CN103421124B - A kind of high degree of substitution quaternary ammonium cationic glutinous rice starch and preparation method thereof - Google Patents
A kind of high degree of substitution quaternary ammonium cationic glutinous rice starch and preparation method thereof Download PDFInfo
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- CN103421124B CN103421124B CN201310389054.7A CN201310389054A CN103421124B CN 103421124 B CN103421124 B CN 103421124B CN 201310389054 A CN201310389054 A CN 201310389054A CN 103421124 B CN103421124 B CN 103421124B
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Abstract
The invention belongs to the production technical field of modified starch, disclose a kind of high degree of substitution quaternary ammonium cationic glutinous rice starch and preparation method thereof.Glutinous rice starch and aqueous ethanolic solution are mixed into glutinous rice starch starch; Then at room temperature add alkaline solution to stir; Then joined by cationic etherifying agent in glutinous rice starch slurry and stir, stirring reaction obtains thick product; The aqueous ethanolic solution of thick product containing acetic acid is soaked, filters, then produce without silver nitride precipitation with Silver Nitrate inspection to filtrate with aqueous ethanolic solution washing; Then vacuum-drying, obtains the high degree of substitution quaternary ammonium cationic glutinous rice starch of white powder.The present invention's glutinous rice starch is that raw material choose semidrying prepares high degree of substitution quaternary ammonium cationic glutinous rice starch, has expanded the use range of glutinous rice starch.
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 ripe at the Application comparison 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 in cationic, in particularly suitable, alkalescence or acidic conditions under copy paper, in today that neutral papermaking technology develops rapidly, it is just becoming indispensable paper making additive, is also a kind of modified starch that the current scope of application is the widest, consumption is maximum.
The domestic production method about cationic starch, mainly contains wet method, dry method and semidrying.Wet method, due to low conversion rate, produces a large amount of waste water in production, and the cationic starch substitution value produced is less than 0.1.Dry method also exist reaction uneven, long reaction time, foreign matter content are high, the high deficiency of equipment requirements.And semidrying preparation technology has technique simply, the features such as reaction efficiency is high, and energy consumption is low, and environmental pollution is little.
The cationic starch substitution value being applied to paper making wet part is at present generally 0.01 ~ 0.07, belongs to Low-substituted Cationic Starch, in order to more this reproducible resource of good utilisation starch, expands the Application Areas of cationic starch at papermaking Jiang Yezhong.Prepare cationic starch with high substitution degree to be applied to paper making wet part and to make retention filtration adjuvant and anion garbage capturing agent.
The raw material preparing cationic starch common at present has W-Gum, tapioca (flour), wheat starch or yam starch etc., is that raw material is prepared cationic starch with high substitution degree and is not seen in report with glutinous rice starch.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of high degree of substitution quaternary ammonium cationic glutinous rice starch.The present invention is that raw material choose semidrying prepares high degree of substitution quaternary ammonium cationic glutinous rice starch with glutinous rice starch, has expanded the use range of glutinous rice starch, has enriched the kind of cationic starch;
Another object of the present invention is to the high degree of substitution quaternary ammonium cationic glutinous rice starch providing above-mentioned preparation method to prepare;
Object of the present invention is achieved through the following technical solutions:
A preparation method for high degree of substitution quaternary ammonium cationic glutinous rice starch, comprises following operation steps:
(1) size mixing: the aqueous ethanolic solution being equivalent to glutinous rice starch quality 20 ~ 25% is joined in glutinous rice starch and is mixed into glutinous rice starch slurry;
(2) alkalize: the alkali wiring solution-forming being 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 being equivalent to glutinous rice starch quality 30 ~ 40% is joined in the glutinous rice starch slurry after step (2) alkalization, stirred at ambient temperature reaction 60 ~ 110 minutes;
(4) immersion, filtration, washing, drying: being starched by the glutinous rice starch after step (3) etherificate by the volume fraction that every 100mL contains 5mL acetic acid is 60 ~ 70% aqueous ethanolic solutions immersions, filter, with volume fraction be 70 ~ 80% aqueous ethanolic solutions washing to filtrate Silver Nitrate inspection produce without silver nitride precipitation, then 40 ~ 50 DEG C of vacuum-dryings, high degree of substitution quaternary ammonium cationic glutinous rice starch is obtained.
The volume fraction of the aqueous ethanolic solution described in step (1) is 40%.
Alkali described in step (2) is sodium hydroxide, potassium hydroxide or calcium hydroxide.
Step (3) described cationic etherifying agent 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 relative to prior art:
(1) preparation method's production technique of the present invention is reasonable, through sizing mixing, alkalizing, etherificate, immersion, filtration, washing, the process system such as drying accurate control, common glutinous rice starch is made to have cationic characteristic and high substitution value, reduce gelatinization point and the retrogradation of glutinous rice starch simultaneously, its effect can reach paper industry requirement completely, effectively can improve paper strength, strengthen drainage effect, keep effect, reduce white water consistency and increase greyness of paper etc.
(2) the present invention is that cationic starch prepared by raw material with glutinous rice starch, has expanded the use range of glutinous rice starch, has enriched the kind of cationic starch.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of 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 thereto.
Embodiment 1
(1) size mixing: by the volume fraction of 12ml be 40% aqueous ethanolic solution join in the glutinous rice starch of 50g be mixed into glutinous rice starch slurry.
(2) alkalize: be that 40% sodium hydroxide solution is added drop-wise in glutinous rice starch slurry by the massfraction of 2ml.
(3) etherificate: join in starch by 2, the 3-epoxypropyltrimethylchloride chlorides of 15g, stirred at ambient temperature reacts 60 minutes.
(4) immersion, filtration, washing, drying: be that 60% aqueous ethanolic solution soaks by the volume fraction that the glutinous rice starch slurry 100mL after step (3) etherificate contains 5mL acetic acid, filter, be that 70% aqueous ethanolic solution 100ml washs 5 times with volume fraction, to filtrate with Silver Nitrate inspection without silver nitride precipitation; 40 DEG C of vacuum-dryings, obtain 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.As can be seen from infrared spectrogram, wave number 1326cm
-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, can the validity of the cation-modified reaction of aid illustration.
Embodiment 2
(1) size mixing: by the volume fraction of 14ml be 40% aqueous ethanolic solution join in the glutinous rice starch of 50g be mixed into glutinous rice starch slurry.
(2) alkalize: be that 40% potassium hydroxide solution is added drop-wise in glutinous rice starch slurry by the massfraction of 2ml.
(3) etherificate: join in starch by 2, the 3-epoxypropyltrimethylchloride chlorides of 18g, stirred at ambient temperature reacts 80 minutes.
(4) immersion, filtration, washing, drying: be that 65% aqueous ethanolic solution soaks by the volume fraction that the glutinous rice starch slurry 100mL after step (3) etherificate contains 5mL acetic acid, filter, be that 75% aqueous ethanolic solution 100ml washs 5 times with volume fraction, to filtrate with Silver Nitrate inspection without silver nitride precipitation; 45 DEG C of vacuum-dryings, obtain 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 40% aqueous ethanolic solution join in the glutinous rice starch of 50g be mixed into glutinous rice starch slurry.
(2) alkalize: be that 40% aqua calcis is added drop-wise in glutinous rice starch slurry by the massfraction of 2ml.
(3) etherificate: join in starch by the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 15g, stirred at ambient temperature reacts 100 minutes.
(4) immersion, filtration, washing, drying: be that 70% aqueous ethanolic solution soaks by the volume fraction that the glutinous rice starch slurry 100mL after step (3) etherificate contains 5mL acetic acid, filter, be that 80% aqueous ethanolic solution 100ml washs 5 times with volume fraction, to filtrate with Silver Nitrate inspection without silver nitride precipitation; 50 DEG C of vacuum-dryings, obtain 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 40% aqueous ethanolic solution join in the glutinous rice starch of 50g be mixed into glutinous rice starch slurry.
(2) alkalize: be that 40% sodium hydroxide solution is added drop-wise in glutinous rice starch slurry by the massfraction of 3ml.
(3) etherificate: join in starch by the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride of 20g, stirred at ambient temperature reacts 110 minutes.
(4) immersion, filtration, washing, drying: be that 70% aqueous ethanolic solution soaks by the volume fraction that the glutinous rice starch slurry 100mL after step (3) etherificate contains 5mL acetic acid, filter, be that 80% aqueous ethanolic solution 100ml washs 5 times with volume fraction, to filtrate with Silver Nitrate inspection without silver nitride precipitation; 50 DEG C of vacuum-dryings, obtain white powder high degree of substitution quaternary ammonium cationic starch.
The present embodiment sample substitution value is 0.304.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (2)
1. a preparation method for 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 being equivalent to glutinous rice starch quality 20 ~ 25% is joined in glutinous rice starch and is mixed into glutinous rice starch slurry; The volume fraction of described aqueous ethanolic solution is 40%;
(2) alkalize: the alkali wiring solution-forming being 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 being equivalent to glutinous rice starch quality 30 ~ 40% is joined in the glutinous rice starch slurry after step (2) alkalization, stirred at ambient temperature reaction 60 ~ 110 minutes; Described cationic etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride or 2,3-epoxypropyltrimethylchloride chloride;
(4) immersion, filtration, washing, drying: being starched by the glutinous rice starch after step (3) etherificate by the volume fraction that every 100mL contains 5mL acetic acid is 60 ~ 70% aqueous ethanolic solutions immersions, filter, with volume fraction be 70 ~ 80% aqueous ethanolic solutions washing to filtrate Silver Nitrate inspection produce without silver nitride precipitation, then 40 ~ 50 DEG C of vacuum-dryings, high degree of substitution quaternary ammonium cationic glutinous rice starch is obtained; Described positively charged ion glutinous rice starch substitution value is 0.213,0.272,0.282 or 0.304.
2. preparation method according to claim 1, is characterized in that: the alkali described in step (2) is sodium hydroxide, potassium hydroxide or calcium hydroxide.
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| CN104140469B (en) * | 2014-07-22 | 2016-06-29 | 金东纸业（江苏）股份有限公司 | A kind of cationic starch solution preparation method, equipment and paper |
| CN104193837B (en) * | 2014-09-05 | 2016-11-30 | 北京联合大学 | A kind of cationic starch flocculant and preparation method thereof |
| CN104193839B (en) * | 2014-09-05 | 2016-08-17 | 广州天赐高新材料股份有限公司 | Cationic starch and its preparation method and application |
| CN104945522B (en) * | 2015-06-17 | 2017-12-01 | 华南理工大学 | A kind of high substituted degree cation cassava starch and preparation method and application |
| 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 |
| CN112551507B (en) * | 2020-12-25 | 2022-11-15 | 浙江工业大学 | Heteroatom-doped starch carbon and preparation method thereof |
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| CN101555287A (en) * | 2009-05-18 | 2009-10-14 | 兖州熙来精细化工有限公司 | Production method of cationic starch |
| CN102504033A (en) * | 2011-10-26 | 2012-06-20 | 泉州华祥纸业有限公司 | Preparation method of modified anion starch for papermaking |
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| JPH0687902A (en) * | 1992-07-02 | 1994-03-29 | Sakamoto Yakuhin Kogyo Kk | Production of cationic modified starch |
| CN102585021B (en) * | 2012-02-21 | 2014-06-11 | 芜湖迅腾新材料有限公司 | Method for synthesizing composite modified starch slurry |
| CN102585020A (en) * | 2012-03-14 | 2012-07-18 | 闽江学院 | Method for synthesizing cationic starch with high substation degree based on basic ionic liquid |
| CN102642905B (en) * | 2012-05-03 | 2013-07-10 | 三明学院 | Green modified starch multifunctional sewage treating agent and method for preparing same |
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| CN101555287A (en) * | 2009-05-18 | 2009-10-14 | 兖州熙来精细化工有限公司 | Production method of cationic starch |
| CN102504033A (en) * | 2011-10-26 | 2012-06-20 | 泉州华祥纸业有限公司 | Preparation method of modified anion starch for papermaking |
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