CN103421124A - High-substitution-degree quaternary ammonium type cationic sticky rice starch and manufacturing method thereof - Google Patents
High-substitution-degree quaternary ammonium type cationic sticky rice starch and manufacturing method thereof Download PDFInfo
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- CN103421124A CN103421124A CN2013103890547A CN201310389054A CN103421124A CN 103421124 A CN103421124 A CN 103421124A CN 2013103890547 A CN2013103890547 A CN 2013103890547A CN 201310389054 A CN201310389054 A CN 201310389054A CN 103421124 A CN103421124 A CN 103421124A
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Abstract
The invention belongs to the technical field of modified starch, and discloses high-substitution-degree quaternary ammonium type cationic sticky rice starch and a manufacturing method thereof. Sticky rice starch and ethanol water solution are mixed to form sticky rice starch slurry; alkaline solution is added in the sticky rice starch slurry at room temperature and the sticky rice starch slurry is stirred; then cationic etherification agent is added in the sticky rice starch slurry to be stirred, and a coarse product is obtained through stirring reaction; the coarse product is soaked in ethanol water solution with acetic acid and is filtered, and is washed by the ethanol water solution until no silver chloride sediment is produced when filter liquor is detected by silver nitrate; then the coarse product is dried in a vacuumized mode, and the high-substitution-degree quaternary ammonium type cationic sticky rice starch in a white powder shape is obtained. According to the high-substitution-degree quaternary ammonium type cationic sticky rice starch and the manufacturing method of the high-substitution-degree quaternary ammonium type cationic sticky rice starch, the sticky rice starch is used as raw materials to be prepared for high-substitution-degree quaternary ammonium type cationic sticky rice starch in a semi-dry method, and the using range of the sticky rice starch is expanded.
Description
Technical field
The invention belongs to the production technical field of modified starch, be specifically related to a kind of high degree of substitution quaternary ammonium cationic glutinous rice starch and preparation method thereof.
Background technology
Cationic starch is a kind of very important starch ether derivative, be widely used in the industries such as papermaking, weaving, oil-field development, tamanori, mining industry and makeup abroad, and domestic only at the application comparative maturity of paper industry, other field is just to be developed, therefore prospect is very wide.Quaternary ammonium cation starch, no matter under acidity or alkaline condition, all be cationic, copy paper in particularly suitable, under alkalescence or acidic conditions, the today developed rapidly in the neutral papermaking technology, it is just becoming indispensable paper making additive, is also that the current scope of application is the widest, the maximum a kind of modified starch of consumption.
The production method of domestic relevant cationic starch, mainly contain wet method, dry method and semidrying.Wet method, due to low conversion rate, produce a large amount of waste water in production, and the cationic starch substitution value of producing is less than 0.1.Dry method exists that inhomogeneous, the long reaction time of reaction, foreign matter content are high, the high deficiency of equipment requirements.And that semidrying preparation technology has technique is simple, the characteristics such as reaction efficiency is high, and energy consumption is low, and environmental pollution is little.
The cationic starch substitution value that is applied at present paper making wet part is generally 0.01～0.07, belongs to Low-substituted Cationic Starch, for this reproducible resource of good utilisation starch more, enlarges the Application Areas of cationic starch at papermaking Jiang Yezhong.Preparing cationic starch with high substitution degree is applied to paper making wet part and makes retention filtration adjuvant and anion garbage capturing agent.
The common raw material for preparing cationic starch has W-Gum, tapioca (flour), wheat starch or yam starch etc. at present, and the glutinous rice starch of take is not seen in report as raw material prepares cationic starch with high substitution degree.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method of high degree of substitution quaternary ammonium cationic glutinous rice starch.The present invention be take glutinous rice starch and is prepared the high degree of substitution quaternary ammonium cationic glutinous rice starch as the raw material choose semidrying, has expanded the use range of glutinous rice starch, has enriched the kind of cationic starch;
The high degree of substitution quaternary ammonium cationic glutinous rice starch that provides above-mentioned preparation method to prepare is provided;
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of high degree of substitution quaternary ammonium cationic glutinous rice starch comprises following operation steps:
(1) size mixing: the aqueous ethanolic solution that will be equivalent to glutinous rice starch quality 20～25% joins in glutinous rice starch and is mixed into the glutinous rice starch slurry;
(2) alkalization: the alkali wiring solution-forming that will be equivalent to glutinous rice starch quality 1.5～3% is added drop-wise in the glutinous rice starch slurry of step (1);
(3) etherificate: the cationic etherifying agent that will be equivalent to glutinous rice starch quality 30～40% joins in the glutinous rice starch slurry after step (2) alkalizes, and under room temperature, stirring reaction is 60～110 minutes;
(4) immersion, filtration, washing, drying: the volume fraction that the slurry of the glutinous rice starch after step (3) etherificate is contained to 5mL acetic acid with every 100mL is that 60～70% aqueous ethanolic solutions soak, filter, the volume fraction of take produces without silver nitride precipitation with Silver Nitrate check as 70～80% aqueous ethanolic solutions wash to filtrate, then 40～50 ℃ of vacuum-dryings, obtain the high degree of substitution quaternary ammonium cationic glutinous rice starch.
The volume fraction of the described aqueous ethanolic solution of step (1) is 40%.
The described alkali of step (2) is sodium hydroxide, potassium hydroxide or calcium hydroxide.
The described cationic etherifying agent of step (3) is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride.
A kind of high degree of substitution quaternary ammonium cationic glutinous rice starch prepared according to above-mentioned preparation method.
The present invention has following advantage and effect with respect to prior art:
(1) preparation method's production technique of the present invention is reasonable, through sizing mixing, the accurate control of the process system such as alkalization, etherificate, immersion, filtration, washing, drying, make common glutinous rice starch there is cationic characteristic and high substitution value, gelatinization point and the retrogradation of glutinous rice starch have been reduced simultaneously, its effect can reach the paper industry requirement fully, can effectively improve paper strength, strengthens the drainage effect, keeps effect, reduces white water consistency and increase greyness of paper etc.
(2) the present invention be take glutinous rice starch and is prepared cationic starch as raw material, has expanded the use range of glutinous rice starch, has enriched the kind of cationic starch.
The accompanying drawing explanation
The infrared spectrogram that Fig. 1 is former glutinous rice starch and high degree of substitution quaternary ammonium cationic glutinous rice starch.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) size mixing: by the volume fraction of 12ml, be that 40% aqueous ethanolic solution joins in the glutinous rice starch of 50g and is mixed into the glutinous rice starch slurry.
(2) alkalization: be that 40% sodium hydroxide solution is added drop-wise in the glutinous rice starch slurry by the massfraction of 2ml.
(3) etherificate: by 2 of 15g, the 3-epoxypropyltrimethylchloride chloride joins in starch, and under room temperature, stirring reaction is 60 minutes.
(4) immersion, filtration, washing, drying: the volume fraction that the slurry of the glutinous rice starch after step (3) etherificate is contained to 5mL acetic acid with 100mL is that 60% aqueous ethanolic solution soaks, filter, take volume fraction as 70% aqueous ethanolic solution 100ml washing 5 times, to filtrate with the Silver Nitrate check without silver nitride precipitation; 40 ℃ of vacuum-dryings, obtain the white powder high degree of substitution quaternary ammonium cationic starch.
The present embodiment sample substitution value is 0.213, and infrared spectrogram as shown in Figure 1.Can be found out wave number 1326cm by infrared spectrogram
-1Place is the stretching vibration absorption peak of C-N, illustrates in glutinous rice starch and introduces positively charged ion, and wave number 1090cm
-1Place is the stretching vibration absorption peak of C-O-C, but the validity of the cation-modified reaction of aid illustration.
Embodiment 2
(1) size mixing: by the volume fraction of 14ml, be that 40% aqueous ethanolic solution joins in the glutinous rice starch of 50g and is mixed into the glutinous rice starch slurry.
(2) alkalization: be that 40% potassium hydroxide solution is added drop-wise in the glutinous rice starch slurry by the massfraction of 2ml.
(3) etherificate: by 2 of 18g, the 3-epoxypropyltrimethylchloride chloride joins in starch, and under room temperature, stirring reaction is 80 minutes.
(4) immersion, filtration, washing, drying: the volume fraction that the slurry of the glutinous rice starch after step (3) etherificate is contained to 5mL acetic acid with 100mL is that 65% aqueous ethanolic solution soaks, filter, take volume fraction as 75% aqueous ethanolic solution 100ml washing 5 times, to filtrate with the Silver Nitrate check without silver nitride precipitation; 45 ℃ of vacuum-dryings, obtain the white powder high degree of substitution quaternary ammonium cationic starch.
The present embodiment sample substitution value is 0.272.
Embodiment 3
(1) size mixing: by the volume fraction of 11ml, be that 40% aqueous ethanolic solution joins in the glutinous rice starch of 50g and is mixed into the glutinous rice starch slurry.
(2) alkalization: be that 40% aqua calcis is added drop-wise in the glutinous rice starch slurry by the massfraction of 2ml.
(3) etherificate: the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 15g is joined in starch, and under room temperature, stirring reaction is 100 minutes.
(4) immersion, filtration, washing, drying: the volume fraction that the slurry of the glutinous rice starch after step (3) etherificate is contained to 5mL acetic acid with 100mL is that 70% aqueous ethanolic solution soaks, filter, take volume fraction as 80% aqueous ethanolic solution 100ml washing 5 times, to filtrate with the Silver Nitrate check without silver nitride precipitation; 50 ℃ of vacuum-dryings, obtain the white powder high degree of substitution quaternary ammonium cationic starch.
The present embodiment sample substitution value is 0.282.
Embodiment 4
(1) size mixing: by the volume fraction of 12ml, be that 40% aqueous ethanolic solution joins in the glutinous rice starch of 50g and is mixed into the glutinous rice starch slurry.
(2) alkalization: be that 40% sodium hydroxide solution is added drop-wise in the glutinous rice starch slurry by the massfraction of 3ml.
(3) etherificate: the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 20g is joined in starch, and under room temperature, stirring reaction is 110 minutes.
(4) immersion, filtration, washing, drying: the volume fraction that the slurry of the glutinous rice starch after step (3) etherificate is contained to 5mL acetic acid with 100mL is that 70% aqueous ethanolic solution soaks, filter, take volume fraction as 80% aqueous ethanolic solution 100ml washing 5 times, to filtrate with the Silver Nitrate check without silver nitride precipitation; 50 ℃ of vacuum-dryings, obtain the white powder high degree of substitution quaternary ammonium cationic starch.
The present embodiment sample substitution value is 0.304.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (5)
1. the preparation method of a high degree of substitution quaternary ammonium cationic glutinous rice starch is characterized in that comprising following operation steps:
(1) size mixing: the aqueous ethanolic solution that will be equivalent to glutinous rice starch quality 20～25% joins in glutinous rice starch and is mixed into the glutinous rice starch slurry;
(2) alkalization: the alkali wiring solution-forming that will be equivalent to glutinous rice starch quality 1.5～3% is added drop-wise in the glutinous rice starch slurry of step (1);
(3) etherificate: the cationic etherifying agent that will be equivalent to glutinous rice starch quality 30～40% joins in the glutinous rice starch slurry after step (2) alkalizes, and under room temperature, stirring reaction is 60～110 minutes;
(4) immersion, filtration, washing, drying: the volume fraction that the slurry of the glutinous rice starch after step (3) etherificate is contained to 5mL acetic acid with every 100mL is that 60～70% aqueous ethanolic solutions soak, filter, the volume fraction of take produces without silver nitride precipitation with Silver Nitrate check as 70～80% aqueous ethanolic solutions wash to filtrate, then 40～50 ℃ of vacuum-dryings, obtain the high degree of substitution quaternary ammonium cationic glutinous rice starch.
2. preparation method according to claim 1, it is characterized in that: the volume fraction of the described aqueous ethanolic solution of step (1) is 40%.
3. preparation method according to claim 1, it is characterized in that: the described alkali of step (2) is sodium hydroxide, potassium hydroxide or calcium hydroxide.
4. preparation method according to claim 1, it is characterized in that: the described cationic etherifying agent of step (3) is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride.
5. the high degree of substitution quaternary ammonium cationic glutinous rice starch prepared according to the described preparation method of claim 1～4 any one.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104140469A (en) * | 2014-07-22 | 2014-11-12 | 金东纸业（江苏）股份有限公司 | Preparation method and device for cationic starch solution and paper |
| CN104193839A (en) * | 2014-09-05 | 2014-12-10 | 广州天赐高新材料股份有限公司 | Cationic starch as well as preparation method and application of cationic starch |
| CN104193837A (en) * | 2014-09-05 | 2014-12-10 | 北京联合大学 | Cationic starch flocculating agent and preparation method thereof |
| CN104945523A (en) * | 2015-07-08 | 2015-09-30 | 广东汇美淀粉科技有限公司 | Environment-friendly cation starch flocculant and preparing method thereof |
| CN104945522A (en) * | 2015-06-17 | 2015-09-30 | 华南理工大学 | Cationic tapioca starch with high substituted degree as well as preparation method and application thereof |
| CN111533817A (en) * | 2020-06-19 | 2020-08-14 | 江苏天将生物科技有限公司 | Production process of hydroxypropyl distarch phosphate |
| CN112551507A (en) * | 2020-12-25 | 2021-03-26 | 浙江工业大学 | Heteroatom-doped starch carbon and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104193839A (en) * | 2014-09-05 | 2014-12-10 | 广州天赐高新材料股份有限公司 | Cationic starch as well as preparation method and application of cationic starch |
| CN104193837A (en) * | 2014-09-05 | 2014-12-10 | 北京联合大学 | Cationic starch flocculating agent and preparation method thereof |
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| CN104945522A (en) * | 2015-06-17 | 2015-09-30 | 华南理工大学 | Cationic tapioca starch with high substituted degree as well as preparation method and application thereof |
| CN104945523A (en) * | 2015-07-08 | 2015-09-30 | 广东汇美淀粉科技有限公司 | Environment-friendly cation starch flocculant and preparing method thereof |
| CN111533817A (en) * | 2020-06-19 | 2020-08-14 | 江苏天将生物科技有限公司 | Production process of hydroxypropyl distarch phosphate |
| CN112551507A (en) * | 2020-12-25 | 2021-03-26 | 浙江工业大学 | Heteroatom-doped starch carbon and preparation method thereof |
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