CN102898665B - Method for preparing adsorptive double cross-linked amphoteric cassava starch - Google Patents
Method for preparing adsorptive double cross-linked amphoteric cassava starch Download PDFInfo
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Abstract
The invention discloses a method for preparing adsorptive double cross-linked amphoteric cassava starch. According to the method, cassava starch serves as a main raw material, dimethyl diallyl ammonium chloride serves as cation graft monomer, acrylic acid ethyl ester and 3-chloro-2-hydroxypropyl methacrylate serve as anion graft monomer, N,N'-Methylenebisacrylamide serves as an inner-crosslinking agent and sodium polyphosphate serves as an external crosslinking agent, and the adsorptive double cross-linked amphoteric cassava starch is prepared by process steps such as cation graft, anion graft and inner and external double cross-linking in an aqueous solution, soaking and washing, drying and crushing. Starch derivatives have a relatively complex net structure, the adsorptive double cross-linked amphoteric cassava starch has special adsorption to metal ions due to double cross-linking, can be repeatedly used, are easy to recycle, and have ideal effects of separating and enriching heavy metal and rare metal, and treating sewage.
Description
Technical field
The present invention relates to a kind of method for preparing adsorptivity double cross connection both sexes tapioca (flour).
Background technology
Crosslinked amphoteric starch is the reactive behavior of utilizing hydroxyl in the starch glucose unit, and it is reacted and obtain with yin, yang ion etherifying agent or zwitter-ion, linking agent respectively.The crosslinked amphoteric starch of adsorptivity refers to the insoluble starch derivative that simultaneously contains positive and negative two kinds of electric charge groups on starch glucose chain link, with the insoluble negatively charged ion or the cationic starch that only contain a kind of electric charge, compares, and its performance is comparatively unique.As with polyelectrolyte relatively, this base polymer presents fairly obvious anti-polyelectrolyte solution behavior at salts solution.Reversible contraction and swelling can occur at environment during as changes such as temperature, pH value, electric fields in the crosslinked amphoteric starch derivative of environmental sensitivity, are made into the artificial intelligence material for the controllable release of medicine, inductor block, artificial-muscle etc.Crosslinked amphoteric starch also can be widely used in and separate and concentrate heavy metal and rare metal etc.The adsorptivity amphoteric starch derivative of high-crosslinking-degree is comparatively unique for the absorption property of metal ion, and this improvement to heavy metal contamination will play a positive role.The adsorptivity amphoteric starch derivative of low crosslinking degree is because cross-linking density is low, high-water expansion, and water molecules easily infiltrates in starch derivative macromolecule network is expanded, and becomes high water suction state.
By natural polymer grafted propylene acetoacetic ester, then the method that is negatively charged ion by alkaline hydrolysis is to prepare the aspects such as carboxyethyl cellulose for Mierocrystalline cellulose mostly.More existing reports as starch is crosslinked with oxyethane, then carry out respectively with Monochloro Acetic Acid and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride the crosslinked amphoteric starch that the yin, yang ion reaction has prepared the single cross connection.But there are the deficiencies such as degree of crosslinking is low, absorption property is limited.Therefore studying the synthetic and performance development of double cross connection both sexes adsorptivity starch derivative, is a novelty and significant work.
Summary of the invention
The objective of the invention is in order to improve the absorption property of starch derivative, shorten the production cycle, a kind of preparation method of adsorptivity double cross connection both sexes tapioca (flour) is provided.
Concrete steps are:
(1) by tapioca (flour) in the vacuum drying oven under 60 ℃ dry 24 hours.
(2) step (1) gained butt tapioca (flour) and deionized water are added in reactor and be made into the starch suspension that massfraction is 30%～35%.
(3) will be equivalent to the dimethyl diallyl ammonium chloride cationic monomer that the massfraction of 1 ~ 3 times of butt tapioca (flour) quality is 60% joins in step (2) gained suspension; Being warming up to temperature of reaction system is 40 ~ 50 ℃, stirs lower reaction 1 ~ 1.5 hour, and the sodium hydroxide solution hierarchy of control pH that in reaction process, the employing massfraction is 10% ~ 20% is 9 ~ 12.
(4) the chloro-2-HPMA of analytical pure ethyl propenoate, analytical pure 3-that will be equivalent to respectively 0.5 ~ 1 times of butt tapioca (flour) quality adds mixing and stirring in Glass Containers, then adds and be equivalent to butt tapioca (flour) quality 3%
n, N'-methylene-bisacrylamide, monomer mixed solution stirs to obtain under room temperature.
(5) take respectively and be equivalent to ammonium persulphate and the sodium bisulfite that step (4) ethyl propenoate massfraction is 0.2% ~ 0.5%, be that 1:1 is dissolved in deionized water by ammonium persulphate and sodium bisulfite mass ratio, stir under room temperature and be made into the initiator solution that massfraction is 10%.
(6) step (3) gained material is heated to 60 ~ 70 ℃, evenly drips step (4) gained monomer mixed solution, and the initiator solution that synchronously evenly the massfraction of dropping step (5) preparation is 10%, in 4 ~ 5 hours, dropwise; Then under agitation continue reaction 20 ~ 30 minutes, then system temperature is cooled to 40 ℃.
(7) take 1% ~ 5% the sodium polyphosphate that is equivalent to butt tapioca (flour) quality and join in step (6) gained material, then add the cupric bromide that is equivalent to butt tapioca (flour) quality 0.1% ~ 0.3%, carry out crosslinking reaction 0.5 ~ 1 hour under 40 ℃.
(8) take and be equivalent to step (4) ethyl propenoate amount of substance and be made into than for the sodium hydrate solid of 1:1 is dissolved in quantitative deionized water the sodium hydroxide solution that massfraction is 10% ~ 15%, again this solution is controlled in 1.5 ~ 2 hours and is added drop-wise in step (7) gained feed liquid with constant pressure funnel, then continue reaction 1 hour.
(9) pH to 5 of HCl solution regulating step (8) the gained system that is 10% with massfraction ~ 6.5;
(10) step (9) gained material is put into to the ethanolic soln that the volume fraction that is equivalent to 4 ~ 7 times of butt tapioca (flour) quality is 80% and soaked 24 hours to remove the impurity such as unreacted monomer, homopolymerization and multipolymer.
(11) with the dehydrated alcohol that is equivalent to 3 ~ 4 times of butt tapioca (flour) quality, the deionized water in step (10) is sloughed.
(12) step (11) products therefrom is placed in to 80 ℃ of baking ovens and is dried to constant weight.
(13) step (12) products therefrom is pulverized, sieving obtains the white granular product.
(14) adopt mass method to measure the product percentage of grafting.The calculation formula of percentage of grafting is as follows:
G?=?(
W 1/
W 0)×100%
In formula:
g---percentage of grafting, %;
w 1---the quality of graft copolymer, the g of unit;
w 0---the quality of tapioca (flour), the g of unit.
(15) mensuration of degree of crosslinking: long-pending less according to sedimentation, the principle that degree of crosslinking is larger, i.e. the sedimentation of cross-linking starch derivative is long-pending is negative correlativing relation with degree of crosslinking; The present invention adopts sedimentation to amass and indirectly characterizes degree of crosslinking.Concrete measuring method is as follows: the modified starch suspension that the preparation massfraction is 2%, in 82 ℃ ~ 85 ℃ water-baths, constant temperature stirs, is incubated 2 minutes, takes out and is cooled to room temperature.Get the tool plug graduated centrifuge tube that two volumes are 10mL, add respectively starch paste liquid 10mL.With the whizzer of 4000 rev/mins centrifugal 2 minutes, then supernatant liquor is poured in the tool plug graduated centrifuge tube of same volume, read a milliliter number, calculated settlement is long-pending.Same sample is measured 3 times, averages.Calculation formula is as follows:
Amass=10-of sedimentation
v
In formula:
v---supernatant liquor volume, Unit/mL.
Double cross connection both sexes adsorptivity tapioca (flour) has superior absorption property.Simultaneously, due to yin, yang ionic group in double cross connection both sexes adsorptivity tapioca (flour) can with metal positive and negative ion generation huge legendary turtle cooperation use, and it can be discharged when iso-electric point, utilize this character separation of metal ions can be reclaimed.But double cross prepared by the present invention connection both sexes adsorptivity tapioca (flour) Reusability, this improvement to heavy metal contamination will play a positive role.
The accompanying drawing explanation
Fig. 1 is former tapioca (flour) IR figure.
The IR figure of the adsorptivity double cross connection both sexes tapioca (flour) that Fig. 2 is the embodiment of the present invention 2 preparations.
Fig. 3 is former tapioca (flour) SEM figure.
The SEM figure of the adsorptivity double cross connection both sexes tapioca (flour) that Fig. 4 is the embodiment of the present invention 2 preparations.
Embodiment
Embodiment 1:
(1) by tapioca (flour) in the vacuum drying oven under 60 ℃ dry 24 hours.
(2) getting 24g step (1) gained butt tapioca (flour) and 56mL deionized water adds in the 500mL four-hole boiling flask and is made into the starch suspension that massfraction is 30%.
(3) the dimethyl diallyl ammonium chloride cationic monomer that is 60% by the 30g massfraction joins in step (2) gained 30% starch suspension; Being warming up to temperature of reaction system is 40 ℃, stirs lower reaction 1 hour, and the sodium hydroxide solution hierarchy of control pH that in reaction process, the employing massfraction is 10% is 10.
(4) respectively 15g analytical pure ethyl propenoate, the chloro-2-HPMA of 15g analytical pure 3-are added to mixing and stirring in Glass Containers, then add 0.72g
n, N'-methylene-bisacrylamide, monomer mixed solution stirs to obtain under room temperature.
(5) take respectively 0.5g ammonium persulphate and 0.5g sodium bisulfite, be dissolved in the 9mL deionized water, stir under room temperature and be made into the initiator solution that massfraction is 10%.
(6) step (3) gained material is heated to 70 ℃, evenly drips step (4) gained monomer mixed solution, and the initiator solution that synchronously evenly the massfraction of dropping step (5) preparation is 10%, in 4 hours, dropwise; Then under agitation continue reaction 30 minutes, then system temperature is cooled to 40 ℃.
(7) take the 0.5g sodium polyphosphate and join in step (6) gained material, then add the 0.24g cupric bromide, carry out crosslinking reaction 0.5 hour under 40 ℃.
(8) take the 6g sodium hydrate solid and be dissolved in the 54mL deionized water and be made into the sodium hydroxide solution that massfraction is 10%, then this solution is controlled to 1.5 hours with constant pressure funnel is added drop-wise in step (7) gained feed liquid, then continue reaction 1 hour.
(9) pH to 6.5 of HCl solution regulating step (8) the gained system that is 10% with massfraction.
(10) step (9) gained material is put into to the ethanolic soln that the 120g volume fraction is 80% and soaked 24 hours to remove the impurity such as unreacted monomer, homopolymerization and multipolymer.
(11) with the 95g dehydrated alcohol, the deionized water in step (10) is sloughed.
(12) step (11) products therefrom is placed in to 80 ℃ of baking ovens and is dried to constant weight.
(13) step (12) products therefrom is pulverized, sieving obtains the white granular product.
(14) measuring percentage of grafting with mass method is 120%, and sedimentation is amassed as 0.25mL.
Embodiment 2:
(1) by tapioca (flour) in the vacuum drying oven under 60 ℃ dry 24 hours.
(2) getting 26g step (1) gained butt tapioca (flour) and 54mL deionized water adds in the 500mL four-hole boiling flask and is made into the starch suspension that massfraction is 32.5%.
(3) the dimethyl diallyl ammonium chloride cationic monomer that is 60% by the 40g massfraction joins in step (2) gained 32.5% starch suspension; Being warming up to temperature of reaction system is 45 ℃, stirs lower reaction 1.5 hours, and the sodium hydroxide solution hierarchy of control pH that in reaction process, the employing massfraction is 10% is 11.
(4) respectively 20g analytical pure ethyl propenoate, the chloro-2-HPMA of 20g analytical pure 3-are added to mixing and stirring in Glass Containers, then add 0.78g
n, N'-methylene-bisacrylamide, monomer mixed solution stirs to obtain under room temperature.
(5) take respectively 0.8g ammonium persulphate and 0.8g sodium bisulfite, be dissolved in the 14.4mL deionized water, stir under room temperature and be made into the initiator solution that massfraction is 10%.
(6) step (3) gained material is heated to 60 ℃, evenly drips step (4) gained monomer mixed solution, and the initiator solution that synchronously evenly the massfraction of dropping step (5) preparation is 10%, in 4.5 hours, dropwise; Then under agitation continue reaction 30 minutes, then system temperature is cooled to 40 ℃.
(7) take the 1.0g sodium polyphosphate and join in step (6) gained material, then add the 0.35g cupric bromide, carry out crosslinking reaction 0.5 hour under 40 ℃.
(8) take the 8g sodium hydrate solid and be dissolved in the 52mL deionized water and be made into the sodium hydroxide solution that massfraction is 13.33%, then this solution is controlled to 2 hours with constant pressure funnel is added drop-wise in step (7) gained feed liquid, then continue reaction 1 hour.
(9) pH to 6.5 of HCl solution regulating step (8) the gained system that is 10% with massfraction;
(10) step (9) gained material is put into to the ethanolic soln that the 150g volume fraction is 80% and soaked 24 hours to remove the impurity such as unreacted monomer, homopolymerization and multipolymer.
(11) with the 120g dehydrated alcohol, the deionized water in step (10) is sloughed.
(12) step (11) products therefrom is placed in to 80 ℃ of baking ovens and is dried to constant weight.
(13) step (12) products therefrom is pulverized, sieving obtains the white granular product.
(14) measuring percentage of grafting with mass method is 215%, and sedimentation is amassed as 0.19mL.
Product is analyzed through IR, 3382.79 cm
-1obviously broaden, this is N, the C of N'-methylene-bisacrylamide-H vibration absorption peak; 1658.23 cm
-1for N, the C=O vibration absorption peak of N'-methylene-bisacrylamide; 1580.34 cm
-1for propionyloxy-COO
-vibration absorption peak; 1424.85 cm
-1for N, the C of N'-methylene-bisacrylamide-N vibration absorption peak; 1209.94 cm
-1for the C of dimethyl diallyl ammonium chloride-N vibration absorption peak; 1157.36 cm
-1~ 1018.30 cm
-1obviously broaden, this is P=O, the vibration absorption peak of P-O.
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 surface is more smooth; Double cross connection both sexes adsorptivity tapioca (flour) polymeric particles tight adhesion and surface irregularity, obvious damaged rill and cave are arranged, the structure of former tapioca (flour) is damaged, its structure generation considerable change, this may be to have destroyed crystallizing field under grafting and alkalescence effect, further illustrates thus the starch conversion success.
Claims (1)
1. the preparation method of adsorptivity double cross connection both sexes tapioca (flour) is characterized in that concrete steps are:
(1) by tapioca (flour) in the vacuum drying oven under 60 ℃ dry 24 hours;
(2) step (1) gained butt tapioca (flour) and deionized water are added in reactor and be made into the starch suspension that massfraction is 30%～35%;
(3) will be equivalent to the dimethyl diallyl ammonium chloride cationic monomer that the massfraction of 1 ~ 3 times of butt tapioca (flour) quality is 60% joins in step (2) gained suspension; Being warming up to temperature of reaction system is 40 ~ 50 ℃, stirs lower reaction 1 ~ 1.5 hour, and the sodium hydroxide solution hierarchy of control pH that in reaction process, the employing massfraction is 10% ~ 20% is 9 ~ 12;
(4) the chloro-2-HPMA of analytical pure ethyl propenoate, analytical pure 3-that will be equivalent to respectively 0.5 ~ 1 times of butt tapioca (flour) quality adds mixing and stirring in Glass Containers, then adds and be equivalent to butt tapioca (flour) quality 3%
n, N'-methylene-bisacrylamide, monomer mixed solution stirs to obtain under room temperature;
(5) take respectively and be equivalent to ammonium persulphate and the sodium bisulfite that step (4) ethyl propenoate massfraction is 0.2% ~ 0.5%, be that 1:1 is dissolved in deionized water by ammonium persulphate and sodium bisulfite mass ratio, stir under room temperature and be made into the initiator solution that massfraction is 10%;
(6) step (3) gained material is heated to 60 ~ 70 ℃, evenly drips step (4) gained monomer mixed solution, and the initiator solution that synchronously evenly the massfraction of dropping step (5) preparation is 10%, in 4 ~ 5 hours, dropwise; Then under agitation continue reaction 20 ~ 30 minutes, then system temperature is cooled to 40 ℃;
(7) take 1% ~ 5% the sodium polyphosphate that is equivalent to butt tapioca (flour) quality and join in step (6) gained material, then add the cupric bromide that is equivalent to butt tapioca (flour) quality 0.1% ~ 0.3%, carry out crosslinking reaction 0.5 ~ 1 hour under 40 ℃;
(8) take and be equivalent to step (4) ethyl propenoate amount of substance and be made into than for the sodium hydrate solid of 1:1 is dissolved in quantitative deionized water the sodium hydroxide solution that massfraction is 10% ~ 15%, again this solution is controlled in 1.5 ~ 2 hours and is added drop-wise in step (7) gained feed liquid with constant pressure funnel, then continue reaction 1 hour;
(9) pH to 5 of HCl solution regulating step (8) the gained system that is 10% with massfraction ~ 6.5;
(10) step (9) gained material is put into to the ethanolic soln that the volume fraction that is equivalent to 4 ~ 7 times of butt tapioca (flour) quality is 80% and soaked 24 hours to remove unreacted monomer, homopolymerization and multipolymer impurity;
(11) with the dehydrated alcohol that is equivalent to 3 ~ 4 times of butt tapioca (flour) quality, the deionized water in step (10) is sloughed;
(12) step (11) products therefrom is placed in to 80 ℃ of baking ovens and is dried to constant weight;
(13) step (12) products therefrom is pulverized, sieving obtains the white granular product.
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| CN109280187A (en) * | 2018-10-21 | 2019-01-29 | 桂林理工大学 | Amination cross-linking type AA/MA/EA is grafted the preparation method of xanthic acid esterification tapioca magnetic blotting microballoon |
| CN109985605A (en) * | 2019-03-01 | 2019-07-09 | 北京师范大学 | A kind of native starch adsorbing material of water soluble organic dye and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1390868A (en) * | 2002-07-11 | 2003-01-15 | 华南理工大学 | Amphiprotic starch graft copolymer and its one-step preparing process |
| CN102585098A (en) * | 2012-03-08 | 2012-07-18 | 桂林理工大学 | Preparation method of cross-linked amphoteric cassava starch |
| CN102603903A (en) * | 2012-03-08 | 2012-07-25 | 桂林理工大学 | Method for preparing double-crosslinking amphoteric tapioca starch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1390868A (en) * | 2002-07-11 | 2003-01-15 | 华南理工大学 | Amphiprotic starch graft copolymer and its one-step preparing process |
| CN102585098A (en) * | 2012-03-08 | 2012-07-18 | 桂林理工大学 | Preparation method of cross-linked amphoteric cassava starch |
| CN102603903A (en) * | 2012-03-08 | 2012-07-25 | 桂林理工大学 | Method for preparing double-crosslinking amphoteric tapioca starch |
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Effective date of registration: 20201228 Address after: No.1 Weier Road, Shanggang Industrial Park, Jianhu County, Yancheng City, Jiangsu Province Patentee after: Jianhu Shanggang Industrial Park Service Co.,Ltd. Address before: Unit 2414-2416, main building, no.371, Wushan Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20201228 Address after: Unit 2414-2416, main building, no.371, Wushan Road, Tianhe District, Guangzhou City, Guangdong Province Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: 541004 the Guangxi Zhuang Autonomous Region Guilin Construction Road No. 12 Patentee before: GUILIN University OF TECHNOLOGY |