CN102603903A - Method for preparing double-crosslinking amphoteric tapioca starch - Google Patents
Method for preparing double-crosslinking amphoteric tapioca starch Download PDFInfo
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Abstract
本发明公开了一种双交联两性木薯淀粉的制备方法。以木薯淀粉为主要原料，水为溶剂，氢氧化1-丁基-3-甲基咪唑和氢氧化钠为醚化反应的催化剂，以N，N′-亚甲基双丙烯酰胺为内交联剂使淀粉形成网状，再通过环氧氯丙烷外交联和二甲基二烯丙基氯化铵阳离子单体、一氯乙酸等两性试剂的改性制备一种双交联两性木薯淀粉，使木薯淀粉兼交联淀粉和两性淀粉的优势。本发明所得双交联两性木薯淀粉对热、酸和剪切力等的影响具有更高的稳定性。产品在造纸助剂和化妆品等方面具有较高的应用价值。同时，由于双交联两性木薯淀粉在水中溶胀而不溶解，在污水处理方面的应用效果更佳。
The invention discloses a preparation method of double-crosslinked amphoteric cassava starch. Tapioca starch is used as the main raw material, water is used as the solvent, 1-butyl-3-methylimidazole hydroxide and sodium hydroxide are used as catalysts for the etherification reaction, and N,N'-methylenebisacrylamide is used as the internal crosslink starch to form a network, and then prepare a double-crosslinked amphoteric tapioca starch through the modification of amphoteric reagents such as epichlorohydrin cross-linking and dimethyl diallyl ammonium chloride cationic monomer, monochloroacetic acid, etc., so that The advantages of tapioca starch and cross-linked starch and amphoteric starch. The obtained double-crosslinked amphoteric cassava starch has higher stability to the influence of heat, acid and shear force. The product has high application value in papermaking auxiliary and cosmetics. At the same time, because the double-crosslinked amphoteric tapioca starch swells in water and does not dissolve, it has a better application effect in sewage treatment.
Description
Technical field
The present invention relates to the preparation method that a kind of double cross joins the both sexes tapioca(flour).
Background technology
China's tapioca(flour) aboundresources, the structure of natural tapioca(flour) can change its inherent character or widen Application Areas through modifying sex change in the practical application.The both sexes modified starch is owing to have negatively charged ion and a cation group simultaneously, has more superior use properties than the starch derivative of single sex change.The external amphoteric starch product of having developed some models is like the CAT073-8002 of American National starch and chemical company production, CAT078-0140, the Y9152 that CATOXX-0220 and Britain Stadex company produce etc.The report of domestic relevant amphoteric starch aspect mainly is the amphoteric starch that is applied to paper industry.Usually massfraction and the states of matter by water in the reaction system is different, and the compound method of amphoteric starch is divided into wet method, dry method, semidrying three major types.Wet method research is comparatively ripe, and it is divided into solvent method and water law.Some solvents that solvent method adopts exist toxicity or problem such as inflammable, and it is higher to reclaim solvent cost; Water law comprises paste method and slurry method again by the starch existence form.Starch is with the gelatinization state response in the paste method, and the reaction mass viscosity is big, the refining difficulty of product, and this method is used less at present; Starch exists with suspension form in the slurry method, and reaction needs adds antithrombotics and avoids its gelatinization, and is lower than the gelatinization point reaction, causes aftertreatment complicated.Dry method, semidrying are the developed recently methods of getting up, and are the crosslinked amphoteric starch of etherifying agent dried preparation as adopting Mono Chloro Acetic Acid and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, and Technology is still immature.The cation group of amphoteric starch is generally uncle's ammonia or quaternary ammonium salts.Usually, widely used in industry is the quaternary ammonium etherifying agent, and tertiary amines etherifying agent such as 2-diethylamino diethylaluminum monochloride (DEC), because it just possesses cationic under acidic conditions, application is restricted.
Obtaining some progress aspect the modification of cross-linked cationic and crosslinked anionic starch both at home and abroad, but reporting less both at home and abroad about the research and development of crosslinked amphoteric starch.And double cross couplet amphoteric starch rarely has report so far both at home and abroad.Join through double cross, the polynary functional group of the alcoholic extract hydroxyl group of amphoteric starch and linking agent forms two ehter bonds or diester linkage, makes to form " bridge formation " between two or more amphoteric starch molecules, is complicated multidimensional network structure.
Summary of the invention
The purpose of this invention is to provide a kind of method that double cross joins the both sexes tapioca(flour) for preparing.
Concrete steps are:
(1) tapioca(flour) is dried to constant weight in 60 ℃ of vacuum drying ovens, gets the butt tapioca(flour);
(2) step (1) gained butt tapioca(flour) and deionized water are added to be made into massfraction in the reactor drum be 30%～35% starch solution;
Dimethyl diallyl ammonium chloride cationic monomer that (3) will be equivalent to 2～4 times of butt tapioca(flour) quality and the N that is equivalent to butt tapioca(flour) quality 3%, N '-methylene-bisacrylamide joins in step (2) the gained starch solution, stirs 15 minutes;
(4) taking by weighing respectively that to be equivalent to dimethyl diallyl ammonium chloride cationic monomer massfraction be 0.2%～0.4% ammonium persulphate and sodium sulfite anhy 96, is to be dissolved in 10mL deionized water at 1: 1 by ammonium persulphate and sodium sulfite anhy 96 mass ratio;
When (5) step (3) gained material being heated to 40 ℃, step (4) gained solution is controlled at constant pressure funnel is added drop-wise in 30 minutes in step (3) the gained material, continue reaction 4～6 hours, again system temperature is cooled to 30 ℃;
(6) take by weighing 1%～2% the epoxy chloropropane and the 0.2～0.4g sodium hydroxide that are equivalent to butt tapioca(flour) quality and add in step (5) the gained material, keeps 30 ℃ to react 1～2 hour;
(7) with 2～4mL massfraction be 25%～40% sodium hydroxide solution and 0.2～0.4g catalyzer hydroxide 1-butyl-3-Methylimidazole in joining step (6) gained material, priming reaction 30～50 minutes;
(8) get 5.86～11.72g Monochloro Acetic Acid and be dissolved in 10～20mL deionized water, with 5～10mL massfraction be that 25%～40% sodium hydroxide solution is mixed to join in step (7) the gained material, regulating and keeping system pH is 10～13; Every is 25%～40% sodium hydroxide solution at a distance from 30 minutes adding 1mL massfractions, 50 ℃ of control reaction temperature, 4～8 hours reaction times;
(9) using volume(tric)fraction is 95% ethanol sedimentation step (8) gained solution, suction filtration, filter cake, with deionized water filter wash cake to AgNO
3Detect and do not have deposition;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and promptly get thick product;
(11) be that Glacial acetic acid min. 99.5-terepthaloyl moietie mixed solvent of 60: 40 was removed homopolymer in 24 hours through the Soxhlet extractor extracting with volume ratio with the thick product of step (10), in 80 ℃ vacuum drying oven, be dried to constant weight and promptly get product.
(12) with the negatively charged ion substitution value of titration measuring product; Concrete operation method is following: accurately the sample of weighing 1.0g is put into the 50mL beaker, and adding 30mL concentration is the HCl solution of 0.1mol/L, the magnetic agitation extremely abundant acidifying of crosslinked amphoteric starch in 3 hours; Suction filtration is washed to AgNO
3Detect and do not have deposition.The sample of this processing is placed the 250mL beaker, add 100mL water, heating for dissolving is cooled to room temperature to clarification.Splash into 2～3 phenolphthalein indicators, with the NaOH standard solution titration of 0.1mol/L to blush.Under the same conditions, carry out blank titration.Negatively charged ion substitution value DS calculating formula is:
In the formula: V
NaOH---the volume of the NaOH standardized solution that sample consumes, mL;
V
Blank---the volume of the NaOH standardized solution that record is consumed, mL;
C
NaOH---the concentration of NaOH standardized solution, mol/L;
The quality of m---sample, g;
162---the molar mass of glucose unit in the starch, g/mol.
(13) mensuration of cationic degree DC: measure Cl with reference to Mohr's method
-Content.Sample behind the purifying is mixed with certain density solution, makes indicator, use the silver nitrate solution titration, be titration end point when brick-red when solution becomes with potassiumchromate.Carry out the blank test under the similarity condition.Cationic degree DC can be calculated as follows:
In the formula: V---sample consumes the volume of silver nitrate solution, mL;
V
Blank---the blank volume that consumes silver nitrate solution, mL;
The quality of m---sample, g;
161.5---the molar mass of dimethyl diallyl ammonium chloride, g/mol;
0.05---AgNO
3The concentration of solution, mol/L.
Gained double cross couplet both sexes tapioca(flour) of the present invention has higher stability to the influence of heat, acid and shearing force etc.Product has higher using value at aspects such as paper making additive and makeup.Simultaneously, because double cross joins both sexes tapioca(flour) swelling and not dissolving in water, the effect aspect WWT is better.
Description of drawings
Fig. 1 is former tapioca(flour) IR figure.
Fig. 2 joins both sexes tapioca(flour) IR figure for the double cross of embodiment of the invention preparation.
Fig. 3 is former tapioca(flour) SEM figure.
Fig. 4 joins both sexes tapioca(flour) SEM figure for the double cross of embodiment of the invention preparation.
Embodiment
Embodiment 1:
(1) tapioca(flour) is dried to constant weight in 60 ℃ of vacuum drying ovens, gets the butt tapioca(flour);
(2) take by weighing 10g step (1) gained butt tapioca(flour) and deionized water and add that to be made into massfraction in the reactor drum be 30%～35% starch solution;
(3) with 25g dimethyl diallyl ammonium chloride cationic monomer and 0.3g N, N '-methylene-bisacrylamide adds in step (2) the gained starch solution, stirs 15 minutes;
(4) take by weighing 0.05g ammonium persulphate and 0.05g sodium sulfite anhy 96 respectively, be dissolved in the 10mL deionized water;
When (5) step (3) gained material being heated to 40 ℃, step (4) solution is controlled at constant pressure funnel is added drop-wise in 30 minutes in step (3) the gained material, continue reaction 5 hours, again system temperature is cooled to 30 ℃;
(6) take by weighing 0.1g epoxy chloropropane and 0.2g sodium hydroxide and join in step (5) the gained material, keep 30 ℃ of reactions 1 hour;
(7) with the 2mL massfraction be 25% sodium hydroxide solution and 0.2g catalyzer hydroxide 1-butyl-3-Methylimidazole in joining step (6) gained material, priming reaction 35 minutes;
(8) get the 5.86g Monochloro Acetic Acid and be dissolved in the 10mL deionized water, with the 5mL massfraction be that 25% sodium hydroxide solution is mixed to join in step (7) the gained material, regulating and keeping system pH is 11～12; Every is 25% sodium hydroxide solution at a distance from 30 minutes adding 1mL massfractions, 50 ℃ of control reaction temperature, 5 hours reaction times;
(9) using volume(tric)fraction is 95% ethanol sedimentation step (8) gained solution, suction filtration, filter cake, with deionized water filter wash cake to AgNO
3Detect and do not have deposition;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and promptly get crude product;
(11) be that Glacial acetic acid min. 99.5-terepthaloyl moietie mixed solvent of 60: 40 is removed homopolymer through Soxhlet extractor extracting 24 hours with volume ratio with step (10) crude product, in 80 ℃ vacuum drying oven, be dried to constant weight and promptly get product.
(12) using the negatively charged ion substitution value of titration measuring product is 0.25, and cationic degree is 0.68.
Embodiment 2:
(1) tapioca(flour) is dried to constant weight in 60 ℃ of vacuum drying ovens, gets the butt tapioca(flour);
(2) take by weighing 20g step (1) gained butt tapioca(flour) and deionized water and add that to be made into massfraction in the reactor drum be 30%～35% starch solution;
(3) with 35g dimethyl diallyl ammonium chloride cationic monomer and 0.6g N, N '-methylene-bisacrylamide joins in step (2) starch solution, stirs 15 minutes;
(4) take by weighing 0.12g ammonium persulphate and 0.12g sodium sulfite anhy 96 respectively, be dissolved in the 10mL deionized water;
When (5) step (3) gains being heated to 40 ℃, step (4) solution is controlled at constant pressure funnel is added drop-wise in 30 minutes in step (3) the gained material, continue reaction 6 hours, again system temperature is cooled to 30 ℃;
(6) take by weighing 0.2g epoxy chloropropane and 0.3g sodium hydroxide and join in step (5) the gained material, keep 30 ℃ of reactions 1 hour;
(7) with the 4mL massfraction be 35% sodium hydroxide solution and 0.4g catalyzer hydroxide 1-butyl-3-Methylimidazole in joining step (6) gained material, priming reaction 50 minutes;
(8) get the 11.72g Monochloro Acetic Acid and be dissolved in the 20mL deionized water, with the 10mL massfraction be that 35% sodium hydroxide solution is mixed to join in step (7) the gained material, regulating and keeping system pH is 10～11; Every is 35% sodium hydroxide solution at a distance from 30 minutes adding 1mL massfractions, 50 ℃ of control reaction temperature, 8 hours reaction times;
(9) using volume(tric)fraction is 95% ethanol sedimentation step (8) gained solution, suction filtration, filter cake, with deionized water filter wash cake to AgNO
3Detect and do not have deposition;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and promptly get crude product;
(11) be that Glacial acetic acid min. 99.5-terepthaloyl moietie mixed solvent of 60: 40 is removed homopolymer through Soxhlet extractor extracting 24 hours with volume ratio with step (8) crude product, in 80 ℃ vacuum drying oven, be dried to constant weight and promptly get product.
(12) using the negatively charged ion substitution value of titration measuring product is 0.23, and cationic degree is 0.75.
Product is analyzed through IR, 1605.65cm
-1For in the Mono Chloro Acetic Acid-COO
-Vibration absorption peak; 1411.47cm
-1Be linking agent N, the stretching vibration absorption peak of C-N in N '-methylene-bisacrylamide; 1251.09cm
-1Stretching vibration absorption peak for cationic monomer C-N; 1158.70cm
-1～1014.80cm
-1Near absorption peak clearly broadens, and this is the stretching vibration absorption peak of C-O in the linking agent epoxy chloropropane.Through sem analysis, the particle surface pattern before and after the contrast modification can find out that the granule-morphology of former tapioca(flour) is circle or sub-circular, and particle is more complete, and the surface is more smooth.Double cross joins both sexes tapioca(flour) particle and is bonded together by many small-particles; Making double cross join both sexes tapioca(flour) particle becomes big and becomes anomocytic type; There are tangible damaged rill and very dark cave in the surface; Make the structure generation considerable change of former tapioca(flour), explain that reaction does not occur over just the unformed area of starch molecular structure, and also occur in crystallizing field.The erosion of this ecto-entad possibly be to penetrate or produce to core with certain form from the surface of starch granules to break but not to surface diffusion.
Claims (1)
1. a double cross joins the preparation method of both sexes tapioca(flour), it is characterized in that concrete steps are:
(1) tapioca(flour) is dried to constant weight in 60 ℃ of vacuum drying ovens, gets the butt tapioca(flour);
(2) step (1) gained butt tapioca(flour) and deionized water are added to be made into massfraction in the reactor drum be 30%～35% starch solution;
Dimethyl diallyl ammonium chloride cationic monomer that (3) will be equivalent to 2～4 times of butt tapioca(flour) quality and the N that is equivalent to butt tapioca(flour) quality 3%, N '-methylene-bisacrylamide joins in step (2) the gained starch solution, stirs 15 minutes;
(4) taking by weighing respectively that to be equivalent to dimethyl diallyl ammonium chloride cationic monomer massfraction be 0.2%～0.4% ammonium persulphate and sodium sulfite anhy 96, is to be dissolved in 10mL deionized water at 1: 1 by ammonium persulphate and sodium sulfite anhy 96 mass ratio;
When (5) step (3) gained material being heated to 40 ℃, step (4) gained solution is controlled at constant pressure funnel is added drop-wise in 30 minutes in step (3) the gained material, continue reaction 4～6 hours, again system temperature is cooled to 30 ℃;
(6) take by weighing 1%～2% the epoxy chloropropane and the 0.2～0.4g sodium hydroxide that are equivalent to butt tapioca(flour) quality and add in step (5) the gained material, keeps 30 ℃ to react 1～2 hour;
(7) with 2～4mL massfraction be 25%～40% sodium hydroxide solution and 0.2～0.4g catalyzer hydroxide 1-butyl-3-Methylimidazole in joining step (6) gained material, priming reaction 30～50 minutes;
(8) get 5.86～11.72g Monochloro Acetic Acid and be dissolved in 10～20mL deionized water, with 5～10mL massfraction be that 25%～40% sodium hydroxide solution is mixed to join in step (7) the gained material, regulating and keeping system pH is 10～13; Every is 25%～40% sodium hydroxide solution at a distance from 30 minutes adding 1mL massfractions, 50 ℃ of control reaction temperature, 4～8 hours reaction times;
(9) using volume(tric)fraction is 95% ethanol sedimentation step (8) gained solution, suction filtration, filter cake, with deionized water filter wash cake to AgNO
3Detect and do not have deposition;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and promptly get thick product;
(11) be that Glacial acetic acid min. 99.5-terepthaloyl moietie mixed solvent of 60: 40 was removed homopolymer in 24 hours through the Soxhlet extractor extracting with volume ratio with the thick product of step (10), in 80 ℃ vacuum drying oven, be dried to constant weight and promptly get product.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898665A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing adsorptive double cross-linked amphoteric cassava starch |
| CN102898666A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing high-degree double-crosslinked amphoteric grafted tapioca starch resin |
| CN103059227A (en) * | 2013-01-27 | 2013-04-24 | 桂林理工大学 | Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch |
| CN103509128A (en) * | 2013-09-05 | 2014-01-15 | 江西顺昌隆实业有限公司 | One-step preparation method for carboxyl-type amphoteric starch by employing semi-dry technology |
| CN103924480A (en) * | 2014-04-04 | 2014-07-16 | 诸城市奥尼生物科技有限公司 | Formula and preparation method of functionalized enhancer for papermaking |
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| CN104177635B (en) * | 2014-09-22 | 2016-09-14 | 广西民族大学 | A kind of preparation method of triple crosslinking binary graft copolymerization starch |
| CN107840463A (en) * | 2017-12-19 | 2018-03-27 | 安徽仁维环保工程科技有限公司 | A kind of sewage-treating agent and preparation method thereof |
| CN109423266A (en) * | 2017-08-22 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of amphoteric ion spherex and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898665A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing adsorptive double cross-linked amphoteric cassava starch |
| CN102898666A (en) * | 2012-11-07 | 2013-01-30 | 桂林理工大学 | Method for preparing high-degree double-crosslinked amphoteric grafted tapioca starch resin |
| CN102898666B (en) * | 2012-11-07 | 2014-01-08 | 桂林理工大学 | A kind of preparation method of highly double-crosslinked amphoteric grafted tapioca starch resin |
| CN102898665B (en) * | 2012-11-07 | 2014-01-08 | 桂林理工大学 | A kind of preparation method of adsorptive double-crosslinked amphoteric tapioca starch |
| CN103059227A (en) * | 2013-01-27 | 2013-04-24 | 桂林理工大学 | Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch |
| CN103509128A (en) * | 2013-09-05 | 2014-01-15 | 江西顺昌隆实业有限公司 | One-step preparation method for carboxyl-type amphoteric starch by employing semi-dry technology |
| CN103924480A (en) * | 2014-04-04 | 2014-07-16 | 诸城市奥尼生物科技有限公司 | Formula and preparation method of functionalized enhancer for papermaking |
| CN103924480B (en) * | 2014-04-04 | 2017-11-21 | 山东奥尼生物科技股份有限公司 | The formula and preparation method of feature paper grade (stock) reinforcing agent |
| CN104177635B (en) * | 2014-09-22 | 2016-09-14 | 广西民族大学 | A kind of preparation method of triple crosslinking binary graft copolymerization starch |
| CN104804139A (en) * | 2015-05-21 | 2015-07-29 | 南京大学 | Flocculation sterilization difunctional grafting starch water treatment agent and preparation method thereof |
| CN109423266A (en) * | 2017-08-22 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of amphoteric ion spherex and its preparation method and application |
| CN109423266B (en) * | 2017-08-22 | 2020-10-16 | 中国石油化工股份有限公司 | Amphoteric ion starch microsphere and preparation method and application thereof |
| CN107840463A (en) * | 2017-12-19 | 2018-03-27 | 安徽仁维环保工程科技有限公司 | A kind of sewage-treating agent and preparation method thereof |
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