CN102603903B - Method for preparing double-crosslinking amphoteric tapioca starch - Google Patents
Method for preparing double-crosslinking amphoteric tapioca starch Download PDFInfo
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- CN102603903B CN102603903B CN 201210062487 CN201210062487A CN102603903B CN 102603903 B CN102603903 B CN 102603903B CN 201210062487 CN201210062487 CN 201210062487 CN 201210062487 A CN201210062487 A CN 201210062487A CN 102603903 B CN102603903 B CN 102603903B
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- 240000003183 Manihot esculenta Species 0.000 title claims abstract description 41
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 title claims abstract description 41
- 229920002472 Starch Polymers 0.000 title claims abstract description 37
- 239000008107 starch Substances 0.000 title claims abstract description 37
- 235000019698 starch Nutrition 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title abstract description 16
- 238000004132 cross linking Methods 0.000 title abstract 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 8
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 7
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical compound C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000013312 flour Nutrition 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 238000005304 joining Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 230000037452 priming Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 abstract description 3
- -1 dimethyl diallyl ammonium chloride cation Chemical class 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000006266 etherification reaction Methods 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000001450 anions Chemical group 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920006320 anionic starch Polymers 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 229960004676 antithrombotic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing double-crosslinking amphoteric tapioca starch. The method includes: using tapioca starch as main materials, water as solvent, hydroxide 1-butyl-3-methyl imidazole and sodium hydroxide as catalysts for etherification reaction, and N, N'-methylene bisacrylamide as inner-crosslinking agent to enable the starch to be in a meshed form, and preparing double-crosslinking amphoteric tapioca starch by means of outer crosslinking of epichlorohydrin and modification of amphoteric agent such as dimethyl diallyl ammonium chloride cation monomers, monochloro acetic acid and the like to enable the tapioca starch to integrate advantages of crosslinking starch and amphoteric starch. The double-crosslinking amphoteric tapioca starch has high application value in papermaking auxiliaries, cosmetics and the like. Further, since the double-crosslinking amphoteric tapioca starch is swellable in water but insoluble, application of the double-crosslinking amphoteric tapioca starch in sewage treatment is more effective.
Description
Technical field
The present invention relates to a kind of preparation method of double cross connection both sexes tapioca (flour).
Background technology
China's tapioca (flour) aboundresources, the structure of natural wood sweet potato starch can change its intrinsic character or broaden application field by 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 such as 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 synthetic 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 the problem such as inflammable, and it is higher to reclaim solvent cost; Water law comprises again paste method and slurry method by the starch existence form.Starch is with the gelatinization state response in the paste method, and the reaction mass viscosity is large, 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 to add 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 dry process 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.
Having made 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 connection amphoteric starch rarely has report so far both at home and abroad.Through the double cross connection, 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 for preparing double cross connection both sexes tapioca (flour).
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 be 30%～35% starch solution;
(3) will be equivalent to the dimethyl diallyl ammonium chloride cationic monomer of 2～4 times of butt tapioca (flour) quality and be equivalent to the N of 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 bisulfite, is to be dissolved in 10mL deionized water at 1: 1 by ammonium persulphate and sodium bisulfite 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, system temperature is cooled to 30 ℃ again;
(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; Added the 1mL massfraction every 30 minutes and be 25%～40% sodium hydroxide solution, 50 ℃ of control temperature of reaction, 4～8 hours reaction times;
(9) with volume fraction be 95% ethanol settling step (8) gained solution, suction filtration gets filter cake, with deionized water filter wash cake to AgNO
3Detect without precipitation;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and namely get thick product;
(11) with the thick product of step (10) take volume ratio as 60: 40 Glacial acetic acid-the ethylene glycol mixed solvent removed homopolymer in 24 hours by the Soxhlet extractor extracting, is dried to constant weight and namely gets product in 80 ℃ vacuum drying oven.
(12) Anion substituting degree of usefulness titration measuring product, concrete operation method is as follows: the sample of accurate 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 without precipitation.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, be titrated to blush with the NaOH standardized solution of 0.1mol/L.Under the same conditions, carry out blank titration.Anion substituting degree 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 consumes, 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 with potassiumchromate, use the silver nitrate solution titration, be titration end point when brick-red when solution becomes.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 connection both sexes tapioca (flour) of the present invention has higher stability to the impact 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 connection both sexes tapioca (flour) swelling and not dissolving in water, the effect aspect sewage disposal is better.
Description of drawings
Fig. 1 is former tapioca (flour) IR figure.
Fig. 2 is the double cross connection both sexes tapioca (flour) IR figure of embodiment of the invention preparation.
Fig. 3 is former tapioca (flour) SEM figure.
Fig. 4 is the double cross connection both sexes tapioca (flour) SEM figure 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 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 respectively 0.05g ammonium persulphate and 0.05g sodium bisulfite, 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, system temperature is cooled to 30 ℃ again;
(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; Added the 1mL massfraction every 30 minutes and be 25% sodium hydroxide solution, 50 ℃ of control temperature of reaction, 5 hours reaction times;
(9) with volume fraction be 95% ethanol settling step (8) gained solution, suction filtration gets filter cake, with deionized water filter wash cake to AgNO
3Detect without precipitation;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and namely get crude product;
(11) with step (10) crude product take volume ratio as 60: 40 Glacial acetic acid-the ethylene glycol mixed solvent removed homopolymer in 24 hours by the Soxhlet extractor extracting, is dried to constant weight and namely gets product in 80 ℃ vacuum drying oven.
(12) Anion substituting degree with the 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 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 respectively 0.12g ammonium persulphate and 0.12g sodium bisulfite, 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, system temperature is cooled to 30 ℃ again;
(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; Added the 1mL massfraction every 30 minutes and be 35% sodium hydroxide solution, 50 ℃ of control temperature of reaction, 8 hours reaction times;
(9) with volume fraction be 95% ethanol settling step (8) gained solution, suction filtration gets filter cake, with deionized water filter wash cake to AgNO
3Detect without precipitation;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and namely get crude product;
(11) with step (8) crude product take volume ratio as 60: 40 Glacial acetic acid-the ethylene glycol mixed solvent removed homopolymer in 24 hours by the Soxhlet extractor extracting, is dried to constant weight and namely gets product in 80 ℃ vacuum drying oven.
(12) Anion substituting degree with the 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 connection both sexes tapioca (flour) particle is bonded together by many small-particles, make double cross connection both sexes tapioca (flour) particle become large and become anomocytic type, there are obvious damaged rill and very dark cave in the surface, make the structure generation considerable change of former tapioca (flour), illustrate 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 may be to penetrate or produce to core with certain form from the surface of starch granules to break but not diffuse to the surface.
Claims (1)
1. the preparation method of double cross connection both sexes tapioca (flour) 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 be 30%～35% starch solution;
(3) will be equivalent to the dimethyl diallyl ammonium chloride cationic monomer of 2～4 times of butt tapioca (flour) quality and be equivalent to the N of 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 bisulfite, is to be dissolved in 10mL deionized water at 1: 1 by ammonium persulphate and sodium bisulfite 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, system temperature is cooled to 30 ℃ again;
(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; Added the 1mL massfraction every 30 minutes and be 25%～40% sodium hydroxide solution, 50 ℃ of control temperature of reaction, 4～8 hours reaction times;
(9) with volume fraction be 95% ethanol settling step (8) gained solution, suction filtration gets filter cake, with deionized water filter wash cake to AgNO
3Detect without precipitation;
(10) step (9) gained filter cake is put into glass dish, be dried to constant weight in the vacuum drying oven under 80 ℃ and namely get thick product;
(11) with the thick product of step (10) take volume ratio as 60: 40 Glacial acetic acid-the ethylene glycol mixed solvent removed homopolymer in 24 hours by the Soxhlet extractor extracting, is dried to constant weight and namely gets product in 80 ℃ vacuum drying oven.
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| CN102898665B (en) * | 2012-11-07 | 2014-01-08 | 桂林理工大学 | Method for preparing adsorptive double cross-linked amphoteric cassava starch |
| CN102898666B (en) * | 2012-11-07 | 2014-01-08 | 桂林理工大学 | Method for preparing high-degree double-crosslinked amphoteric grafted tapioca starch resin |
| CN103059227B (en) * | 2013-01-27 | 2015-01-21 | 桂林理工大学 | Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch |
| 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 |
| 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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| JPS53130789A (en) * | 1978-04-27 | 1978-11-15 | Sanyo Chem Ind Ltd | Preparation of water absorbing resin |
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|---|---|---|---|---|
| CN1667007A (en) * | 2005-04-01 | 2005-09-14 | 大连民生环保科技有限公司 | Starch-base macromolecules environmental protection flocculant, process for preparing same and use thereof |
| CN101319031A (en) * | 2008-07-23 | 2008-12-10 | 哈尔滨工业大学 | Starch graft acrylic acid/modified verdelite high-water-absorption resin and preparing method thereof |
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| 《Synthesis of a Novel Double Crosslinking Amphoteric Cassava Starch》;Huqiang Lv et al.;《Advanced Materials Research》;20120103;第430-432卷;第476-479页，实验部分 * |
| Huqiang Lv et al..《Synthesis of a Novel Double Crosslinking Amphoteric Cassava Starch》.《Advanced Materials Research》.2012,第430-432卷第476-479页. |
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