CN1075516C - Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether - Google Patents
Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether Download PDFInfo
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- CN1075516C CN1075516C CN98113136A CN98113136A CN1075516C CN 1075516 C CN1075516 C CN 1075516C CN 98113136 A CN98113136 A CN 98113136A CN 98113136 A CN98113136 A CN 98113136A CN 1075516 C CN1075516 C CN 1075516C
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- CN
- China
- Prior art keywords
- starch
- reaction
- parts
- substitution value
- carboxymethyl
- Prior art date
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- 238000006467 substitution reaction Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 33
- 239000008107 starch Substances 0.000 claims abstract description 33
- 235000019698 starch Nutrition 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 3
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 229940106681 chloroacetic acid Drugs 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 240000003183 Manihot esculenta Species 0.000 description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000013312 flour Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000013256 coordination polymer Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention belongs to a starch chemical modification process. In the prior art, a process for preparing carboxymethyl starch ether comprises a dry process and a wet process but the dry process has uneven reaction and a low substitution value, and the wet process has a large liquor ratio and consumes a large number of organic solvents. Thus, the cost of a product is high. The present invention provides a homogeneous reaction process causing the starch to form base gelatinization by a low liquor ratio. The process has the advantage of reaction time shortening at high temperature. In the process for preparing the carboxymethyl starch ether, which is supplied by the present invention, the consumption amount of an organic solvent is reduced by 80 to 90%, and chloroacetic acid is reduced by 30 to 40%. A product enhances viscosity by 2 to 3 times and enhances the substitution value by 1 to 2 times.
Description
The present invention relates to the chemical modification of starch.
High viscosity carboxymethyl starch with high substitution degree (HCMS) is a kind of of treated starch, and its outward appearance is white or pale yellow powder shape (or particulate state), and (CMC) is close for performance and carboxymethyl cellulose.Have good thickening, emulsification dispersion and binding property, belong to the anionic polymer electrolyte, can be widely used for fields such as textile printing and dyeing, food-processing, material of construction, petroleum drilling, fine chemistry industry and medicine industry.(CN1075140) in the prior art (95 years the 7th phases of chemistry world) manufacturing of common carboxymethyl starch ether is divided into dry method and two kinds of technologies of wet method, dry method is evenly to sneak into dried ground caustic in starch material, spray into chloroacetic acid solution again, after turning reaction for some time at a certain temperature, obtain treated starch.Though the dry method bath raio is low, need not filter, carboxymethylation reaction is inhomogeneous, and substitution value is low, and poorly water-soluble, product chromaticness Huang are alkalescence.And wet production is to be medium with organic solvent (methyl alcohol, ethanol, acetone, Virahol), under big bath raio, make alkali and Mono Chloro Acetic Acid and starch reaction, generate carboxymethyl starch ether, for keeping the starch granules shape, avoid the alkali swelling, necessary with excessive organic solvent, consumption is about 1-4 times of starch weight, such condition is still carried out reaction at starch particle surface, reagent is difficult to enter starch crystals inside and reacts.Product substitution value and stick with paste that fluid viscosity is all difficult to be improved, though products obtained therefrom through organic solvent washing repeatedly, chromaticness and basicity take a turn for the better to some extent, the organic solvent consumption is very big, the 3-6 that is about amount of starch doubly causes product cost to improve.Owing to be liquid-solid phase reaction, so the substitution value of product, viscosity, uniformity coefficient, water-soluble all being difficult to improve.
The advantage that the objective of the invention is two kinds of starch conversion dry method and wet method in the comprehensive prior art adopts the principle of pre-gelatinized starch, proposes a kind of new starch conversion, makes the method for carboxymethyl starch ether.
The method of modifying that the present invention proposes is that the mixture with organic solvent and water is a medium, under low bath raio, make starch be in alkali gelatinization homogeneous reaction, the crystalline texture of completely destroy starch, make reagent and starch molecular chain in the short period of time, be equal phase reaction, adopt the moulding of heat drum rolling dryer particle simultaneously.Processing condition are: temperature of reaction 20-140 ℃, in 10 minutes-6 hours reaction times, basic recipe is formed (parts by weight):
100 parts of starch;
Organic solvent 5-40 part;
Mono Chloro Acetic Acid 5-40 part;
Solid alkali 10-25 part;
Deionized water 30-50 part.
The bath raio of preferred starch and reaction solution is 1: 0.7-1.5.
Organic solvent can adopt methyl alcohol, ethanol, acetone, Virahol.
Manufacture method provided by the present invention is compared with wet method with dry method of the prior art, the product substitution value can reach more than 0.9, stick with paste more than the fluid viscosity 5000mpa.s, compare with wet method, the organic solvent consumption reduces 80-90%, Mono Chloro Acetic Acid reduces 30-40%, and product viscosity improves 2-3 doubly, and substitution value improves 1-2 doubly.This method has reasonable, the advantages such as technology is simple, with low cost, good quality of product of prescription.The effect of manufacture method provided by the invention and dry method of the prior art, wet method and product performance contrast see the following form:
| Reagent and performance index | Wet method | Dry method | Manufacture method of the present invention |
| Starch (part) | 100 | ?100 | ?100 |
| Solid alkali (part) | 12～40 | ?10～20 | ?10～25 |
| Organic solvent (part) | Reaction is with 100～300 | ?5～20 | ?5～40 |
| Washing is with 300 * 3 | |||
| Deionized water (part) | Dissolving NaOH20～200 | ?20～30 | ?30～60 |
| Mono Chloro Acetic Acid (part) | 7～70 | ?5～20 | ?5～40 |
| 2% soltion viscosity (mpa.s) | 200～2000 | ?50～600 | ?50～5500 |
| Substitution value (D.S) | 0.1～0.55 | ?0.01～0.2 | ?0.01～1.0 |
| PH value | 6.5～9.0 | ?7.5～10 | ?7～9.5 |
| Color | White, little Huang | Yellowish | White, little Huang |
Embodiment 1: this example is to be raw material with horse official seal sweet potato starch, and alcohol/water is medium.
High-quality horse official seal sweet potato starch: 100 parts
Solid alkali (CP level NaOH): 19 parts
Deionized water: 39 parts
Industry Mono Chloro Acetic Acid: 21.6 parts
CP level second ferment: 30 parts
Sodium hydroxide and Mono Chloro Acetic Acid are dissolved into respectively in water and the ethanol, in cooling bath, slowly mix this two kinds of solution and cool to room temperature.Spray into mixed solution in the starch and in kneader room temperature mediated 1 hour, material is the dough shape.Material is put in Φ 150 * 300m/m heat drum roller press, and dry 4 hours of 45 ℃ of roll extrusion are pulverized and are also crossed 60 mesh sieves.Product white, PH=9, substitution value (D.S)=0.53,2% stick with paste liquid chamber temperature viscosities il=5100mpa.s, are soluble in cold water, solution homogeneous transparent, good stability.
Embodiment 2: this example is raw material with the tapioca (flour), and isopropanol is a medium.
High-quality tapioca (flour): 100 parts
Solid alkali (CP level NaOH): 27.3 parts
Deionized water: 50 parts
Industry Mono Chloro Acetic Acid: 31 parts
CP level isopropanol: 36 parts
Material blending process such as example 1.Material drops in the heat drum roller press with the dry discharging in 30 minutes of 80 ℃ of roll extrusion.Product white is with little Huang.Substitution value (D.S)=0.93,2% is stuck with paste liquid η=3200mpa.s, and PH=8 is soluble in cold water, solution homogeneous transparent, good stability.
Embodiment 3: this example is raw material with the W-Gum, and propanol/water is a medium.
High-quality viscous maize starch: 100 parts
Industrial solid alkali: 21 parts
Deionized water: 41 parts
Industry Mono Chloro Acetic Acid: 23 parts
Industrial acetone: 30 parts
The material preparation is as example 1.Material is put in the pre-gelatinization single-drum of the Φ 600 * 2000m/m type formula drying machine, is distributed in the drum surface and forms thin layer, is dried to water content about 5% in about 10 minutes after (120-140 ℃) gelatinization of being heated, and is scraped and crushing screening by scraper.Product white, D.S=0.48,2% sticks with paste liquid η=2600mpa.s, and PH=7.6 is soluble in cold water, and solution is even.
Embodiment 4: this example is a raw material with fresh cassava starch, and alcohol/water is medium.
High-quality fresh tapioca (flour): 100 parts
Industrial solid alkali: 19 parts
Deionized water: 39 parts
Industry Mono Chloro Acetic Acid: 22 parts
Industrial spirit: 29 parts
The material preparation is as example 1.Process equipment manipulation such as example 3.The little yellow of product tape, D.S=0.38,2% sticks with paste liquid η=4200mpa.s, and PH=8 is soluble in cold water, solution homogeneous transparent, good stability.
Embodiment 5: this example is raw material with the tapioca (flour), is medium with alcohol/water.
High-quality fresh tapioca (flour): 100 parts
Industrial solid alkali: 19 parts
Deionized water: 66 parts
Industry Mono Chloro Acetic Acid: 22 parts
Industrial spirit: 5 parts
Material preparation and process equipment manipulation such as example 3.The little yellow of product tape.D.S=0.31,2% sticks with paste liquid η=1800mpa.s, and PH=7.2 is soluble in cold water, and solution evenly has white vaporific, and transparency is relatively poor, and stability of solution descends to some extent.
Claims (2)
1. the manufacture method of a high viscosity high-substitution value carboxymethyl amyloether, this method is to be raw material with starch, adopting the mixture of organic solvent and water is medium, make Mono Chloro Acetic Acid and starch reaction, it is characterized in that adopting under the low bath raio, make starch be in the homogeneous reaction of alkali gelatinization, temperature of reaction 20-140 ℃, in 10 minutes to 6 hours reaction times, its prescription is formed (parts by weight):
100 parts of starch;
Organic solvent 5-40 part;
Mono Chloro Acetic Acid 5-40 part;
Solid alkali 10-25 part;
Deionized water 30-50 part.
2,, it is characterized in that described starch and reaction solution bath raio are 1: 0.7-1.5 according to the manufacture method described in the claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113136A CN1075516C (en) | 1998-03-04 | 1998-03-04 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113136A CN1075516C (en) | 1998-03-04 | 1998-03-04 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1191222A CN1191222A (en) | 1998-08-26 |
| CN1075516C true CN1075516C (en) | 2001-11-28 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113136A Expired - Fee Related CN1075516C (en) | 1998-03-04 | 1998-03-04 | Process for preparing high-viscosity and high-substitution value carboxymethyl amyloether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1075516C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161684B (en) * | 2007-11-23 | 2010-05-19 | 华南理工大学 | Infra-red synthesis of crosslinked carboxymethyl fecula |
| CN102229675B (en) * | 2011-05-19 | 2012-11-28 | 湖北达雅化工技术发展有限公司 | Preparation method of food grade high viscosity sodium carboxymethyl starch |
| CN102344498B (en) * | 2011-10-26 | 2013-07-17 | 邹平福海科技发展有限公司 | Special starch ether for mortar and production method thereof |
| CN104530247B (en) * | 2014-12-22 | 2018-11-02 | 山东聊城阿华制药股份有限公司 | A kind of carboxyrnethyl starch sodium preparation method |
| 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 |
| CN108914693A (en) * | 2018-09-11 | 2018-11-30 | 潍坊中瑞造纸纺织助剂有限公司 | A kind of dry method powder sizing agent and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1372450A (en) * | 1971-04-19 | 1974-10-30 | Diamalt Ag | Process for the preparation of carboxymethyl-starch |
| DE2410560A1 (en) * | 1974-03-06 | 1975-09-18 | Akzo Gmbh | Di-carboxy-methyl ethers of poly- or oligo-saccharides - with high degree of substn., used as sequestrants in detergents |
| JPS5534207A (en) * | 1978-08-30 | 1980-03-10 | Duskin Franchise Co Ltd | Preparation of carboxymethyl starch and its alkali salt |
| JPS6143601A (en) * | 1984-08-07 | 1986-03-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Preparation of carboxymethyl starch having high etherification degree |
| CN1064081A (en) * | 1992-01-31 | 1992-09-02 | 中国科学院上海有机化学研究所 | The manufacturing novel method of sodium starch glycolate |
| CN1118359A (en) * | 1994-09-09 | 1996-03-13 | 扬中县江岛精细化工厂 | Modified corn starch dyeing paste and its preparation |
-
1998
- 1998-03-04 CN CN98113136A patent/CN1075516C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1372450A (en) * | 1971-04-19 | 1974-10-30 | Diamalt Ag | Process for the preparation of carboxymethyl-starch |
| DE2410560A1 (en) * | 1974-03-06 | 1975-09-18 | Akzo Gmbh | Di-carboxy-methyl ethers of poly- or oligo-saccharides - with high degree of substn., used as sequestrants in detergents |
| JPS5534207A (en) * | 1978-08-30 | 1980-03-10 | Duskin Franchise Co Ltd | Preparation of carboxymethyl starch and its alkali salt |
| JPS6143601A (en) * | 1984-08-07 | 1986-03-03 | Dai Ichi Kogyo Seiyaku Co Ltd | Preparation of carboxymethyl starch having high etherification degree |
| CN1064081A (en) * | 1992-01-31 | 1992-09-02 | 中国科学院上海有机化学研究所 | The manufacturing novel method of sodium starch glycolate |
| CN1118359A (en) * | 1994-09-09 | 1996-03-13 | 扬中县江岛精细化工厂 | Modified corn starch dyeing paste and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1191222A (en) | 1998-08-26 |
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