of 1 ℃ of intensification in every 1-2 minute; When rising to 85 ℃ for 60 ℃: 60 ℃ heat up with 1 ℃ the speed of heating up in every 2-3 minute when rising to 75 ℃, and 75 ℃ heat up with 1 ℃ the speed of heating up in every 6-9 minute when rising to 80 ℃, and 80 ℃ heat up with 1 ℃ the speed of heating up in per 1218 minutes when rising to 85 ℃.
Hydrolysis gelatinization condition is: it is 20%～50% that aqueous solution of alcohol contains the alcohol amount, and the pH value is 1.5～3.0, and the time is 2.5～5h.To the condition optimizing of hydrolysis gelatinization be aqueous solution of alcohol to contain the alcohol amount be 25%～30%, the pH value is 1.6～1.8.Alcohol in the aqueous solution of alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, Virahol or isopropylcarbinol.
B, carboxymethylation.
Carboxymethylation material mole ratio is: 1 part of starch, 1.8～2.5 parts in sodium hydroxide, 1～1.5 part of Mono Chloro Acetic Acid.Particularly, behind the employing of the starch after hydrolysis gelatinization sodium hydroxide adjust pH to 6～8, add chloroacetic acid solution, add sodium hydroxide solution again, be warming up to 50 ℃～70 ℃, reaction 3～5h.
C, sedimentation pulpous state product, standing over night is filtered, and alcohol precipitation dissolves repeatedly, precipitates, and promptly gets carboxymethylstach sodium.
Usually can directly will handle again after the solution sedimentation after the carboxymethylation, the standing over night.But the contriver finds, if before sedimentation, earlier with sedimentation again behind solution adjust pH to 5～8 after the step B carboxymethylation, standing over night, then can improve the stability of product, and product clarification, long storage do not produce precipitation.
Medicinal carboxymethylstach sodium is to its purity requirement height, the contriver has adopted the separation purification method (in the past adopting charcoal absorption) that is different from common carboxymethylstach sodium, with centrifugal settling and the removal of impurities of Plate Filtration bonded mode, with pure and mild purified water repeated treatments carboxymethylstach sodium, avoid using gac and bring into and come unnecessary impurity, reduced cost, the carboxymethylstach sodium clarification, the long storage that have guaranteed to adopt the carboxymethylstach sodium of the inventive method preparation to make do not produce precipitation yet.
By carboxymethylstach sodium water white transparency, the uniform and smooth that method for preparing gets, containing sodium carboxymethyl is more than 12.5%, and the specific optical rotation of carboxymethylstach sodium is more than+175 °, and intrinsic viscosity is 20～45, and muriate must not cross 5 ‰, meets ministerial standard.
Claims (8)
1. the preparation method of carboxymethylstach sodium, it comprises the steps:
A, with starch hydrolysis gelatinization in aqueous solution of alcohol;
B, carboxymethylation;
C, sedimentation pulpous state product, standing over night is filtered, and alcohol precipitation dissolves repeatedly, precipitates, and promptly gets carboxymethylstach sodium;
It is characterized in that: adopt the mode of gradient increased temperature to rise to 85 ℃ during described steps A hydrolysis gelatinization and heat by room temperature.
2. the preparation method of carboxymethylstach sodium according to claim 1 is characterized in that: adopting the mode of gradient increased temperature to heat during described steps A hydrolysis gelatinization is to rise to 60 ℃ by room temperature, 0.5-1 ℃ of per minute intensification earlier; Rise to 85 ℃ by 60 ℃ again, 0.05-0.5 ℃ of per minute intensification.
3. the preparation method of carboxymethylstach sodium according to claim 2 is characterized in that: adopting the mode of gradient increased temperature to heat during described steps A hydrolysis gelatinization is when rise to 60 ℃ for 30 ℃, to heat up 1 ℃ speed intensification in every 1-2 minute; When rising to 85 ℃ for 60 ℃, 60 ℃ heat up with 1 ℃ the speed of heating up in every 2-3 minute when rising to 75 ℃, and 75 ℃ heat up with 1 ℃ the speed of heating up in every 6-9 minute when rising to 80 ℃, and 80 ℃ heat up with 1 ℃ the speed of heating up in every 12-18 minute when rising to 85 ℃.
4. the preparation method of carboxymethylstach sodium according to claim 1, it is characterized in that: described steps A hydrolysis gelatinization condition is: it is 20%～50% that aqueous solution of alcohol contains the alcohol amount, and the pH value is 1.5～3.0, and the hydrolysis gelatinization time is 2.5～5h.
5. the preparation method of carboxymethylstach sodium according to claim 4, it is characterized in that: the alcohol in the described aqueous solution of alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, Virahol or isopropylcarbinol.
6. the preparation method of carboxymethylstach sodium according to claim 1 is characterized in that: during described step B carboxymethylation, the material mole ratio is: 1 part of starch, 1.8～2.5 parts in sodium hydroxide, 1～1.5 part of Mono Chloro Acetic Acid.
7. the preparation method of carboxymethylstach sodium according to claim 6, it is characterized in that: the carboxymethylated condition of described step B is for after adopting sodium hydroxide adjust pH to 6～8 with the starch after the hydrolysis gelatinization, add chloroacetic acid solution, add sodium hydroxide solution again, be warming up to 50 ℃～70 ℃, reaction times 3～5h.
8. the preparation method of carboxymethylstach sodium according to claim 7 is characterized in that: with the solution adjust pH to 5 after the step B carboxymethylation～8 back sedimentation, standing over night again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008103052869A CN101407554B (en) | 2008-10-30 | 2008-10-30 | Sodium carboxymethylstarch and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008103052869A CN101407554B (en) | 2008-10-30 | 2008-10-30 | Sodium carboxymethylstarch and preparation thereof |
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| CN101407554A CN101407554A (en) | 2009-04-15 |
| CN101407554B true CN101407554B (en) | 2011-06-15 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101536978B (en) * | 2009-05-08 | 2011-09-14 | 西安力邦制药有限公司 | Carboxymethyl starch sodium oral solution and preparation method thereof |
| CN105777612A (en) * | 2016-03-07 | 2016-07-20 | 王保亮 | Medicine composition for treating children recurrent respiratory infection |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103760A (en) * | 1985-05-13 | 1986-11-12 | 中国科学院上海有机化学研究所 | Sodium starch glycolate and contain the manufacture method of the preparation of this material |
-
2008
- 2008-10-30 CN CN2008103052869A patent/CN101407554B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103760A (en) * | 1985-05-13 | 1986-11-12 | 中国科学院上海有机化学研究所 | Sodium starch glycolate and contain the manufacture method of the preparation of this material |
Non-Patent Citations (2)
| Title |
|---|
| 张友松主编.第七章醚化淀粉 第二节羧甲基淀粉.变性淀粉生产与应用手册.中国轻工业出版社,1999,第134-137页. * |
| 高嘉安主编.第二章淀粉的物理化学性质.淀粉与淀粉制品工艺学.中国农业出版社,2001,第32-39页. * |
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Inventor after: Tang Jiuan Inventor after: Xiang Shipi Inventor after: Zhao Xuecai Inventor before: Gao Yulin Inventor before: Gao Liping |
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Free format text: CORRECT: INVENTOR; FROM: GAO YULIN GAO LIPING TO: TANG JIUAN XIANG SHIPI ZHAO XUECAI |
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Effective date of registration: 20190221 Address after: 618300 No. 33, West Section of Shenzhen Road, Guanghan City, Deyang City, Sichuan Province Patentee after: Sichuan Tong Yuan Pharmaceutical Group Co., Ltd. Address before: 610000 Quanshui Village Group 10, Dongzikou Township, Jinniu District, Chengdu City, Sichuan Province Patentee before: Gao Liping |