CN103059227B - Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch - Google Patents
Preparation method of crosslinked acrylic graft hydroxypropyl cassava starch Download PDFInfo
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- 229920002472 Starch Polymers 0.000 title claims abstract description 60
- 235000019698 starch Nutrition 0.000 title claims abstract description 60
- 239000008107 starch Substances 0.000 title claims abstract description 60
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 title claims abstract description 39
- -1 hydroxypropyl Chemical group 0.000 title claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 241000658379 Manihot esculenta subsp. esculenta Species 0.000 title 1
- 240000003183 Manihot esculenta Species 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 235000013312 flour Nutrition 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 238000003811 acetone extraction Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000006266 etherification reaction Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000001341 hydroxy propyl starch Substances 0.000 abstract 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 7
- 244000017020 Ipomoea batatas Species 0.000 description 4
- 235000002678 Ipomoea batatas Nutrition 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001592 potato starch Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 241000212978 Amorpha <angiosperm> Species 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of crosslinked acrylic graft hydroxypropyl cassava starch, which comprises the following steps: by using cassava starch as a main raw material and anhydrous ethanol as a solvent, carrying out etherification reaction with epoxypropane in an alkaline medium to obtain hydroxypropyl cassava starch; and by using acrylic acid as a graft monomer, an organic alkali ethylenediamine as a neutralizer and N-N'-methylene-bis-acrylamide as a crosslinking agent, under the actions of initiators ammonium persulfate and sodium bisulfite, grafting and crosslinking to synthesize the water-soluble crosslinked acrylic graft hydroxypropyl cassava starch. The hydroxypropyl substitution degree of the product is less than or equal to 0.37, and the grafting efficiency and monomer conversion rate are respectively up to 56.0 and 63.5%. The hydroxypropyl starch is remodified by crosslinking and grafting reaction, so that the synthesized product has a complex space network structure, can be sufficiently dissolved and dispersed in water, has excellent adsorptivity and viscosity, can be adsorbed and combined with ions and some insoluble granules or heavy metal ions in water, and is widely used in the environmental protection fields of water treatment, heavy metal adsorption and the like.
Description
Technical field
The present invention relates to a kind of preparation method of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch.
Background technology
Hydroxypropylated starch is a kind of non-ionic type modified starch being carried out etherification reaction in the basic conditions by starch and propylene oxide and synthesized, and can disperse and soluble in water.Compared with ative starch, functional group main in hydroxypropylated starch structural unit becomes hydroxypropyl from hydroxyl, water-soluble had with viscosity greatly improve, be widely used in the fields such as papermaking, weaving, food, oil, medicine, building.Mainly utilize it water-soluble to the study on the modification of hydroxypropylated starch, by the modifying method such as crosslinked, grafting, esterification, further sex change is carried out to it, improve its structure to introduce new active function groups, extended functionality and Application Areas.
At present, in the sex change of hydroxypropylated starch, mainly comprise the product such as hydroxypropyl Staragel 90V, hydroxypropyl Staragel 90V starch, acetylize hydroxypropylated starch ester, cross-linked hydroxypropylated starch, hydroxypropyl acetylated starch, hydroxypropyl Staragel 90V through esterification, acidylate, the processing method exploitation such as crosslinked both at home and abroad.Because hydroxypropylated starch is by after the higher hydroxyl of reactive behavior on epoxy group(ing) etherificate substituted starch, the group that can react in its structure reduces, and when continuing to react with other modifiers, its difficulty also increases gradually.Key in synthesis technique is the selection of solvent and the raising of substitution value.The synthetic system of above-mentioned modification hydroxypropylated starch, generally with water or compound alcohol for solvent.During with water as solvent, the easy gelatinization of starch in reaction system, causes the substitution value of reaction not high; And when adopting compound alcohol to be solvent, although can reach higher substitution value, the recovery process of waste liquid is complicated in last handling process, production cost is caused to increase.And the improvement of the performances such as the functional especially adsorptivity of corresponding product is not ideal enough.
Summary of the invention
The object of the invention is the application performance in order to improve hydroxypropylated starch, a kind of preparation method of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch is provided.
System of the present invention take dehydrated alcohol as solvent, on synthesis Hydroxypropyl Tapioca Starch basis, then is grafted monomer with vinylformic acid, organic bases quadrol is neutralizing agent, N, N '-methylene-bisacrylamide is linking agent, synthesizes a kind of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch.The intermediate product of synthesis process is without the need to being separated, i.e. one pot process the finished product, simplify the postprocessing working procedures of product.
Concrete steps are:
(1) tapioca (flour) is dried to constant weight in the vacuum drying oven of 50 DEG C, obtains butt tapioca (flour).
(2) get step (1) gained butt tapioca (flour) 6 ~ 10g and 20 ~ 30mL analytical pure dehydrated alcohol adds in four-hole boiling flask, stirred at ambient temperature is even, is made into starch suspension.
(3) get the sodium hydroxide solution that 5 ~ 20mL massfraction is 5% ~ 15%, add in the starch suspension of step (2) gained at 10 ~ 20 minutes, the pH regulating reaction system is 10 ~ 13.
(4) get 2.5 ~ 5mL analytical pure propylene oxide to add in step (3) gained reaction system, after stirring, be warming up to 30 ~ 40 DEG C, react 6 ~ 10 hours; Then be 6 ~ 7 with analytical pure Glacial acetic acid regulation system pH, obtain hydroxypropylated starch solution.
(5) successively 1.0 ~ 5.0mL analytical pure vinylformic acid, 5 ~ 15mL deionized water are added in 50mL small beaker, after stirring, adopt 1 ~ 5mL analytical pure quadrol to regulate the pH of this solution to be 5 ~ 7; Again by 0.05 ~ 0.10g linking agent N, N '-methylene-bisacrylamide, 10 ~ 20mL deionized water add in beaker, and stirring and dissolving evenly obtains monomer mixed solution.
(6) take 0.02 ~ 0.1g ammonium persulphate and 0.04 ~ 0.2g sodium bisulfite adds in another 50mL small beaker, then add 10 ~ 15mL deionized water, after being uniformly dissolved under room temperature, obtain initiator mixing solutions.
(7) step (4) gained material is heated to 40 ~ 45 DEG C, evenly drips step (5) gained monomer mixed solution, and synchronously evenly drip step (6) gained initiator mixing solutions, control to dropwise for 20 ~ 60 minutes; Then under agitation continue reaction 1 ~ 3 hour, then system temperature is cooled to less than 40 DEG C, obtain cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch crude product in solution.
(8) after step (7) gained crude product in solution being precipitated with 30 ~ 80mL dehydrated alcohol, elimination supernatant liquor, then use 20 ~ 50mL absolute ethanol washing three times, then use 20 ~ 40mL analytical pure acetone rinsing and suction filtration; Vacuum drying oven filter cake being put into 50 DEG C is dried to constant weight and is namely obtained the thick product of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch.
(9) product thick in step (8) is put into apparatus,Soxhlet's, add 50 ~ 100mL analytical pure acetone extraction 12 ~ 24 hours; Take out the material after extracting, put into 50 DEG C of vacuum drying ovens and be dried to constant weight, obtain product.
(10) spectrophotometry etherificate substitution value: successively the cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch sample of 0.1g, the sulphuric acid soln of 25mL concentration 0.5mol/L are added in 100mL volumetric flask, after dissolving in 90 ~ 100 DEG C of water-baths, be cooled to room temperature again, add deionized water and be diluted to scale; Draw this solution of 1mL to add in cock test tube, and slowly add the vitriol oil that 30mL massfraction is 98%, heat 5 minutes in boiling water bath after mixing, make the hydroxypropyl in cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch be decomposed into propylene glycol; Pipette in part solution to spectrophotometric 1cm cuvette after being cooled to room temperature, do reference with blank after leaving standstill, under 595nm, measure its absorbancy; Do blank assay simultaneously, and calculate etherificate substitution value DS according to following relational expression:
Wherein, the relational expression of propylene glycol absorbance and concentration is:
C=12.1A-0.475
In formula: C---the concentration of propylene glycol in the sample of being tried to achieve by point luminosity photometer value, unit μ g/mL;
A---from the absorbance that spectrophotometer reads;
C
former---the concentration of the ative starch empty propylene glycol of being tried to achieve by point luminosity photometer value, unit μ g/mL;
V---in test process, sample is by the volume diluted, Unit/mL;
W---hydroxypropyl quality accounts for the percentage composition of starch quality, %;
W---the quality of test specimen in use, unit g;
W
former---the quality of blank assay tapioca (flour) used, unit g;
58---the relative molecular mass of propylene oxide;
162---the relative molecular mass of starch minimal structure unit;
76---the relative molecular mass of propylene glycol.
(11) adopt mass method to measure grafting efficiency and monomer conversion, calculation formula is as follows:
In formula: GE---cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch grafting efficiency, %;
C---monomer conversion, %;
The hydroxypropyl quality recorded in w---step (10) accounts for the percentage composition of starch quality, %;
M
1---the quality of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch, unit g;
M
2---the quality of log sweet potato starch, unit g;
M
3---the quality of the thick product of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch, unit g;
M
4---add the total mass of vinylformic acid in system, quadrol, N, N '-methylene-bisacrylamide, unit g.
The present invention is reacted hydroxypropylated starch modification again by cross-linked graft; the product of synthesis has complicated space net structure; can fully dissolve and be dispersed in water, there is excellent adsorptivity and stickiness, can with the ion in water and some insoluble particles or heavy metal ion adsorbed combination.Product can be widely used in the field of Environment Protection such as water treatment and heavy metal adsorption.
Accompanying drawing explanation
The infrared spectrogram of Fig. 1 log sweet potato starch.
The infrared spectrogram of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch prepared by Fig. 2 embodiment of the present invention 1.
The SEM figure of Fig. 3 log sweet potato starch.
The SEM figure of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch prepared by Fig. 4 embodiment of the present invention 1.
Embodiment
Embodiment 1:
(1) tapioca (flour) is dried to constant weight in the vacuum drying oven of 50 DEG C, obtains butt tapioca (flour).
(2) get step (1) gained butt tapioca (flour) 6g and 20mL analytical pure dehydrated alcohol adds in four-hole boiling flask, stirred at ambient temperature is even, is made into starch suspension.
(3) get the sodium hydroxide solution that 5mL massfraction is 10%, add in the starch suspension of step (2) gained at 10 minutes, the pH regulating reaction system is 13.
(4) get 2.5mL analytical pure propylene oxide to add in step (3) gained reaction system, after stirring, be warming up to 40 DEG C, react 8 hours; Then be 7 with analytical pure Glacial acetic acid regulation system pH, obtain hydroxypropylated starch solution.
(5) successively 3.0mL analytical pure vinylformic acid, 10mL deionized water are added in 50mL small beaker, after stirring, adopt 2mL analytical pure quadrol to regulate the pH of this solution to be 7; Again by 0.05g linking agent N, N '-methylene-bisacrylamide, 10mL deionized water add in beaker, and stirring and dissolving evenly obtains monomer mixed solution.
(6) take 0.05g ammonium persulphate and 0.1g sodium bisulfite adds in another 50mL small beaker, then add 10mL deionized water, after being uniformly dissolved under room temperature, obtain initiator mixing solutions.
(7) step (4) gained material is heated to 40 DEG C, evenly drips step (5) gained monomer mixed solution, and synchronously evenly drip step (6) gained initiator mixing solutions, control to dropwise for 30 minutes; Then under agitation continue reaction 2 hours, then system temperature is cooled to less than 40 DEG C, obtain cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch crude product in solution.
(8) after step (7) gained crude product in solution being precipitated with 50mL dehydrated alcohol, elimination supernatant liquor, then use 50mL absolute ethanol washing three times, then use 40mL analytical pure acetone rinsing and suction filtration; Vacuum drying oven filter cake being put into 50 DEG C is dried to constant weight and is namely obtained the thick product of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch.
(9) product thick in step (8) is put into apparatus,Soxhlet's, add 100mL analytical pure acetone extraction 12 hours; Take out the material after extracting, put into 50 DEG C of vacuum drying ovens and be dried to constant weight, obtain product.
(10) adopting spectrophotometry to record etherificate substitution value is 0.20; Calculating product grafting efficiency is 30.7%, and monomer conversion is 54.0%.
Embodiment 2:
(1) tapioca (flour) is dried to constant weight in the vacuum drying oven of 50 DEG C, obtains butt tapioca (flour).
(2) get step (1) gained butt tapioca (flour) 8g and 30mL analytical pure dehydrated alcohol adds in four-hole boiling flask, stirred at ambient temperature is even, is made into starch suspension.
(3) get the sodium hydroxide solution that 7mL massfraction is 10%, add in the starch suspension of step (2) gained at 20 minutes, the pH regulating reaction system is 11.
(4) get 5mL analytical pure propylene oxide to add in step (3) gained reaction system, after stirring, be warming up to 40 DEG C, react 10 hours; Then be 7 with analytical pure Glacial acetic acid regulation system pH, obtain hydroxypropylated starch solution.
(5) successively 5.0mL analytical pure vinylformic acid, 15mL deionized water are added in 50mL small beaker, after stirring, adopt 4mL analytical pure quadrol to regulate the pH of this solution to be 7; Again by 0.07g linking agent N, N '-methylene-bisacrylamide, 10mL deionized water add in beaker, and stirring and dissolving evenly obtains monomer mixed solution.
(6) take 0.1g ammonium persulphate and 0.2g sodium bisulfite adds in another 50mL small beaker, then add 15mL deionized water, after being uniformly dissolved under room temperature, obtain initiator mixing solutions.
(7) step (4) gained material is heated to 45 DEG C, evenly drips step (5) gained monomer mixed solution, and synchronously evenly drip step (6) gained initiator mixing solutions, control to dropwise for 60 minutes; Then under agitation continue reaction 2 hours, then system temperature is cooled to less than 40 DEG C, obtain cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch crude product in solution.
(8) after step (7) gained crude product in solution being precipitated with 50mL dehydrated alcohol, elimination supernatant liquor, then use 50mL absolute ethanol washing three times, then use 40mL analytical pure acetone rinsing and suction filtration; Vacuum drying oven filter cake being put into 50 DEG C is dried to constant weight and is namely obtained the thick product of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch.
(9) product thick in step (8) is put into apparatus,Soxhlet's, add 100mL analytical pure acetone extraction 24 hours; Take out the material after extracting, put into 50 DEG C of vacuum drying ovens and be dried to constant weight, obtain product.
(10) recording etherificate substitution value by spectrophotometry is 0.37; Calculating product grafting efficiency is 56.0%, and monomer conversion is 63.5%.
Product is analyzed through IR, at 1569.69cm
-1for the vibration absorption peak of C=O key in carboxylic acid ion, 1410.80cm
-1place is C-O key symmetric vibration stretching absorbance peak, 3447.97cm
-1place is the vibration stretching absorbance peak of N-H, simultaneously because the vibration of intermolecular O-H key forms wider absorption peak.Sem analysis result shows, and log sweet potato starch is the particulate state of rule, smooth surface; Through modified, there is little hole in surface, and illustrate that the specific surface area increase of starch is comparatively large, pars amorpha and the crystallizing field of starch granules all there occurs reaction.
Claims (1)
1. a preparation method for cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch, is characterized in that concrete steps are:
(1) tapioca (flour) is dried to constant weight in the vacuum drying oven of 50 DEG C, obtains butt tapioca (flour);
(2) get step (1) gained butt tapioca (flour) 6 ~ 10g and 20 ~ 30mL analytical pure dehydrated alcohol adds in four-hole boiling flask, stirred at ambient temperature is even, is made into starch suspension;
(3) get the sodium hydroxide solution that 5 ~ 20mL massfraction is 5% ~ 15%, add in the starch suspension of step (2) gained at 10 ~ 20 minutes, the pH regulating reaction system is 10 ~ 13;
(4) get 2.5 ~ 5mL analytical pure propylene oxide to add in step (3) gained reaction system, after stirring, be warming up to 30 ~ 40 DEG C, react 6 ~ 10 hours; Then be 6 ~ 7 with analytical pure Glacial acetic acid regulation system pH, obtain hydroxypropylated starch solution;
(5) successively 1.0 ~ 5.0mL analytical pure vinylformic acid, 5 ~ 15mL deionized water are added in 50mL small beaker, after stirring, adopt 1 ~ 5mL analytical pure quadrol to regulate the pH of this solution to be 5 ~ 7; Again by 0.05 ~ 0.10g linking agent
n, N'-methylene-bisacrylamide, 10 ~ 20mL deionized water add in beaker, obtain monomer mixed solution;
(6) take 0.02 ~ 0.1g ammonium persulphate and 0.04 ~ 0.2g sodium bisulfite adds in another 50mL small beaker, then add 10 ~ 15mL deionized water, after being uniformly dissolved under room temperature, obtain initiator mixing solutions;
(7) step (4) gained material is heated to 40 ~ 45 DEG C, evenly drips step (5) gained monomer mixed solution, and synchronously evenly drip step (6) gained initiator mixing solutions, control to dropwise for 20 ~ 60 minutes; Then under agitation continue reaction 1 ~ 3 hour, then system temperature is cooled to less than 40 DEG C, obtain cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch crude product in solution;
(8) after step (7) gained crude product in solution being precipitated with 30 ~ 80mL dehydrated alcohol, elimination supernatant liquor, then use 20 ~ 50mL absolute ethanol washing three times, then use 20 ~ 40mL analytical pure acetone rinsing and suction filtration; Vacuum drying oven filter cake being put into 50 DEG C is dried to constant weight and is namely obtained the thick product of cross-linked acrylic acid grafting Hydroxypropyl Tapioca Starch;
(9) product thick in step (8) is put into apparatus,Soxhlet's, add 50 ~ 100mL analytical pure acetone extraction 12 ~ 24 hours; Take out the material after extracting, put into 50 DEG C of vacuum drying ovens and be dried to constant weight, obtain product.
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| CN103242458B (en) * | 2013-05-27 | 2015-07-15 | 江西鑫川实业有限公司 | Double-etherification modified starch and preparation method thereof |
| CN104291973B (en) * | 2014-09-26 | 2016-08-24 | 广州市高士实业有限公司 | Slow-released carrier and the application in the sustained release of moisture or fertilizer needed for potted plant crop thereof |
| CN106188404A (en) * | 2016-07-24 | 2016-12-07 | 泉州海岸线新材料科技有限公司 | The formula of a kind of Technologies of Water-absorbing Resin: Corn Starch Grafting and preparation technology |
| CN107986416A (en) * | 2017-12-19 | 2018-05-04 | 安徽仁维环保工程科技有限公司 | A kind of starch derivatives for sewage disposal and preparation method thereof |
| CN114989355B (en) * | 2022-05-09 | 2023-08-22 | 华南理工大学 | Hydroxypropyl grafted acrylamide starch for dry-mixed masonry mortar and preparation method thereof |
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