CN114716575A - Preparation method of starch microgel - Google Patents
Preparation method of starch microgel Download PDFInfo
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- CN114716575A CN114716575A CN202210200372.3A CN202210200372A CN114716575A CN 114716575 A CN114716575 A CN 114716575A CN 202210200372 A CN202210200372 A CN 202210200372A CN 114716575 A CN114716575 A CN 114716575A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 163
- 239000008107 starch Substances 0.000 title claims abstract description 163
- 235000019698 starch Nutrition 0.000 title claims abstract description 163
- 238000002360 preparation method Methods 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 192
- 229920000881 Modified starch Polymers 0.000 claims abstract description 59
- 235000019426 modified starch Nutrition 0.000 claims abstract description 58
- 239000004368 Modified starch Substances 0.000 claims abstract description 57
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 150000001450 anions Chemical class 0.000 claims abstract description 26
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 116
- 235000013336 milk Nutrition 0.000 claims description 35
- 239000008267 milk Substances 0.000 claims description 35
- 210000004080 milk Anatomy 0.000 claims description 35
- 229920002261 Corn starch Polymers 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000008120 corn starch Substances 0.000 claims description 21
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 19
- 229940106681 chloroacetic acid Drugs 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 125000002091 cationic group Chemical group 0.000 abstract description 21
- 125000000129 anionic group Chemical group 0.000 abstract description 8
- 230000000975 bioactive effect Effects 0.000 abstract description 7
- 239000004615 ingredient Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- 238000001035 drying Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 229920006320 anionic starch Polymers 0.000 description 13
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 238000007873 sieving Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 6
- 230000003113 alkalizing effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000013270 controlled release Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013376 functional food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
- C08B31/006—Crosslinking of derivatives of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of starch microgel, which comprises the steps of carrying out anion modification or cation modification on non-crystallized starch to prepare modified starch; and adding deionized water into the modified starch for dissolving, and then adding sodium trimetaphosphate and sodium hydroxide for mixing to obtain the starch microgel. After the starch is modified anionically and cationically, an anionic and cationic modified starch is prepared, and sodium trimetaphosphate and sodium hydroxide are added to the modified starch to mix and perform a cross-linking reaction, so as to provide a starch microgel with different surface charges for different bioactive ingredients.
Description
Technical Field
The invention relates to the field of functional food additives, and particularly discloses a preparation method of a starch microgel.
Background
In recent years, the microgel has a three-dimensional porous structure, is an excellent carrier of some bioactive ingredients (including medicines), and can cause swelling and shrinkage of the microgel under tiny environmental changes such as temperature and pH, so the microgel has potential application prospects in the aspects of controlled release of medicines and the like. Starch is a renewable degradable polysaccharide high molecular substance widely existing in nature, has the advantages of safety, no toxicity, low price, capability of discharging metabolites out of the body and the like, and is favored by a plurality of researchers for developing microgel by taking starch as a matrix. The traditional preparation method is to disperse starch in aqueous solution and then form microgel with a three-dimensional network structure through the cross-linking effect of a cross-linking agent.
However, starch has poor water solubility and dispersibility in solution, and besides, different bioactive ingredients have different charges in solution and different affinities when combined with the microgel, which affect the stability and controlled release capacity of the transporter.
Disclosure of Invention
The main objective of the present invention is to provide a method for preparing starch microgel, which aims to provide starch microgel with different surface charges for different bioactive components.
In order to achieve the above objects, the present invention provides a method for preparing starch microgel, comprising: carrying out anion modification or cation modification on the non-crystallized starch to prepare modified starch;
and adding deionized water into the modified starch for dissolving, and then adding sodium trimetaphosphate and sodium hydroxide for mixing to obtain the starch microgel.
Optionally, the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is (3-4: 1).
Optionally, the mass ratio of the sodium trimetaphosphate to the modified starch is 0.1-0.5.
Optionally, the step of performing anionic modification or cationic modification on the amorphized starch to obtain modified starch comprises:
adding the non-crystallized starch into an ethanol solution with the volume fraction of 90-95% and mixing to obtain starch milk;
adding sodium hydroxide into the starch milk to react to obtain a first emulsion;
and sequentially adding an ethanol solution containing chloroacetic acid and sodium hydroxide into the first emulsion, and reacting for 3-4 h at the temperature of 60-65 ℃ to obtain the anion modified starch.
Optionally, the step of adding sodium hydroxide into the starch milk to react to obtain a first emulsion comprises:
and adding sodium hydroxide into the starch milk, and reacting at 40-45 ℃ for 40-50 min to obtain a first emulsion.
Optionally, the molar ratio of the chloroacetic acid to the amorphized starch is 0.5-0.8.
Optionally, the step of performing anionic modification or cationic modification on the non-crystallized starch to obtain modified starch comprises:
mixing the non-crystallized starch with an ethanol solution to obtain starch milk;
and sequentially adding a CTA etherifying agent and a sodium hydroxide alkali catalyst into the starch milk, and reacting for 6-6.5 h at the temperature of 55-60 ℃ to obtain the cation modified starch.
Optionally, the molar ratio of the sodium hydroxide base catalyst to the non-crystallized starch is 0.6-1.4.
Optionally, the molar ratio of the CTA etherifying agent to the amorphized starch is 0.5-0.9.
Optionally, before the step of preparing the amorphized starch, the method further comprises:
mixing 50-55% volume fraction ethanol solution with corn starch, condensing and refluxing for 3-4 h at 80-85 deg.C, and oven drying to obtain non-crystallized starch.
According to the preparation method of the microgel, after the starch is subjected to anionic modification and cationic modification, the anionic and cationic modified starch is prepared, sodium trimetaphosphate and sodium hydroxide are added into the modified starch to be mixed for crosslinking reaction, so that the starch microgel with different surface charges is provided and is suitable for different bioactive components.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart illustrating an embodiment of a method for preparing a starch microgel according to the present invention;
FIG. 2 is an XRD pattern of the alcohol-heat treated amorphous starch prepared in example 1;
FIG. 3 is a graph showing the degree of substitution of the anion modified starch prepared in examples 1 to 3 as a function of the amount of chloroacetic acid added;
FIG. 4 is a graph showing the relationship between the degree of substitution and the amount of addition of an etherifying agent in the cation modified starch prepared in examples 4 to 6;
FIG. 5 is a scanning electron micrograph of the anionic starch microgel prepared in example 2;
FIG. 6 is a graph showing a distribution of particle size distribution of anionic starch microgels prepared in examples 1 to 3;
FIG. 7 is a scanning electron micrograph of the cationic starch microgel prepared in example 5;
FIG. 8 is a graph showing the distribution of particle size distribution of cationic starch microgels prepared in examples 4 to 6.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition to the poor water solubility and dispersibility of starch in solution, the different bioactive ingredients have different charges in solution and different affinities when combined with microgels, which affect the stability and controlled release capacity of the transporter. Therefore, the development of starch microgels with different surface charges to be suitable for different bioactive ingredients has been a new approach to solve this problem.
In view of the above, the present invention provides a method for preparing a starch microgel, comprising:
s10, carrying out anion modification or cation modification on the non-crystallized starch to obtain modified starch;
in the technical scheme of the invention, the non-crystallized starch has the advantages of wide raw material source, low price, safety, no toxicity and better biocompatibility.
Specifically, the step of performing anion modification on the amorphized starch comprises the following steps:
s110, adding the non-crystallized starch into an ethanol solution with the volume fraction of 90% -95% and mixing to obtain starch milk;
s111, adding sodium hydroxide into the starch milk to react to obtain a first emulsion;
preferably, sodium hydroxide is added into the starch milk at the temperature of 40-45 ℃ for reaction for 40-50 min to obtain a first emulsion.
And S112, sequentially adding an ethanol solution containing chloroacetic acid and sodium hydroxide into the first emulsion, and reacting at the temperature of between 60 and 65 ℃ for 3 to 4 hours to obtain the anion modified starch.
Specifically, the mol ratio of the chloroacetic acid to the non-crystallized starch is 0.5-0.8. The addition mode of the chlorine-containing acetic acid and sodium hydroxide solution is dropwise addition, so that the reaction can be more complete. And after the reaction is finished, performing suction filtration washing, drying and crushing to obtain the dried anionic starch.
Specifically, the step of performing cationic modification on the non-crystallized starch comprises the following steps:
s120, mixing the non-crystallized starch with an ethanol solution to obtain starch milk;
s121, sequentially adding a CTA etherifying agent and a sodium hydroxide alkali catalyst into the starch milk, and reacting for 6-6.5 hours at 55-60 ℃ to obtain the cation modified starch.
Preferably, the molar ratio of the sodium hydroxide base catalyst to the non-crystallized starch is 0.6-1.4; the molar ratio of the CTA etherifying agent to the non-crystallized starch is 0.5-0.9.
And S20, adding deionized water into the modified starch to dissolve, and then adding sodium trimetaphosphate and sodium hydroxide to mix to obtain the starch microgel.
The mass ratio of the sodium trimetaphosphate to the sodium hydroxide is (3-4: 1), and the mass ratio of the sodium trimetaphosphate to the modified starch is 0.1-0.5. Preferably, deionized water is added into the modified starch for dissolution, sodium trimetaphosphate and sodium hydroxide in a mass ratio of 3: 1 are added into the starch for full stirring and uniform mixing, and the formed microgel is kept overnight in a refrigerator at 4 ℃. And taking out the microgel, crushing, washing, drying and grinding into powder to obtain the dried anionic starch microgel.
It is worth to say that the non-crystallized starch can be a finished product purchased in the market or can be manufactured by self, the preparation process of the anionic starch and the cationic starch is simple, the operation is simple, the reaction is mild, and the prepared starch microgel can be respectively provided with opposite charges and is beneficial to being combined with active substances with different charges.
Preferably, the step of preparing the amorphized starch further comprises:
s100, mixing 50-55% by volume of ethanol solution with corn starch, carrying out condensation reflux treatment for 3-4 h at the temperature of 80-85 ℃, and drying to obtain the non-crystallized starch.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain the starch subjected to alcohol heat treatment, thereby obtaining the non-crystallized starch.
(2) Adding 15g of non-crystallized starch into 60mL of 95% ethanol to obtain starch milk;
(3) adding 2g of sodium hydroxide into the starch milk, and alkalizing for 40min at 40 ℃ to obtain a first emulsion;
(4) and (2) dropwise adding an ethanol solution containing chloroacetic acid into the first emulsion, adding 1.3g of sodium hydroxide again, heating to 60 ℃ for carboxymethylation reaction for 3h, washing with ethanol after the reaction is finished, drying, crushing, and sieving with a 100-mesh sieve to obtain the anion modified starch.
Wherein the mol ratio of the chloroacetic acid to the amorphous starch is 0.5.
(5) Dissolving 4g of anionic modified starch in 40ml of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the anionic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 3: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.1.
Example 2
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain the starch subjected to alcohol heat treatment, thereby obtaining the non-crystallized starch.
(2) Adding 15g of non-crystallized starch into 60mL of 95% ethanol to obtain starch milk;
(3) adding 2g of sodium hydroxide into the starch milk, and alkalizing for 40min at 40 ℃ to obtain a first emulsion;
(4) dropwise adding an ethanol solution containing chloroacetic acid into the first emulsion, adding 1.3g of sodium hydroxide again, heating to 60 ℃ for carboxymethylation reaction for 3 hours, washing with ethanol after the reaction is finished, drying, crushing, and sieving with a 100-mesh sieve to obtain the anion modified starch.
Wherein the mol ratio of the chloroacetic acid to the amorphous starch is 0.5.
(5) Dissolving 4g of anion modified starch in 40mL of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the anion starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 3: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.4.
Example 3
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain starch subjected to alcohol heat treatment, thereby obtaining non-crystallized starch.
(2) Adding 15g of non-crystallized starch into 60mL of 95% ethanol to obtain starch milk;
(3) adding 2g of sodium hydroxide into the starch milk, and alkalizing for 40min at 40 ℃ to obtain a first emulsion;
(4) and (2) dropwise adding an ethanol solution containing chloroacetic acid into the first emulsion, adding 1.3g of sodium hydroxide again, heating to 60 ℃ for carboxymethylation reaction for 3h, washing with ethanol after the reaction is finished, drying, crushing, and sieving with a 100-mesh sieve to obtain the anion modified starch.
Wherein the mol ratio of the chloroacetic acid to the amorphous starch is 0.5.
(5) Dissolving 4g of anion modified starch in 40mL of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the anion starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 3: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.5.
Example 4
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain the starch subjected to alcohol heat treatment, thereby obtaining the non-crystallized starch.
(2) Mixing the non-crystallized starch with 60mL of 95% ethanol solution to obtain starch milk;
(3) and at room temperature, sequentially dropwise adding an etherifying agent CTA and a sodium hydroxide alkali catalyst into the starch milk, stirring, reacting for 6 hours at 55 ℃, washing with ethanol, drying, crushing, and sieving with a 100-mesh sieve to obtain the cation modified starch.
Wherein, the mol ratio of the etherifying agent CTA and the amorphous starch is 0.8, and the mol ratio of the sodium hydroxide alkali catalyst and the starch is 1.2.
(4) Dissolving 4g of cationic modified starch in 40mL of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the cationic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 3: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.1.
Example 5
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain starch subjected to alcohol heat treatment, thereby obtaining non-crystallized starch.
(2) Mixing the non-crystallized starch with 60mL of 95% ethanol solution to obtain starch milk;
(3) and at room temperature, sequentially dropwise adding an etherifying agent CTA and a sodium hydroxide alkali catalyst into the starch milk, stirring, reacting for 6 hours at 55 ℃, washing with ethanol, drying, crushing, and sieving with a 100-mesh sieve to obtain the cation modified starch.
Wherein, the molar ratio of the etherifying agent CTA to the amorphous starch is 0.8, and the molar ratio of the sodium hydroxide alkali catalyst to the starch is 1.2.
(4) Dissolving 4g of cationic modified starch in 40ml of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the cationic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 3: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.3.
Example 6
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain the starch subjected to alcohol heat treatment, thereby obtaining the non-crystallized starch.
(2) Mixing the non-crystallized starch with 60mL of 95% ethanol solution to obtain starch milk;
(3) and at room temperature, sequentially dropwise adding an etherifying agent CTA and a sodium hydroxide alkali catalyst into the starch milk, stirring, reacting for 6 hours at 55 ℃, washing with ethanol, drying, crushing, and sieving with a 100-mesh sieve to obtain the cation modified starch.
Wherein, the mol ratio of the etherifying agent CTA and the amorphous starch is 0.8, and the mol ratio of the sodium hydroxide alkali catalyst and the starch is 1.2.
(4) Dissolving 4g of cationic modified starch in 40mL of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the cationic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 3: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.5.
Example 7
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 50% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 3h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain the starch subjected to alcohol heat treatment, thereby obtaining the non-crystallized starch.
(2) Adding 15g of non-crystallized starch into 60mL of 90% ethanol to obtain starch milk;
(3) adding 2g of sodium hydroxide into the starch milk, and alkalizing for 50min at 40 ℃ to obtain a first emulsion;
(4) and (2) dropwise adding an ethanol solution containing chloroacetic acid into the first emulsion, adding 1.3g of sodium hydroxide again, heating to 65 ℃ for carboxymethylation reaction for 4 hours, washing with ethanol after the reaction is finished, drying, crushing, and sieving with a 100-mesh sieve to obtain the anion modified starch.
Wherein the mol ratio of the chloroacetic acid to the amorphous starch is 0.5.
(5) Dissolving 4g of anionic modified starch in 40ml of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the anionic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 4: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.1.
Example 8
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 55% ethanol, mixing, carrying out condensation reflux treatment at 85 ℃ for 4h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain the starch subjected to alcohol heat treatment, thereby obtaining the non-crystallized starch.
(2) Mixing the non-crystallized starch with 60mL of 95% ethanol solution to obtain starch milk;
(3) and at room temperature, sequentially dropwise adding an etherifying agent CTA and a sodium hydroxide alkali catalyst into the starch milk, stirring, reacting at 60 ℃ for 6.5 hours, washing with ethanol, drying, crushing, and sieving with a 100-mesh sieve to obtain the cation modified starch.
Wherein, the molar ratio of the etherifying agent CTA to the amorphous starch is 0.5, and the molar ratio of the sodium hydroxide alkali catalyst to the starch is 0.6.
(4) Dissolving 4g of anionic modified starch in 40ml of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the anionic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 4: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.5.
Example 9
(1) Weighing 25g of corn starch, adding the corn starch into 100mL of 55% ethanol, mixing, carrying out condensation reflux treatment at 805 ℃ for 4h, repeatedly washing with 95% ethanol after the reaction is finished, and finally drying and crushing to obtain starch subjected to alcohol heat treatment, thereby obtaining non-crystallized starch.
(2) Mixing the non-crystallized starch with 60mL of 95% ethanol solution to obtain starch milk;
(3) and (2) at room temperature, sequentially dropwise adding an etherifying agent CTA and a sodium hydroxide alkali catalyst into the starch milk, stirring, reacting for 6.5 hours at 60 ℃, washing with ethanol, drying, crushing, and sieving with a 100-mesh sieve to obtain the cation modified starch.
Wherein, the molar ratio of the etherifying agent CTA to the amorphous starch is 0.9, and the molar ratio of the sodium hydroxide alkali catalyst to the starch is 1.4.
(5) Dissolving 4g of cationic modified starch in 40ml of deionized water, sequentially adding sodium trimetaphosphate and sodium hydroxide, and fully stirring and uniformly mixing to obtain the cationic starch microgel. Wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is 4: 1, the mass ratio of the sodium trimetaphosphate to the anion modified starch is 0.5.
Analysis of results
Referring to FIG. 2, the XRD pattern of the alcohol-heat treated starch prepared in example 1 is shown. The crystallinity of the starch decreases after the alcohol heat treatment, mainly because the heat treatment of the ethanol solution destroys the crystalline part of the starch, leaving an amorphous part, resulting in a decrease in crystallinity.
FIG. 3 is a graph showing the relationship between the degree of substitution and the amount of chloroacetic acid added in the anion-modified starches prepared in examples 1 to 3. The degree of substitution of the anionically modified starch increases and then decreases with increasing chloroacetic acid addition, and reaches a maximum when the molar ratio of chloroacetic acid to amorphized starch is 0.6. Excessive chloroacetic acid is added, so that the pH value in a reaction system is reduced, side reactions are increased, and the modification reaction is not facilitated.
Fig. 4 is a graph showing the relationship between the degree of substitution and the amount of addition of the etherifying agent in the cation modified starches prepared in examples 4 to 6. The substitution degree of the cation modified starch is increased and then decreased along with the increase of the addition amount of the etherifying agent. The addition of a proper amount of etherifying agent can promote full contact reaction between the etherifying agent and starch, and is favorable for the reaction.
FIG. 5 is a scanning electron micrograph of the anionic starch microgel prepared in example 2. Scanning electron microscope images show that the prepared anionic starch microgel has a rough surface and a plurality of pore channels.
FIG. 6 is a graph showing the distribution of particle size distribution of anionic starch microgels prepared in examples 1 to 3. The particle size range of the anionic starch microgel is distributed in the range of 7-24 mu m, and the particle size is reduced along with the increase of the crosslinking degree.
FIG. 7 is a scanning electron micrograph of the cationic starch microgel prepared in example 5. The prepared cationic starch microgel presents a three-dimensional network porous structure and has developed pore channels.
FIG. 8 is a graph showing the distribution of particle size of cationic starch microgel prepared in examples 4 to 6. The particle size range of the cationic starch microgel is 4-10 mu m and is smaller than that of the prepared anionic starch microgel.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A method for preparing a starch microgel, comprising:
carrying out anion modification or cation modification on the non-crystallized starch to prepare modified starch;
and adding deionized water into the modified starch for dissolving, and then adding sodium trimetaphosphate and sodium hydroxide for mixing to obtain the starch microgel.
2. The method of preparing the starch microgel of claim 1, wherein the mass ratio of the sodium trimetaphosphate to the sodium hydroxide is (3-4: 1).
3. The method of preparing the starch microgel of claim 1, wherein the mass ratio of the sodium trimetaphosphate to the modified starch is 0.1 to 0.5.
4. The method of preparing a starch microgel as claimed in claim 1, wherein the step of modifying the amorphized starch anionically or cationically to obtain a modified starch comprises:
adding the non-crystallized starch into an ethanol solution with the volume fraction of 90-95% and mixing to obtain starch milk;
adding sodium hydroxide into the starch milk to react to obtain a first emulsion;
and sequentially adding an ethanol solution containing chloroacetic acid and sodium hydroxide into the first emulsion, and reacting for 3-4 h at the temperature of 60-65 ℃ to obtain the anion modified starch.
5. The method of preparing starch microgel of claim 4, wherein the step of adding sodium hydroxide to the starch milk to react to obtain a first emulsion comprises:
and adding sodium hydroxide into the starch milk, and reacting at 40-45 ℃ for 40-50 min to obtain a first emulsion.
6. The method of preparing a starch microgel according to claim 4, wherein the molar ratio of chloroacetic acid to the amorphized starch is 0.5 to 0.8.
7. The method of preparing a starch microgel as claimed in claim 1, wherein the step of modifying the amorphized starch anionically or cationically to obtain a modified starch comprises:
mixing the non-crystallized starch with an ethanol solution to obtain starch milk;
sequentially adding a CTA etherifying agent and a sodium hydroxide alkali catalyst into the starch milk, and reacting for 6-6.5 h at the temperature of 55-60 ℃ to obtain the cation modified starch.
8. The method of preparing the starch microgel of claim 7, wherein the molar ratio of the sodium hydroxide base catalyst to the amorphized starch is from 0.6 to 1.4.
9. The method for preparing a starch microgel according to claim 7, wherein the molar ratio of the CTA etherifying agent to the amorphized starch is 0.5 to 0.9.
10. The method of preparing a starch microgel as claimed in claim 1, further comprising, before the step of preparing the amorphized starch:
mixing 50-55% volume fraction ethanol solution with corn starch, condensing and refluxing for 3-4 h at 80-85 deg.C, and oven drying to obtain non-crystallized starch.
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| CN101024699A (en) * | 2007-01-26 | 2007-08-29 | 华南理工大学 | Method for preparing non-crystal starch particles with loose structure by post crosslinking method |
| CN101348528A (en) * | 2008-08-29 | 2009-01-21 | 华南理工大学 | Preparation of amorphous particulate carboxymethyl starch |
| CN105153318A (en) * | 2015-07-24 | 2015-12-16 | 江南大学 | Preparation method for starch-based microgel |
| CN110655673A (en) * | 2019-09-30 | 2020-01-07 | 大连民族大学 | Preparation method of porous starch microgel with dual responses of pH and salt ions |
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| CN101024699A (en) * | 2007-01-26 | 2007-08-29 | 华南理工大学 | Method for preparing non-crystal starch particles with loose structure by post crosslinking method |
| CN101348528A (en) * | 2008-08-29 | 2009-01-21 | 华南理工大学 | Preparation of amorphous particulate carboxymethyl starch |
| CN105153318A (en) * | 2015-07-24 | 2015-12-16 | 江南大学 | Preparation method for starch-based microgel |
| CN110655673A (en) * | 2019-09-30 | 2020-01-07 | 大连民族大学 | Preparation method of porous starch microgel with dual responses of pH and salt ions |
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Application publication date: 20220708 |